CN117049874A - Bismuth vanadate-based medium-low entropy oxygen ion conductor material and preparation method thereof - Google Patents
Bismuth vanadate-based medium-low entropy oxygen ion conductor material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 13
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000010416 ion conductor Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 230000004913 activation Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
Abstract
The invention discloses a bismuth vanadate-based medium-low entropy oxygen ion conductor material and a preparation method thereof. (1) Bi as a raw material 2 O 3 And placing the mixture and CuO in a drying oven to dry for 12 hours at 180 ℃, and weighing according to the designed stoichiometric ratio. Weighing Bi with purity of more than 99 percent (mass percent) 2 O 3 、V 2 O 5 、CuO、NiO、Nb 2 O 5 、TiO 2 、Ga 2 O 3 、MoO 3 、SiO 2 、Ta 2 O 5 、ZrO 2 Placing the raw materials in a mortar, mixing with alcohol as a dispersing agent, fully grinding for more than 1 hour, uniformly mixing, and drying under an infrared lamp to obtain sample powder; (2) The powder sample was weighed 0.5g and placed in a tabletting mill and pressed at a pressure of 4Mpa for 30 seconds to form tablets having a diameter of 10mm and a thickness of about 1-2 mm. Placing the mixture into a crucible, presintering for 12 hours at 600 ℃, continuously grinding and tabletting the sample, and finally sintering and preserving heat for 12 hours at 890 ℃ to obtain the target product. The invention is made ofThe prepared bismuth vanadate-based medium-low entropy oxygen ion conductor material has low cost, excellent electrical property and conductivity up to 10 ‑2 S/cm。
Description
Technical Field
The invention belongs to the field of inorganic materials and solid chemistry, and particularly relates to a bismuth vanadate-based medium-low entropy oxygen ion conductor material and a preparation method thereof.
Background
Solid Oxide Fuel Cells (SOFCs) are a clean energy device that converts chemical energy into electrical energy with high efficiency, and are of great interest due to their all-solid structure, fuel diversity, and the like. The electrolyte is a critical component of a solid oxide fuel cell and determines the operating temperature of the cell. The electrolyte material in practical application at present is oxygen ion8mol% Yttrium Stabilized Zirconia (YSZ) of subconductors. However, YSZ generally needs to be maintained above 800 ℃ because of its low oxygen ion conductivity at medium to low temperatures (400-700 ℃). The high operating temperature shortens the service life of each component, causes side reactions between the electrodes and the electrolyte and the like, thereby limiting the application of SOFCs in transportation and portable power. In order to reduce the operation temperature to a middle-low temperature region (400-700 ℃), the development of a high conductivity in the temperature region is required>10 -3 S/cm) and has excellent thermodynamic and chemical stability, the main problem of the novel electrolyte materials reported at present is that the thermal stability and chemical stability of the materials are poor, so that the practical application requirements cannot be met. Therefore, development of an electrolyte having high conductivity in a medium-low temperature region (400-700 ℃) and excellent thermodynamic and chemical stability is urgently required.
At the end of the 80 s of the 20 th century, a new family with excellent low temperature ion conductivity properties was proposed, named bimevaox (where Bi is bismuth, me is a metal ion, V is vanadium, ox is oxygen). These materials are derived from the parent compound Bi 4 V 2 O 11 (also written as Bi) 2 VO 5.5 ) Is obtained by partially replacing vanadium with metal cations. These compounds exhibit excellent ionic conductivity, in particular at low and medium temperatures, up to 10 at 300 DEG C -3 S cm -1 Can reach 10 at 600 DEG C -1 S cm -1 . Through V 5+ Is (Me=Cu) 2+ ，Co 2+ ，Zn 2+ ，Fe 3+ ，Al 3+ ，Ti 4+ ，Sn 4+ ，P 5+ ，Nb 5+ ) And the like, and explores various synthesis methods including a coprecipitation method, a sol-gel method, a combustion method and a mechanical-chemical activation method. The current solid phase reaction method is the most widely used preparation method. For the parent material Bi 2 VO 5.5 It is generally considered to be a single layer Aurivillius phase (of the general formula Bi 2 A n-1 B n O 3n+3 ) And Bi is 2 VO 5.5 Is a knot of (2)The structure undergoes two transitions to form three phases, namely, a monoclinic phase alpha-Bi at 450 ℃ from room temperature 2 VO 5.5 To orthorhombic phase beta-Bi 2 VO 5.5 Then becomes tetragonal phase gamma-Bi at 570 DEG C 2 VO 5.5 . gamma-Bi2VO5.5 phase in>Has high oxygen ion conductivity at 570 ℃ and alpha-Bi 2 VO 5.5 The lower low temperature conductivity of the phase is associated with ordered oxygen vacancies. There is sufficient evidence that metal cation doping can increase Bi 2 VO 5.5 Which helps to stabilize the gamma phase to room temperature. So far, the studied doped Cu has the highest ionic conductivity, which is about 3.2X10 at 300 DEG C -3 S/cm。
Bismuth vanadate in this work has the chemical formula Bi 2 VO 5.5 . Based on the parent compound Bi 2 VO 5.5 The material adopts the traditional solid phase reaction method to dope Cu in the vanadium site part 2+ 、Ni 2+ 、Nb 5+ 、Ti 4+ 、Ga 3+ 、Mo 6+ 、Si 4+ 、Ta 5+ 、Zr 4+ Three novel quadruple substituted BIMeVOx, bi respectively, were prepared 2 V (1-x) (CuNiNbTi) x O 5.5-σ 、Bi 2 V (1-x) (GaSiTaZr) x O 5.5-σ And Bi (Bi) 2 V (1-x) (GaMoTaZr) x O 5.5-σ And their phase and electrical properties have been studied intensively.
