CN105140526B - A kind of preparation method of fuel cell and fuel cell - Google Patents
A kind of preparation method of fuel cell and fuel cell Download PDFInfo
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- CN105140526B CN105140526B CN201510434675.1A CN201510434675A CN105140526B CN 105140526 B CN105140526 B CN 105140526B CN 201510434675 A CN201510434675 A CN 201510434675A CN 105140526 B CN105140526 B CN 105140526B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses the preparation method of a kind of fuel cell and fuel cell, negative electrode, anode and the intermediate layer of the fuel cell are pressed into potsherd；The intermediate layer is located between the negative electrode and the anode；Wherein, the intermediate layer is prepared by bloodstone material, and the composition and percentage by weight that the bloodstone material includes are：Fe2O3More than 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%.Fuel cell that the present invention is provided and preparation method thereof, the making material for solving fuel cell generally existing in the prior art is expensive, and is difficult the technical problem of acquisition.There is provided a kind of operating temperature is low, performance more preferably, cost is low, the high fuel cell of electrical conductivity.
Description
Technical field
The present invention relates to SOFC technical field, more particularly to a kind of fuel cell and fuel cell
Preparation method.
Background technology
SOFC is due to efficient energy conversion height and the few advantage of disposal of pollutants, having attracted extensively
Concern and research, quick development is obtained in the past few decades.But, SOFC is for a long time
The challenge of high-temperature material and high cost is faced, the electrolyte yttria stabilized zirconia for example most generally used, it needs
Enough electrical conductivity could be produced under 800-1000 DEG C of high temperature.Due to the limitation of its electrolyte oxygen ionic conductivity, solid oxidation
Thing fuel cell is not commercialized also so far.Therefore the research main trend of current solid oxide fuel cell is grasped for low temperature
Make, to solve the insoluble numerous technical barriers of high-temperature operation.
In research in recent years, on the one hand scientist develops the new material for having enough high ionic conductivities in low temperature, attempts
The conductive characteristic of Solid Oxide Fuel Cells is improved with nanometer technology, it is desirable to reach reduction SOFC
The purpose of operating temperature.On the other hand, development can be applied to the two-phase composite functional material of cryogenic conditions also as a weight
The strategy wanted.For example, L.Fan etc. report doped cerium oxide-carbonate two-phase compound electrolyte material embody it is excellent from
Subconductivity performance and low-temperature catalytic activity, the electrolytelike conductance is and traditional up to 0.1S/cm under 300 DEG C of low temperature
SOFC will can be only achieved same level at 1000 DEG C.B.Zhu etc. propose it is a kind of based on semiconductor from
The new electroless matter fuel cell of sub- conductor composite nano materials, the device has abandoned the complexity that electrolyte isolates anode cathode
Structure, anode cathode electrolyte is integrated in one to form " three-in-one " battery.This fuel cell can be 300-600 DEG C in low temperature
It is lower to operate and obtain excellent power output.In addition, a kind of semiconductor α-LiFeO of S.Tao latest reports2With insulator γ-
LiAlO2The nano composite material synthesized by solid reaction process, 0.50S is obtained in 650 DEG C of hydrogen or air atmosphere
cm-1Ionic conductivity.
In the studies above, electroless matter fuel cell has opened up a brand-new science as a kind of new battery technology
Disciplinary Frontiers.Natural nanometer technology selects electroless matter fuel cell to report and be named as the bright spot of research in 2011:" three close
One ".This fuel cell technology avoids the possibility reacted between battery component and other various high temperature and complicated
Limitation, the manufacture of the electrochemical device of complicated high cost is changed into simple low-cost mechanical and manufactured, fuel electricity will be realized
The commercialization in pond.It is very important problem to select suitable material to make electroless matter fuel cell.
In summary, the making material of fuel cell is the important subject in the current field, combustion of the prior art
Expect that battery generally existing making material is expensive, be difficult the technical problem obtained.
The content of the invention
A kind of preparation method of the present invention by providing fuel cell and fuel cell, solves fuel electricity in the prior art
The making material of pond generally existing is expensive, and is difficult the technical problem of acquisition.
