CN110218091A - A kind of method that sol-gel auto-combustion method prepares Fe element doping barium cerate solid electrolyte - Google Patents
A kind of method that sol-gel auto-combustion method prepares Fe element doping barium cerate solid electrolyte Download PDFInfo
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 23
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000009767 auto-combustion synthesis reaction Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 244000248349 Citrus limon Species 0.000 claims description 4
- 235000005979 Citrus limon Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000002001 electrolyte material Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 abstract 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 239000000446 fuel Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 101150058765 BACE1 gene Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910002761 BaCeO3 Inorganic materials 0.000 description 1
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
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- H—ELECTRICITY
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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- H—ELECTRICITY
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract
A kind of method that sol-gel auto-combustion method prepares Fe element doping barium cerate solid electrolyte, is related to solid electrolyte material preparation technical field.By BaCe1‑xFexO3‑xMetallic element ratio weighs cerous nitrate, barium nitrate and ferric nitrate and is dissolved in distilled water, is uniformly mixing to obtain mixed solution；Citric acid and ethylene glycol are added into mixed solution, is added in mixed solution and stirs evenly after weighing；Heating stirring obtains foam-like gel after regulation system pH value, and gel drying is obtained xerogel；Xerogel is placed in Muffle furnace, is kept the temperature after heating pre-burning, obtains the loose powder of pre-burning；The loose powder of pre-burning is ground into after fine powder and is charged with binder and is carried out tabletting again, is finally sintered.In the series of electrolyte material being prepared, there is good lower Conductance activation energy, ionic conductivity.With preferable electrolyte property, it was demonstrated that the feasibility of Fe doping barium cerate base electrolyte material.
Description
Technical field
The present invention relates to solid electrolyte material preparation technical fields, are specifically related to a kind of sol-gel auto-combustion method system
The method of standby Fe element doping barium cerate solid electrolyte.
Background technique
From the whole world on the whole from the point of view of, energy shortage problem and ecological environmental pollution problem are increasingly serious, each state, the world
Family is all carrying out constantly research and development to fuel cell technology, tries to explore the electricity that research and development are able to achieve efficient energy conversion
Pool technology wants to reduce the damage to environment with this.
China is energy consumption big country, and SOFC has boundless application market prospect, although SOFC is with many excellent
Point, the research and development of domestic scientific research institutes also have certain basis, and the domestic periodical last decade delivered in the field SOFC, which is presented, rapidly to be increased
It is long, but the mating deficiency of domestic industry, cause SOFC business application to lag behind advanced international standard.Meanwhile developed country is at present
Detailed SOFC developing goal has been put into effect, and has formulated corresponding subsidy policy, it is desirable to the following country and various regions government
There can be relevant support policy to put into effect.Kinds of fuel cells used at present is various, there is direct methanol fuel cell DMPC, alkalinity
Fuel cell etc., wherein outstanding behaviours is in terms of motor vehicle fuel.SOFC, which is applied to distributed energy, has generating efficiency high, remaining
Hot quality is high, without friction and low noise, the advantages such as in green emissions, and the major company of the several developed countries of Abroad in Recent Years is in SOFC quotient
Industry application achieves large development, but there is also higher operating costs problems at present, affect the progress of industrialization.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of sol-gel auto-combustion method preparation Fe members
The method of element doping barium cerate solid electrolyte, can the excellent electrolyte of processability.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a kind of sol-gel auto-combustion method prepares Fe
The method of element doping barium cerate solid electrolyte, steps are as follows:
1., by preparing product BaCe1-xFexO3-xMiddle metallic element ratio accurately weighs the Ce calculated on an electronic balance
(NO3)3·6H2O、Ba(NO3)2、Fe(NO3)3·9H2O is accordingly successively dissolved them in distilled water, is uniformly mixing to obtain mixed
Close solution；Prepare product BaCe1-xFexO3-xMiddle x value is 0-0.4；
2., citric acid and ethylene glycol are added into mixed solution, be added in mixed solution and stir evenly after weighing；
3., ammonia water conditioning system pH value is added between 4-6 in Xiang Shangshu mixed solution；
4., mixed solution is put into water bath with thermostatic control magnetic stirring apparatus, heating stirring obtains foam-like gel；Then it will coagulate
Glue is put among baking oven, and xerogel is dried to obtain；
5., xerogel is placed in Muffle furnace, kept the temperature after heating pre-burning, obtain the loose powder of pre-burning；
6., the loose powder of pre-burning is fully ground under sodium lamp with agate mortar, weigh one after being ground into fine powder
The powder for determining quality is charged with binder and is carried out tabletting again, is finally sintered.