Disclosure of Invention
The invention aims to provide a bismuth vanadate-based medium-low entropy oxygen ion conductor material and a preparation method thereof. The preparation method of the bismuth vanadate-based medium-low entropy oxygen ion conductor material comprises the following specific steps:
(1) Before weighing, firstly, raw material Bi is added 2 O 3 And placing the mixture and CuO in a drying oven to dry for 12 hours at 180 ℃, and weighing according to the designed stoichiometric ratio. Weighing Bi with purity of more than 99 percent (mass percent) 2 O 3 、V 2 O 5 、CuO 、NiO 、Nb 2 O 5 、TiO 2 、Ga 2 O 3 、MoO 3 、SiO 2 、Ta 2 O 5 、ZrO 2 The raw materials are placed in an agate mortar, mixed with alcohol as a dispersing agent, fully ground by using pressure and friction force, generally ground for more than 1 hour, uniformly mixed and dried under an infrared lamp to obtain sample powder.
(2) Weighing 0.5g of powder sample, placing into tablet grinding tool, using rotary plunger of tablet press to provide pressure and friction, pressing at 4Mpa for 30 s to obtain tablet with diameter
10mm, a wafer with a thickness of about 1-2 mm. Loading the tablets into an alumina crucible, presintering for 12 hours at 600 ℃ in a muffle furnace, continuously grinding and tabletting the presintered samples, repeating the steps before presintering, and finally sintering and preserving heat for 12 hours at 890 ℃ to obtain the target product.
(3) Crushing the ceramic sheet prepared in the step (2), and determining that the prepared sample is a single phase through XRD and SEM-EDS tests. The electrochemical impedance spectrum is utilized to research the electrical property and the conductivity type of the bismuth vanadate-based medium-low entropy oxygen ion conductor material, and the test result shows that the conductivity gradually decreases along with the increase of the doping amount, and the highest conductivity can reach 10 -2 S/cm。
Drawings
FIG. 1 is example 1 Bi 2 V (1-x) (CuNiNbTi) x O 5.5-σ XRD patterns of (x=0.05, 0.1) system materials.
FIG. 2 is example 1 Bi 2 V (1-x) (CuNiNbTi) x O 5.5-σ (x=0.05, 0.1) SEM-EDS elemental profile of the system material.
FIG. 3 is example 1 Bi 2 V (1-x) (CuNiNbTi) x O 5.5-σ (x=0.05, 0.1) Arrehnius plot of conductivity of system material as a function of doping amount and Arrehnius plot of conductivity of material at different partial pressures of oxygen at x=0.05.
FIG. 4 is example 2 Bi 2 V (1-x) (GaSiTaZr) x O 5.5-σ XRD patterns of (x=0.05, 0.1, 0.15) system materials.
FIG. 5 is example 2 Bi 2 V (1-x) (GaSiTaZr) x O 5.5-σ (x=0.05, 0.1, 0.15) SEM-EDS elemental profile for system material x=0.1.
FIG. 6 is example 2 Bi 2 V (1-x) (GaSiTaZr) x O 5.5-σ Arrehnius plot of conductivity of (x=0.05, 0.1, 0.15) system material as a function of doping amount and Arrehnius plot of conductivity of material at different partial pressures of oxygen for x=0.05 and x=0.1.