On the one hand, the embodiment of the present application provides following technical scheme：
A kind of fuel cell, negative electrode, anode and the intermediate layer of the fuel cell are pressed into potsherd；The intermediate layer
Between the negative electrode and the anode；
Wherein, the intermediate layer is prepared by bloodstone material, composition and percentage by weight that the bloodstone material includes
For：Fe2O3More than 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%.
Optionally, the intermediate layer is specially：The bloodstone material；Or the bloodstone material is aoxidized with lanthanum-strontium ferro-cobalt
First composite of thing formation；Or the bloodstone material and the second composite of La-Ce-Pr oxide formation.
Optionally, when the intermediate layer is the bloodstone material, the negative electrode is the bloodstone material and lanthanum-strontium
Cobalt iron oxide presses 1:Mixture prepared by 1 volume ratio；The anode is the bloodstone material and nickel cobalt aluminium oxidate for lithium
By 1:Mixture prepared by 1 volume ratio；When the intermediate layer is first composite, the negative electrode and the anode
It is nickel cobalt aluminium oxidate for lithium and the electrode material of nickel foam formation；When the intermediate layer is second composite, institute
It is nickel cobalt aluminium oxidate for lithium and the electrode material of nickel foam formation to state negative electrode and the anode.
On the other hand there is provided a kind of preparation method of fuel cell, including：
It is powdered to grind bloodstone material, and the composition and percentage by weight that the bloodstone material includes are：Fe2O3Greatly
In 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%；
Intermediate layer material is prepared with the powdered bloodstone material；
Cathode material, anode material and the intermediate layer material are pressed into potsherd；The intermediate layer material is located at institute
State between cathode material and the anode material.
Optionally, it is described to prepare intermediate layer material with the powdered bloodstone material, be specially：With powdered institute
Bloodstone material is stated as the intermediate layer material；Or by the first mass bloodstone material more powdered than mixed grinding and
Lanthanum-strontium cobalt iron oxide the first mixture of formation；First mixture is sintered into the first duration at the first temperature；Grinding is burnt
First mixture after knot obtains the first composite；The intermediate layer material is used as using first composite；Or
The powdered bloodstone material and La-Ce-Pr carbonate is weighed by the second mass ratio；By the La-Ce-Pr carbonate weighed
Add in deionized water；The deionized water formation suspension is stirred, and dust technology is added into the suspension, so that described
Suspended things dissolving in suspension, forms the first solution；The bloodstone material weighed is added in first solution；Stir
First solution is mixed for suspended shape；First solution is evaporated, block is formed；The block second is sintered at the second temperature
Duration；After the block after cooling sintering, it is the second powdered composite to grind the block；It is multiple with described second
Condensation material is used as the intermediate layer material.
Optionally, first mass ratio is 13:7；First temperature is 700 DEG C；A length of 2 hours when described first.
Optionally, second mass ratio is 2:3；The concentration of the dust technology is 0.5mol/L；The second temperature is
750℃；A length of 2 hours when described second.
Optionally, when the intermediate layer material is the powdered bloodstone material：The making of the cathode material
Method is：By 1:1 volume ratio, mixes the bloodstone material and lanthanum-strontium cobalt iron oxide of simultaneously abrasive flour shape, forms institute
State cathode material；The preparation method of the anode material is：By 1:1 volume ratio, mixes the red iron of simultaneously abrasive flour shape
Pit wood material and nickel cobalt aluminium oxidate for lithium, form the anode material.
Optionally, when the intermediate layer material is first composite or second composite：Described the moon
The preparation method of pole material and the anode material is：Nickel cobalt aluminium lithium oxide powder is added to containing glycerine by the first proportioning
Alcoholic solution in, stir the alcoholic solution and obtain black slurry；The black slurry is coated to foam nickel surface, and
Drying is coated with the nickel foam of the black slurry at a temperature of 3rd；Using the nickel foam of drying as the cathode material and
The anode material.
Optionally, first proportioning adds 0.4g nickel cobalt aluminium lithium oxide powders for every milliliter of alcoholic solution；Institute
State the glycerine that alcoholic solution contains 10% volume fraction；3rd temperature is 300 DEG C.