As the optimal technical scheme of preparation method of the invention, in preparation method:
Step 2. in the additional amount of citric acid be 1.5 times of amount of metal ion total material, the additional amount of ethylene glycol is lemon
1.2 times of the amount of lemon acid substance.
Step 4. in mixed solution is put into 80 DEG C of water bath with thermostatic control magnetic stirring apparatus, heating stirring 2h obtains foam-like
Gel；Then gel is put among baking oven, the dry 12h at 120 DEG C, to obtain xerogel.
Step 5. in xerogel be put into be ground into fine powder in agate mortar, be subsequently placed in Muffle furnace, 800
DEG C heat preservation 2h, obtain the loose powder of pre-burning.
Step 6. in the loose powder of pre-burning is fully ground under sodium lamp with agate mortar, weighed after being ground into fine powder
The powder of certain mass out is charged with binder PVA solution and is carried out tabletting again, finally place it on potsherd in
1300 DEG C of sintering 5h.
Compared with prior art, beneficial effects of the present invention are shown:
1), by a series of processing such as powder sintering obtained granulation, milling, tabletting, calcinings.And tested and found by XRD,
Powder characteristic peak is completely coincident with standard card, has cubic fluorite structure, without the second phase or other impurities.
2), make BaCe after the electrolyte powder tabletting that will be made is sintered at 1300 DEG C again1-xFexO3-xElectrolyte
Material possesses preferable consistency.The analysis for carrying out different amplification to the microstructure of sintered body by SEM again, explores and burns
Knot process is mainly the influence of consistency to product structure and performance.
3), with the chemical property of electrochemical workstation test product, there is good conductivity, electric conductivity by test
It can substantially improve and evaluate its application value in solid oxide fuel cell.Selection for middle low-temperature electrolytic material provides
It is a kind of may, be expected to obtain further development in middle low temperature SOFC research.
4), in the BaCe being prepared1-xFexO3-xIn series of electrolyte material, BaCe1-xFexO3-xWith good lower
Conductance activation energy, ionic conductivity.Its ionic conductivity at 800 DEG C is 0.02295S/cm；Conductance activation energy is
0.68eV has preferable electrolyte property, it was demonstrated that the feasibility of Fe doping barium cerate base electrolyte material.
Detailed description of the invention
Fig. 1 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-x(x=0.2) thermogravimetric analysis figure；
Fig. 2 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-xXRD diagram；
Fig. 3 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-xScanning electron microscope (SEM) photograph, a-f successively table
Show the totally 6 groups of doping ratios of x=0,0.1,0.2,0.25,0.3,0.4；
Fig. 4 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-x(x=0.4) at different temperatures
Impedance spectra；
Fig. 5 is the conductivity and temperature relation figure for preparing Fe element doping barium cerate solid electrolyte；
Fig. 6 is the Arrhenius figure for the ionic conductivity for preparing Fe element doping barium cerate solid electrolyte.
Specific embodiment
It is solid to sol-gel auto-combustion method preparation Fe element doping barium cerate of the invention with attached drawing with reference to embodiments
The method of body electrolyte, which is made, to be discussed further.
Embodiment 1
A kind of method that sol-gel auto-combustion method prepares Fe element doping barium cerate solid electrolyte, steps are as follows:
1., by preparing product BaCe1-xFexO3-xMiddle metallic element ratio accurately weighs the Ce calculated on an electronic balance
(NO3)3·6H2O、Ba(NO3)2、Fe(NO3)3·9H2O is accordingly successively dissolved them in the beaker containing 100mL distilled water,
It is uniformly mixing to obtain mixed solution.6 groups of experiments are carried out in embodiment 1 altogether, respectively correspond in product x value be 0,0.1,0.2,
0.25、0.3、0.4。
2., citric acid and ethylene glycol, the additional amount of citric acid is added into mixed solution is the amount of metal ion total material
1.5 times, the additional amount of ethylene glycol is 1.2 times of the amount of lemon acid substance, after weighing be added mixed solution in stir evenly.