FIG. 7 is example 3Bi 2 V (1-x) (GaMoTaZr) x O 5.5-σ (x is more than or equal to 0.05 and less than or equal to 0.15) XRD spectrum of the system material.
FIG. 8 is example 3Bi 2 V (1-x) (GaMoTaZr) x O 5.5-σ (0.05.ltoreq.x.ltoreq.0.15) the SEM-EDS element distribution diagram of the material when x=0.15.
FIG. 9 is example 3Bi 2 V (1-x) (GaMoTaZr) x O 5.5-σ (0.05.ltoreq.x.ltoreq.0.15) Arrehnius diagram of conductivity of the system material as a function of doping amount and Arrehnius diagram of conductivity of the material at different partial pressures of oxygen when x=0.05, x=0.1 and x=0.15.
Detailed Description
The following detailed description is made by way of specific examples, which are given by way of illustration of detailed embodiments and specific operation procedures on the premise of the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
example 1 design to yield 1mol of the target product Bi 2 V 0.8 (CuNiNbTi) 0.05 O 5.325 A material. 1mol Bi is weighed 2 O 3 、0.05 mol CuO 、0.05 mol NiO 、0.025 mol Nb 2 O 5 、0.4 mol V 2 O 5 And 0.05 mol TiO 2 Then placing the weighed raw materials in a mortar, adding a proper amount of alcohol, and fully grinding for more than 1 hour to obtain mixed powder. Tabletting the mixture, presintering at 600deg.C for 12 hr, grinding, weighing about 0.5g of the powder, filling into 10mm diameter mold, tabletting, sintering at 890 deg.C for 12 hr, and heating and cooling at a speed of about 5 deg.C/minAnd (3) heating to obtain a compact ceramic sheet.
FIGS. 1-3 are examples 1 Bi, respectively 2 V (1-x) (CuNiNbTi) x O 5.5-s (x=0.05, 0.1) XRD patterns of the system materials, EDS element profiles at x=0.05, 0.1, arrenius patterns of conductivity as a function of doping amount, arrenius patterns of conductivity of the materials at different oxygen partial pressures at x=0.05, table 1 shows the conductivities and activation energies of the system materials.
Table 1 example 1 Bi 2 V (1-x) (CuNiNbTi) x O 5.5-σ (x=0.0, 0.05) conductivity and activation energy of the system material.
| x | σ 250℃ (S cm -1 ) | σ 500℃ (S cm -1 ) | σ 800℃ (S cm -1 ) | E a LT (eV)T≤500℃ | E a HT (eV)T＞500℃ |
| 0.0 | 3.67×10 -6 | 1.13×10 -2 | 3.24×10 -2 | 0.01 | 1.21 |
| 0.05 | 4.88×10 -6 | 1.32×10 -3 | 1.81×10 -2 | 0.65 | - |
Example 2:
example 2 design to yield 1mol of the target product Bi 2 V 0.8 (GaSiTaZr) 0.05 O 5.4 A material. 1mol Bi is weighed 2 O 3 、0.05 mol Ga 2 O 3 、0.05 mol SiO 2 、0.025 mol Ta 2 O 5 、0.05 mol ZrO 2 Then placing the weighed raw materials in a mortar, mixing with alcohol as a dispersing agent, fully grinding by using pressure and friction force, generally grinding for more than 1 hour, uniformly mixing, and drying under an infrared lamp to obtain sample powder. The material was placed in a tabletting mill and compressed for 30 seconds at a pressure of 4Mpa using a tabletting machine rotary plunger to provide pressure and friction, and a disc of 10mm diameter and about 1-2mm thickness was pressed. Loading the tablets into an alumina crucible, presintering for 12 hours at 600 ℃ in a muffle furnace, continuously grinding and tabletting the presintered samples, repeating the steps before presintering, and finally sintering at 890 ℃ for 12 hours, wherein the temperature rising and reducing rate is 5 ℃/min to obtain the target product.
FIGS. 4-6 are examples 1 Bi, respectively 2 V (1-x) (GaSiTaZr) x O 5.5-σ (x=0.05, 0.1, 0.15) XRD patterns of the system material, EDS element profile at x=0.1, arrenius pattern of conductivity as a function of doping amount, arrenius pattern of conductivity at different oxygen partial pressures for the material at x=0.05 and x=0.1, table 2 shows the conductivity and activation energy of the system material.