The one or more technical schemes provided in the embodiment of the present application, have at least the following technical effects or advantages：
1st, the embodiment of the present application is provided fuel cell and the preparation method of fuel cell, using bloodstone material in
Interbed basic material, and bloodstone is nature mineral matter, there is abundant reserves in China, it is with low cost, and due to the pit wood
It is that crude sedimentation is formed, its main component semiconductor Fe2O3With insulator SiO2Between Interface Mechanism, and carbonate answers
Cooperation use, create its excellent ionic conductivity, the temperature of fuel cell made using bloodstone is low, performance more
Good, cost is low, and electrical conductivity is high, effectively promotes the business application of fuel cell.
2nd, the embodiment of the present application provide fuel cell and fuel cell preparation method, using the bloodstone material with
First composite of lanthanum-strontium cobalt iron oxide formation is applied to show after fuel cell excellent low as intermediate layer material
Warm service behaviour；Can as intermediate layer material using the second composite of the bloodstone material and the formation of La-Ce-Pr oxide
The higher battery open circuit voltage of acquisition and power output.The synthesis technique of two kinds of composites is simple and quick, with low cost, institute's group
The fuel battery performance of dress is excellent, and a new direction is provided for the development of low-temperature fuel cell technology.
3rd, the embodiment of the present application is provided fuel cell and the preparation method of fuel cell, using the bloodstone and two kinds
Composite embodies proton conductivity as intermediate layer material, and the bloodstone is applied to the nature of its raw material
Fuel cell can play good ion transmitting effect, and fuel is applied to by the two kinds of composites formed after modification
Battery obtains more excellent battery performance.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only embodiments of the invention, for ability
For the those of ordinary skill of domain, on the premise of not paying creative work, it can also obtain other according to the accompanying drawing of offer
Accompanying drawing.
Fig. 1 is the flow chart of the preparation method of fuel cell in the embodiment of the present application two；
Fig. 2 is the X-ray diffractogram of the bloodstone material employed in the embodiment of the present application；
Fig. 3 is the X-ray diffractogram of the first composite L W-LSCF described in the embodiment of the present application
Fig. 4 is the electrical conductivity situation test chart of bloodstone material described in the embodiment of the present application；
Fig. 5 is the electrical conductivity situation test chart of the first composite L W-LSCF described in the embodiment of the present application；
Fig. 6 is the electrical conductivity situation test chart of the second composite L W-LCP described in the embodiment of the present application；
Fig. 7 is the electrochemical impedance spectrogram of bloodstone material described in the embodiment of the present application；
Fig. 8 is that the first composite L W-LSCF is tested under air atmosphere and different temperatures described in the embodiment of the present application
Electrochemical impedance spectrogram；
Fig. 9 is the first composite L W-LSCF described in the embodiment of the present application in hydrogen or air atmosphere and different temperatures
The electrochemical impedance spectrogram of lower test, and equivalent circuit diagram；
Figure 10 is I-V the and I-P curves of three part fuel cells prepared by bloodstone material described in the embodiment of the present application
Figure；
Figure 11 is the I- of electroless matter fuel cell prepared by the first composite L W-LSCF described in the embodiment of the present application
V and I-P curve maps；
Figure 12 is the I-V of electroless matter fuel cell prepared by the second composite L W-LCP described in the embodiment of the present application
With I-P curve maps.
Embodiment
A kind of preparation method of the embodiment of the present application by providing fuel cell and fuel cell, is solved in the prior art
The making material of fuel cell generally existing is expensive, and is difficult the technical problem of acquisition.There is provided a kind of operating temperature is low, performance
More preferably, cost is low, the high fuel cell of electrical conductivity.
In order to solve the above technical problems, the general thought that the embodiment of the present application provides technical scheme is as follows：
The application provides a kind of fuel cell, and negative electrode, anode and the intermediate layer of the fuel cell are pressed into potsherd；
The intermediate layer is located between the negative electrode and the anode；
Wherein, the intermediate layer is prepared by bloodstone material, composition and percentage by weight that the bloodstone material includes
For：Fe2O3More than 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%.