3., ammonia water conditioning system pH value is added between 4-6 in Xiang Shangshu mixed solution.
4., mixed solution is put into 80 DEG C of water bath with thermostatic control magnetic stirring apparatus, heating stirring 2h obtains foam-like gel.
Then gel is put among baking oven, the dry 12h at 120 DEG C, to obtain xerogel.
5., xerogel be put into be ground into fine powder in agate mortar, be subsequently placed in Muffle furnace, protected at 800 DEG C
Warm 2h obtains the loose powder of pre-burning.
6., the loose powder of pre-burning is fully ground under sodium lamp with agate mortar, weigh one after being ground into fine powder
The powder for determining quality is charged with two drop PVA solutions as binder and is carried out tabletting again, finally places it in potsherd
On in 1300 DEG C of sintering 5h.
The performance characterization of Fe element doping barium cerate solid electrolyte
One, thermogravimetric analysis
Fig. 1 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-x(x=0.2) thermogravimetric analysis figure
The temperature of (TG-DTA thermal analysis curve), instrument setting is from 40 DEG C to 800 DEG C, and the rate of heating is 20K/min.It can basis
TG-DTA curvilinear motion is roughly divided into three parts: the quality of gel starts slowly to reduce at the beginning, TG curve decline, to 300
DEG C or so stop, it is inferred that this quality disappearance be mainly sample in band water or other volatile impurity；At this
DTA curve declines in one stage, it should be that a large amount of heat has been taken away in the volatilization evaporation of moisture and impurity.At 300 DEG C to 650 DEG C,
This period example weight be basically unchanged, because of BaCe1-xFexO3-XThe firing temperature of system is 1300 DEG C, in the first stage
After moisture and the removal of some impurity, reacted in this temperature range without substance, so mass conservation, TG curve is substantially steady
It is fixed.Because not reacting, no heat release endothermic thermal event, so this stage heats with instrument, the temperature of sample is slowly increased,
DTA curve is in rising trend.After 650 DEG C, second of beginning is weightless, and TG curve also reflects this phenomenon, after analysis, feels
Should be that the relatively high impurity of some reaction temperatures starts to react in this temperature range, so there is weightlessness, DTA
There is a unexpected downward trend in curve, and has proved the generation of reaction, it should be an endothermic reaction, make sample
Temperature reduces, and after fully reacting, sample is heated, and temperature slowly rises, and DTA curve continues to rise.
Two, XRD analysis
Fig. 2 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-xXRD diagram, as seen from the figure 6
In the XRD spectra of composite granule sample after the doping of kind of ratio, when X=0.10, diffraction maximum is more bright compared to other doping ratios
Aobvious to protrude, diffraction curve is more smooth.As X=0.40, diffraction miscellaneous peak becomes more, shows that composite granule sample is brilliant when X=0.40
It spends impure.When X=0.20,0.25,0.30, the XRD diagram spectral curve under three doping ratios is more similar, diffraction maximum and X=
0.10 compares both unobvious protrusions or without excessive miscellaneous peak.The maximum diffraction peak value for finally comparing five groups of components from figure, can
When obviously obtaining X=0.10, peak value highest shows that the powder sample crystalline substance degree of X=0.10 doping is the purest, and crystal structure is more
It is good.
Three, sem analysis
Fig. 3 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-xScanning electron microscope (SEM) photograph, a-f successively table
Show the totally 6 groups of doping ratios of x=0,0.1,0.2,0.25,0.3,0.4.Although the potsherd of 6 components is all as seen from the figure
Perovskite material, but the pattern of the potsherd of 6 components is slightly different, and is sintered with finding out by 1300 DEG C of heat preservation 5h
Afterwards, for the component surface of sheet without sky, structure is very fine and close, can also further illustrate that the temperature is to prepare BaCe1-xFexO3-XBody
It is suitable sintering temperature；The more smooth densification of the powder surface is suitble to the test of electrical property in conjunction with uniform close.
Four, porosity test
The parameter value under each X value difference sintering temperature is recorded, and resulting numerical value is measured after being sintered after calculating
Porosity value, as shown in table 1.
Table 1
As shown in Table 1, different X value doping ratios prepare the difference of porosity corresponding to product, and wherein X=0.40 is 1300
DEG C porosity is minimum, and X=0.20 is in 1300 DEG C of porosity highests.