Table 2 example 2 Bi 2 V (1-x) (GaSiTaZr) x O 5.5-σ (x=0.0, 0.05, 0.1) conductivity and activation energy of the system material.
| x | σ 250℃ (S cm -1 ) | σ 500℃ (S cm -1 ) | σ 800℃ (S cm -1 ) | E a LT (eV)T≤500℃ | E a HT (eV)T＞500℃ |
| 0.0 | 3.67×10 -6 | 1.13×10 -2 | 3.24×10 -2 | 0.01 | 1.21 |
| 0.05 | 1.03×10 -4 | 2.47×10 -2 | 5.62×10 -2 | 0.80 | 0.17 |
| 0.1 | 2.68×10 -6 | 5.05×10 -4 | 1.0×10 -2 | 0.90 | - |
Example 3:
example 3 design of 1mol of Bi as target product 2 V 0.8 (GaMoTaZr) 0.05 O 5.45 A material. 1mol Bi is weighed 2 O 3 、0.05 mol Ga 2 O 3 、0.05 mol MoO 3 、0.025 mol Ta 2 O 5 、0.05 mol ZrO 2 Then placing the weighed raw materials in a mortar, mixing with alcohol as a dispersing agent, fully grinding by using pressure and friction force, generally grinding for more than 1 hour, uniformly mixing, and drying under an infrared lamp to obtain sample powder. The material was placed in a tabletting mill and compressed for 30 seconds at a pressure of 4Mpa using a tabletting machine rotary plunger to provide pressure and friction, and a disc of 10mm diameter and about 1-2mm thickness was pressed. Loading the tablets into an alumina crucible, presintering for 12 hours at 600 ℃ in a muffle furnace, continuously grinding and tabletting the presintered samples, repeating the steps before presintering, and finally sintering at 890 ℃ for 12 hours, wherein the temperature rising and reducing rate is 5 ℃/min to obtain the target product.
FIGS. 7-9 are examples 1 Bi, respectively 2 V (1-x) (GaMoTaZr) x O 5.5-σ (0.05.ltoreq.x.ltoreq.0.15) XRD pattern of the system material, EDS element distribution pattern when x=0.15, arrehnius pattern of conductivity with doping amount, arrehnius pattern of conductivity of the material at different partial pressures of oxygen when x=0.05, x=0.1 and x=0.15, and Table 3 shows the conductivity and activation energy of the system material.
Table 3 example 3Bi 2 V (1-x) (GaMoTaZr) x O 5.5-σ (x=0.0, 0.05, 0.1, 0.15) conductivity and activation energy of the system material.
| x | σ 250℃ (S cm -1 ) | σ 500℃ (S cm -1 ) | σ 800℃ (S cm -1 ) | E a LT (eV)T≤500℃ | E a HT (eV)T＞500℃ |
| 0.0 | 3.67×10 -6 | 1.13×10 -2 | 3.24×10 -2 | 0.01 | 1.21 |
| 0.05 | 4.02×10 -5 | 1.86×10 -2 | 2.44×10 -2 | 0.93 | 0.04 |
| 0.1 | 5.47×10 -7 | 1.05×10 -3 | 1.47×10 -2 | 1.05 | 0.58 |
| 0.15 | 1.22×10 -7 | 4.13×10 -4 | 1.33×10 -2 | 1.13 | 0.67 |
TABLE 4 Bi based on the parent compound 2 VO 5.5 The material is doped with different elements and entropy values with different proportions are calculated.