Fuel cell and the preparation method of fuel cell that the embodiment of the present application is provided, centre is used as using bloodstone material
Layer basic material, and bloodstone is nature mineral matter, there is abundant reserves in China, it is with low cost, and because the pit wood is
Crude sedimentation is formed, its main component semiconductor Fe2O3With insulator SiO2Between Interface Mechanism, and carbonate is compound
Effect, creates its excellent ionic conductivity, and the temperature of fuel cell made using bloodstone is low, performance more preferable,
Cost is low, and electrical conductivity is high, effectively promotes the business application of fuel cell.
In order to be better understood from above-mentioned technical proposal, below in conjunction with Figure of description and specific embodiment to upper
State technical scheme to be described in detail, it should be understood that the specific features in the embodiment of the present invention and embodiment are to the application skill
The detailed description of art scheme, rather than the restriction to technical scheme, in the case where not conflicting, the embodiment of the present application
And the technical characteristic in embodiment can be mutually combined.
Embodiment one
A kind of fuel cell is provided in the present embodiment, and negative electrode, anode and the intermediate layer of the fuel cell are pressed
Into potsherd；The intermediate layer is located between the negative electrode and the anode；
Wherein, the intermediate layer is prepared by bloodstone material, composition and percentage by weight that the bloodstone material includes
For：Fe2O3More than 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%.
In specific implementation process, the negative electrode, the anode and the intermediate layer are pressed into using layering dry pressing
Potsherd.
In specific implementation process, at the two ends of the potsherd, i.e., the cathode terminal, the sun in the potsherd
Silver paste is to be prepared into three part fuel cells on extremal graph.
In the embodiment of the present application, the intermediate layer is specially：
The bloodstone material；Or
The bloodstone material and the first composite of lanthanum-strontium cobalt iron oxide formation；Or
The bloodstone material and the second composite of La-Ce-Pr oxide formation.
In the embodiment of the present application, when the intermediate layer is the bloodstone material, the negative electrode is the bloodstone
Material presses 1 with lanthanum-strontium cobalt iron oxide:Mixture prepared by 1 volume ratio；The anode is the bloodstone material and nickel cobalt
Aluminium oxidate for lithium presses 1:Mixture prepared by 1 volume ratio；
When the intermediate layer is first composite, the negative electrode and the anode are nickel cobalt aluminium oxidate for lithium
With the electrode material of nickel foam formation；
When the intermediate layer is second composite, the negative electrode and the anode are nickel cobalt aluminium oxidate for lithium
With the electrode material of nickel foam formation.
Based on same inventive concept, present invention also provides the preparation method of the fuel cell of embodiment one, embodiment is seen
Two.
Embodiment two
In the present embodiment there is provided a kind of preparation method of fuel cell, Fig. 1 is refer to, Fig. 1 is combustion in embodiment two
The step of preparation method for expecting battery, schemes, as shown in figure 1, methods described includes：
Step S101, grinding bloodstone material is powdered, composition and percentage by weight that the bloodstone material includes
For：Fe2O3More than 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%；
Step S102, intermediate layer material is prepared with the powdered bloodstone material；
Step S103, potsherd is pressed into by cathode material, anode material and the intermediate layer material；The intermediate layer material
Material position is between the cathode material and the anode material.
In the embodiment of the present application, step S102, i.e., it is described to prepare intermediate layer material with the powdered bloodstone material
Material, be specially：
The intermediate layer material is used as using the powdered bloodstone material；Or
Mixed by the first mass bloodstone material more powdered than mixed grinding and lanthanum-strontium cobalt iron oxide formation first
Compound；First mixture is sintered into the first duration at the first temperature；First mixture after grinding and sintering is obtained
First composite；The intermediate layer material is used as using first composite；Or
The powdered bloodstone material and La-Ce-Pr carbonate is weighed by the second mass ratio；By the lanthanum cerium weighed
Praseodymium carbonate is added in deionized water；The deionized water formation suspension is stirred, and dust technology is added into the suspension,
So that the suspended things dissolving in the suspension, forms the first solution；The bloodstone material weighed is added described first
In solution；First solution is stirred for suspended shape；First solution is evaporated, block is formed；Institute is sintered at the second temperature
State the duration of block second；After the block after cooling sintering, it is the second powdered composite to grind the block；With
Second composite is used as the intermediate layer material.