Five, AC impedance and conductivity analysis
Fig. 4 is to prepare Fe element doping barium cerate solid electrolyte BaCe1-xFexO3-x(x=0.4) at different temperatures
Impedance spectra, it is real axis (Z ') and the imaginary axis (- Z ") respectively that transverse and longitudinal coordinate, which respectively represents different meanings, in figure.Because crystal grain is conductive
Process and electrode have different influences in reaction, so the transformation period constant with the time is different, so table in figure
Reveal different semi arches, this is the meaning of resistance.When temperature is relatively low, there are two deformations in upper figure
Different semi arch and a ray, with gradually increasing for temperature, the process of crystal boundary gradually becomes smaller front end and real axis
Crosspoint shows as grain resistance Rgi, and it is grain boundary resistance Rgb and electricity that two and half diameter of a circles, which respectively indicate different meanings respectively,
Pole polarization resistance Rc.
Fig. 5 is the conductivity and temperature relation figure for preparing Fe element doping barium cerate solid electrolyte；As we know from the figure: institute
There is test sample BaCe1-xFexO3-XConductivity increase with the raising of temperature.Wherein maximum conductivity appears in 800 DEG C,
X=0.30 is 2.29 × 10-2S/cm.It can be seen that Fe2+Doping significantly improve the conductivity of cationic conductor.
Fig. 6 gives BaCe1-xFexO3-XRelation curve (the Arrhenius of ln (σ T) and 1000/T under different doping ratios
Curve).As seen from the figure in experimental temperature (400 DEG C~800 DEG C) range, the ln (σ T) and 1000/T in sample are in more standard
Linear relationship, by fitting, find with temperature raising, activation energy shows as first increasing to be subtracted afterwards.On the whole, iron appropriate
Doping can be very good change BaCeO3Electrical property.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (6)
1. a kind of method that sol-gel auto-combustion method prepares Fe element doping barium cerate solid electrolyte, which is characterized in that step
It is rapid as follows:
1., by preparing product BaCe1-xFexO3-xMiddle metallic element ratio accurately weighs the Ce calculated on an electronic balance
(NO3)3·6H2O、Ba(NO3)2、Fe(NO3)3·9H2O is accordingly successively dissolved them in distilled water, is uniformly mixing to obtain mixed
Close solution；Prepare product BaCe1-xFexO3-xMiddle x value is 0-0.4；
2., citric acid and ethylene glycol are added into mixed solution, be added in mixed solution and stir evenly after weighing；
3., ammonia water conditioning system pH value is added between 4-6 in Xiang Shangshu mixed solution；
4., mixed solution is put into water bath with thermostatic control magnetic stirring apparatus, heating stirring obtains foam-like gel；Then gel is put
Enter among baking oven, is dried to obtain xerogel；
5., xerogel is placed in Muffle furnace, kept the temperature after heating pre-burning, obtain the loose powder of pre-burning；
6., the loose powder of pre-burning is fully ground under sodium lamp with agate mortar, weigh certain matter after being ground into fine powder
The powder of amount is charged with binder and is carried out tabletting again, is finally sintered.
2. preparation method as described in claim 1, which is characterized in that step 2. in the additional amount of citric acid be that metal ion is total
1.5 times of the amount of substance, the additional amount of ethylene glycol are 1.2 times of the amount of lemon acid substance.
3. preparation method as described in claim 1, which is characterized in that step 4. in mixed solution is put into 80 DEG C of thermostatted water
It bathes in magnetic stirring apparatus, heating stirring 2h obtains foam-like gel；Then gel is put among baking oven, is done at 120 DEG C
Dry 12h, to obtain xerogel.
4. preparation method as described in claim 1, which is characterized in that step 5. in xerogel be put into agate mortar grind
It at fine powder, is subsequently placed in Muffle furnace, in 800 DEG C of heat preservation 2h, obtains the loose powder of pre-burning.
5. preparation method as described in claim 1, which is characterized in that step 6. in by the loose powder agate mortar of pre-burning
Be fully ground under sodium lamp, be ground into the powder for weighing certain mass after fine powder, be charged with binder carry out again into
Row tabletting finally places it on potsherd in 1300 DEG C of sintering 5h.
6. preparation method as claimed in claim 5, which is characterized in that binder uses PVA solution.
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