| Chemical formula | Entropy value |
| Bi 2 V 0.8 (CuNiNbTi) 0.05 O 5.325 | 0.74R |
| Bi 2 V 0.8 (GaSiTaZr) 0.05 O 5.4 | 0.74R |
| Bi 2 V 0.6 (GaSiTaZr) 0.1 O 5.3 | 0.96R |
| Bi 2 V 0.8 (GaMoTaZr) 0.05 O 5.45 | 0.74R |
| Bi 2 V 0.6 (GaMoTaZr) 0.1 O 5.4 | 0.96R |
| Bi 2 V 0.4 (GaMoTaZr) 0.15 O 5.35 | 1.10R |
Claims (2)
1. The bismuth vanadate-based medium-low entropy oxygen ion conductor material and the preparation method thereof are characterized by comprising the following specific steps:
(1) Before weighing, firstly, raw material Bi is added 2 O 3 Placing the mixture and CuO in a drying oven at 180 ℃ for drying for 12 hours, and weighing according to the designed stoichiometric ratio; weighing Bi with purity of more than 99 percent (mass percent) 2 O 3 、V 2 O 5 、CuO 、NiO 、Nb 2 O 5 、TiO 2 、Ga 2 O 3 、MoO 3 、SiO 2 、Ta 2 O 5 、ZrO 2 Placing the raw materials in an agate mortar, mixing with alcohol as a dispersing agent, fully grinding by using pressure and friction force, generally grinding for more than 1 hour, uniformly mixing, and drying under an infrared lamp to obtain sample powder;
(2) Weighing 0.5g of powder sample, placing into tablet grinding tool, using rotary plunger of tablet press to provide pressure and friction, pressing at 4Mpa for 30 s to obtain tablet with diameter
A wafer of 10mm and a thickness of about 1-2 mm; loading the tablets into an alumina crucible, presintering for 12 hours at 600 ℃ in a muffle furnace, continuously grinding and tabletting the presintered samples, repeating the steps before presintering, and finally sintering and preserving heat for 12 hours at 890 ℃ to obtain a target product;
(3) Crushing the ceramic sheet prepared in the step (2), and determining that the prepared sample is a single phase through XRD (X-ray diffraction) and SEM-EDS (electron beam diffraction-electron beam ionization) tests; using electrochemical impedance spectroscopyThe electrical property and the conductivity type of the bismuth vanadate-based medium-low entropy oxygen ion conductor material are researched, and the test result shows that the conductivity is gradually reduced along with the increase of the doping amount, and the highest conductivity can reach 10 -2 S/cm。
2. The novel bismuth vanadate-based medium-low entropy oxygen ion conductor material and the preparation method thereof as claimed in claim 1, wherein the conventional solid phase reaction method is adopted to dope Cu in the vanadium site part 2+ 、Ni 2+ 、Nb 5+ 、Ti 4+ 、Ga 3+ 、Mo 6+ 、Si 4+ 、Ta 5 + 、Zr 4+ Preparation of Bi 2 V (1-x) (CuNiNbTi) x O 5.5-σ (x=0.05、0.1)、Bi 2 V (1-x) (GaMoTaZr) x O 5.5-σ (0.05≤x≤0.15)、Bi 2 V (1-x) (GaSiTaZr) x O 5.5-σ (x=0.05, 0.1, 0.15) ceramic material based on the parent compound Bi 2 VO 5.5 Co-doping Cu in vanadium site part 2+ 、Ni 2+ 、Nb 5+ 、Ti 4+ Or Ga 3+ 、Mo 6+ 、Si 4+ 、Ta 5+ 、Zr 4+ Or Ga 3+ 、Si 4+ 、Ta 5+ 、Zr 4+ A single phase is formed, the proportion of doping elements can reach x=0.15, and the calculated entropy value is divided into medium entropy or low entropy materials according to different doping proportions.
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| US5227257A (en) * | 1989-07-18 | 1993-07-13 | Universite Des Sciences Et Techniques De Lille Flandres Artois Ecole Nationale Superieure De Chimie De Lille Institut National Polytechnique De Grenoble | Compositions derived from bi4v2011 |
| FR2698016A1 (en) * | 1992-11-13 | 1994-05-20 | Air Liquide | New bismuth vanadium oxide cpd. - used as solid electrolyte for oxygen sepn. from gas mixt. |
| US5387330A (en) * | 1991-07-17 | 1995-02-07 | Matsushita Electric Industrial Co., Ltd. | Mixed ionic conductors |
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| US20200036028A1 (en) * | 2018-07-24 | 2020-01-30 | University Of Maryland, College Park | Stable high conductivity oxide electrolyte |
| US20220364240A1 (en) * | 2020-02-14 | 2022-11-17 | Henkel Ag & Co. Kgaa | Bismuth compositions for metal pretreatment applications |
| CN116639727A (en) * | 2022-11-09 | 2023-08-25 | 西北工业大学 | Modified bismuth vanadate-based oxygen ion conductor material and preparation method thereof |
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| US5387330A (en) * | 1991-07-17 | 1995-02-07 | Matsushita Electric Industrial Co., Ltd. | Mixed ionic conductors |
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| CN101054195A (en) * | 2007-04-12 | 2007-10-17 | 武汉理工大学 | Method for synthesizing middle and low temperature oxygen ion conductor material |
| US20200036028A1 (en) * | 2018-07-24 | 2020-01-30 | University Of Maryland, College Park | Stable high conductivity oxide electrolyte |
| US20220364240A1 (en) * | 2020-02-14 | 2022-11-17 | Henkel Ag & Co. Kgaa | Bismuth compositions for metal pretreatment applications |
| CN116639727A (en) * | 2022-11-09 | 2023-08-25 | 西北工业大学 | Modified bismuth vanadate-based oxygen ion conductor material and preparation method thereof |
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