In the embodiment of the present application, first mass ratio is 13:7；First temperature is 700 DEG C；When described first
A length of 2 hours.
In the embodiment of the present application, second mass ratio is 2:3；The concentration of the dust technology is 0.5mol/L；It is described
Second temperature is 750 DEG C；A length of 2 hours when described second.
It is that the bloodstone material, the intermediate layer material are described first to be combined to divide the intermediate layer material separately below
Material, and the intermediate layer material are described second composite, three kinds of situations, the preparation method fuel cell is discussed in detail：
The first, the intermediate layer material is the bloodstone material.
First, the bloodstone material is handled：Red powder is obtained after bloodstone material is ground.
Then, by the red powder and nickel cobalt aluminium oxidate for lithium according to volume ratio 1:1 mixed after be fully ground use
Make the anode material of the fuel cell, the composition of the nickel cobalt aluminium oxidate for lithium is Ni0.8Co0.15Al0.05LiO2-δ。
Next, by the red powder and lanthanum-strontium cobalt iron oxide according to volume 1:1 is mixed and is used as after being ground
The cathode material of the fuel cell；The composition of the lanthanum-strontium cobalt iron oxide is La0.8Sr0.2Co0.2Fe0.8O3-δ。
Subsequently, according to 6:3:2 part by weight, weigh the 0.3g red bloodstone material powder of anode material, 0.15g respectively
End and 0.1g cathode materials, these three materials are pressed into " NCAL anodes/LW electrolyte/LSCF negative electrodes " using layering dry pressing
The potsherd of structure, wherein, NCAL writes a Chinese character in simplified form for nickel cobalt aluminium oxidate for lithium, and LW writes a Chinese character in simplified form for bloodstone material, LSCF lanthanum-strontium cobalts
Ferriferous oxide is write a Chinese character in simplified form.
Finally, silver paste is coated at potsherd two ends and is prepared into three traditional part fuel cells.
Second, the intermediate layer material is first composite.
First, the bloodstone material is handled：Red powder is obtained after bloodstone material is ground.
Next, preparing first composite：It is 13 according to the first mass ratio:7, the bloodstone for weighing 0.26g is red
The lanthanum-strontium cobalt iron oxide of color powder and 0.14g, is fully ground after both are directly mixed as the first mixture, will be described
First mixture sinters 2h at 700 DEG C in air ambient, and then the first mixture again after grinding and sintering is obtained uniformly
Two-phase composite material LW-LSCF.
Subsequently, cathode material and anode material are prepared：It is lithium that 0.4g nickel cobalt aluminium is added according to every milliliter of alcoholic solution
Thing powder first proportioning, weigh 4g nickel cobalt aluminium lithium oxide powders be added to 10mL containing 10% volume fraction glycerine alcohol it is molten
In liquid, black slurry is obtained after stirring the alcoholic solution；The black slurry is coated to a kind of bubble of three dimensional network structure
Foam nickel surface, and the nickel foam after coating is dried at 300 DEG C, electroless matter fuel electricity is used as with the reticulated foam nickel of drying
The electrode in pond, i.e. NCAL-Ni electrodes.
Finally, first composite of above-mentioned preparation and electrode material are pressed into by ceramics using layering dry pressing
Piece, forms the fuel cell of " NCAL-Ni electrodes/composite bloodstone LW-LSCF/NCAL-Ni electrodes " symmetrical structure, i.e., one
Plant the electroless matter fuel cell that semiconductor ion conductor composite makes.
The third, the intermediate layer material is second composite.
First, the bloodstone material is handled：Red powder is obtained after bloodstone material is ground.
Next, preparing second composite, specifically it is prepared for using the method for wet-chemical in solution environmental
Ion conductor composite, i.e., described second composite：By second mass ratio 2:3 weigh the red of 4g bloodstone materials
Powder and weigh 6g La-Ce-Pr carbonate；First, 6g La-Ce-Pr carbonate is added in 50mL deionized water, uses magnetic force
Agitator stirs the deionized water solution and forms white suspension；It is slow suspended to the white under conditions of being kept stirring for
The dust technology that concentration is 0.5mol/L is added dropwise in liquid, until white suspended things are just completely dissolved, that is, first solution is formed.
Then the red powder of 4g bloodstone materials is added in first solution, treats that first solution is stirred 30min left
Suspension is formed behind the right side again；The suspension is evaporated at 200 DEG C, red block is formed, then by the block at 750 DEG C
Lower sintering 2h；Finally, the product of sintering is cooled down and obtains powdered second composite after being fully ground.Due to lanthanum
Cerium praseodymium carbonate is La-Ce-Pr oxide by the product of high temperature sintering, therefore second composite formed is LW-
LCP, wherein, LCP is writing a Chinese character in simplified form for La-Ce-Pr.
Subsequently, cathode material and anode material are prepared：It is lithium that 0.4g nickel cobalt aluminium is added according to every milliliter of alcoholic solution
Thing powder first proportioning, weigh 4g nickel cobalt aluminium lithium oxide powders be added to 10mL containing 10% volume fraction glycerine alcohol it is molten
In liquid, black slurry is obtained after stirring the alcoholic solution；The black slurry is coated to a kind of bubble of three dimensional network structure
Foam nickel surface, and the nickel foam after coating is dried at 300 DEG C, electroless matter fuel electricity is used as with the reticulated foam nickel of drying
The electrode in pond, i.e. NCAL-Ni electrodes.
Finally, second composite of above-mentioned preparation and electrode material are pressed into by ceramics using layering dry pressing
Piece, forms the fuel cell of " NCAL-Ni electrodes/composite bloodstone LW-LCP/NCAL-Ni electrodes " symmetrical structure, i.e., one
The electroless matter fuel cell that semiconductor ion conductor composite makes is planted, wherein, the sintering temperature of the potsherd is 700
℃。
The fuel cell that present inventor prepares to above-mentioned three kinds of methods is put under the atmosphere of hydrogen or air
Electrically operated, operating temperature range is 500-600 DEG C, and tests the open-circuit voltage of the fuel cell and short using electronic load instrument
Road electric current, after tested：
The fuel cell of first method manufacture obtains 0.94V open-circuit voltage and 225mW cm at 600 DEG C-2Work(
Rate density；
The fuel cell of second method manufacture obtains 0.99V open-circuit voltage and 467mW cm at 600 DEG C-2Work(
Rate density；
The fuel cell of the third method manufacture obtains 1.02V open-circuit voltage and 405mW cm at 600 DEG C-2Work(
Rate density；
It can be seen that, fuel cell prepared by above-mentioned three kinds of methods is respectively provided with that operating temperature is low, performance is good, and cost is low, electrical conductivity
High advantage.
Further, in order to from principle verify the application provide fuel cell and fuel cell preparation method it is beneficial
Effect, present inventor has done following test：
Fig. 2 is the X-ray diffractogram with the bloodstone material of the present invention, can be observed respectively in figure real
The bloodstone Fe for the hexagonal crystal system that heart rhombus is represented2O3, the hollow circular hexagonal crystal system represented quartzy SiO2And open triangles
The spurrite Ca that shape is represented2SiO4-CaCO3Corresponding diffractive features peak, it is a kind of to show the natural bloodstone material
The mixture of bloodstone, quartz and grey ferro-silicon-calcium.
Fig. 3 is the X-ray diffractogram of the first composite L W-LSCF, and the first composite described in figure drives
Diffraction maximum can be attributed to mineral and LSCF diffractive features peak, show bloodstone material with lanthanum-strontium cobalt iron oxide at them
Coexisted in the composite formed, obvious interaction does not occur therebetween.
Fig. 4, Fig. 5, Fig. 6 are respectively the bloodstone material, first composite and described in the present invention
The electrical conductivity situation of two composites.Wherein, black triangle represents hydrogen or air conditionses；Solid circles represent air bar
Part；Solid squares in Fig. 4 indicate that the solid squares in no ionic conduction condition, Fig. 5 and Fig. 6 represent I-V curve calculated value.Root
There is up to 0.07S cm in hydrogen or air atmosphere according to the visible bloodstone materials of Fig. 4-1Electrical conductivity (500-600 DEG C),
But its electronic conductivity but only has 0.01-0.02S cm-1, illustrate insulator SiO2Presence significantly reduce Fe2O3's
Electronic conductivity；The first composite L W-LSCF in Fig. 5 also shows excellent conductance in hydrogen or air atmosphere
Rate 0.12-0.15S cm-1, because the ionic conductivity of electronic conductor LSCF presence, therefore first composite is compared
Compared with being reduced for minal material, but its electronic conductivity is comparatively speaking but greatly improved, and has reached 0.12S intersection point
The process of electric charge transmission has been reacted, the bulk resistance Rb=0.9 Ω of material are can obtain；Second composite L W- described in Fig. 6
LCP shows 0.17-0.19S cm in identical hydrogen or air atmosphere-1High conductivity, by being tested with air atmosphere
Result compare, it is possible to find obtain certain proton conductivity in second composite, this kind of proton conduction phenomenon
Equally also it can be observed in figures 4 and 5.This is due to the semiconductor Fe in mineral material2O3With insulator SiO2Between boundary
Face mechanism, and there is provided special O for the compound action of carbonate2-And H+Transmission channel.
Fig. 7 is the electrochemical impedance spectroscopy of the bloodstone testing of materials in the present invention, and Range of measuring temp is 400-600
℃.It can be observed by Fig. 7, in the atmosphere of hydrogen or air, bloodstone material Impedance measurement in whole temperature range
Spectrogram is the semicircle of a flattening, and the change of its bulk resistor is not obvious, as the rise of temperature by 0.91 Ω is reduced to 0.80 Ω, hinders
Anti- spectrum is about 0.07S cm in front end and real axis total conductivity-1.Meanwhile, also reflect the bloodstone material to anode-side H2
Oxidation reaction and cathode side O2Reduction reaction have preferable catalytic effect.
Fig. 8 is the electrochemical impedance spectroscopy that the first composite L W-LSCF is tested under air atmosphere and different temperatures
Figure.As seen from Figure 8, in atmosphere, the bulk resistor change of first composite is not obvious, as the rise of temperature is by 1.15
Ω reduces 1.06 Ω, but the grain boundary resistance that the diameter of the semi arch of material is reflected then there occurs obvious change, by 14
Ω is reduced to 3 Ω.
Fig. 9 is the electrochemistry that the first composite L W-LSCF is tested under hydrogen or air atmosphere and different temperatures
Impedance spectra, and the corresponding equivalent circuit diagram in the upper right corner.From Fig. 9 middle impedances spectrum in front end and the intersection point of real axis, institute
The bulk resistor of the first composite is stated as the rise of temperature by 1.39 Ω reduces 0.78 Ω, can calculate obtain its electrical conductivity from
0.084S cm at 400 DEG C-10.15S cm when increasing to 600 DEG C-1, it is consistent with the result of the probe test of direct current four；Its
Impedance spectrum has reacted the grain boundary resistance of material in the intersection point of low frequency end and real axis, as the rise of temperature from 9.0 Ω is reduced to 2.9
Ω。
Figure 10 is to use the bloodstone materials application in the present invention in I-V the and I-P curves of three part fuel cells, can
See, the fuel cell obtains 0.94V open-circuit voltage and 225mW cm under 600 DEG C of operation temperature-2Power density.
Figure 11 be with heretofore described first composite L W-LSCF prepare electroless matter fuel cell I-V with
I-P curves, as its open-circuit voltage of the rise of operation temperature is from 0.89V liftings to 0.99V, its power output is also increased simultaneously
Maximum 467mW cm are reached at 600 DEG C-2。
Figure 12 be with heretofore described second composite L W-LCP, preparation electroless matter fuel cell I-V and
I-P curves, 1.02V open-circuit voltage and 405mW cm is obtained at 600 DEG C-2Power output.
From above-mentioned test chart, fuel cell prepared by the method that the application is provided has that operating temperature is low, performance is good,
Cost is low, the high advantage of electrical conductivity.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
1st, the embodiment of the present application is provided fuel cell and the preparation method of fuel cell, using bloodstone material in
Interbed basic material, and bloodstone is nature mineral matter, there is abundant reserves in China, it is with low cost, and due to the pit wood
It is that crude sedimentation is formed, its main component semiconductor Fe2O3With insulator SiO2Between Interface Mechanism, and carbonate answers
Cooperation use, create its excellent ionic conductivity, the temperature of fuel cell made using bloodstone is low, performance more
Good, cost is low, and electrical conductivity is high, effectively promotes the business application of fuel cell.
2nd, the embodiment of the present application provide fuel cell and fuel cell preparation method, using the bloodstone material with
First composite of lanthanum-strontium cobalt iron oxide formation is applied to show after fuel cell excellent low as intermediate layer material
Warm service behaviour；Can as intermediate layer material using the second composite of the bloodstone material and the formation of La-Ce-Pr oxide
The higher battery open circuit voltage of acquisition and power output.The synthesis technique of two kinds of composites is simple and quick, with low cost, institute's group
The fuel battery performance of dress is excellent, and a new direction is provided for the development of low-temperature fuel cell technology.
3rd, the embodiment of the present application is provided fuel cell and the preparation method of fuel cell, using the bloodstone and two kinds
Composite embodies proton conductivity as intermediate layer material, and the bloodstone is applied to the nature of its raw material
Fuel cell can play good ion transmitting effect, and fuel is applied to by the two kinds of composites formed after modification
Battery obtains more excellent battery performance.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.So, if these modifications and variations of the present invention belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising including these changes and modification.
Claims (10)
1. a kind of fuel cell, it is characterised in that negative electrode, anode and the intermediate layer of the fuel cell are pressed into potsherd；
The intermediate layer is located between the negative electrode and the anode；
Wherein, the intermediate layer uses material, composition and weight that the bloodstone material includes based on bloodstone material
Percentage is：Fe2O3More than 60%, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%.
2. fuel cell as claimed in claim 1, it is characterised in that the intermediate layer is specially：
The bloodstone material；Or
The bloodstone material and the first composite of lanthanum-strontium cobalt iron oxide formation；Or
The bloodstone material and the second composite of La-Ce-Pr oxide formation.
3. fuel cell as claimed in claim 2, it is characterised in that：
When the intermediate layer is the bloodstone material, the negative electrode is that the bloodstone material is pressed with lanthanum-strontium cobalt iron oxide
1:Mixture prepared by 1 volume ratio；The anode is that the bloodstone material presses 1 with nickel cobalt aluminium oxidate for lithium:1 volume ratio
The mixture of preparation；
When the intermediate layer is first composite, the negative electrode and the anode are nickel cobalt aluminium oxidate for lithium and bubble
The electrode material of foam nickel formation；
When the intermediate layer is second composite, the negative electrode and the anode are nickel cobalt aluminium oxidate for lithium and bubble
The electrode material of foam nickel formation.
4. a kind of preparation method of fuel cell, it is characterised in that methods described includes：
It is powdered to grind bloodstone material, and the composition and percentage by weight that the bloodstone material includes are：Fe2O3It is more than
60%th, SiO2More than 15%, CaSiO4And CaCO3Total amount be more than 5%；
Intermediate layer material is prepared with material based on the powdered bloodstone material；
Cathode material, anode material and the intermediate layer material are pressed into potsherd；The intermediate layer material is located at described the moon
Between pole material and the anode material.
5. method as claimed in claim 4, it is characterised in that described to prepare intermediate layer with the powdered bloodstone material
Material, be specially：
The intermediate layer material is used as using the powdered bloodstone material；Or
By the first mass bloodstone material more powdered than mixed grinding and lanthanum-strontium cobalt iron oxide the first mixture of formation；
First mixture is sintered into the first duration at the first temperature；First mixture after grinding and sintering obtains first and answered
Condensation material；The intermediate layer material is used as using first composite；Or
The powdered bloodstone material and La-Ce-Pr carbonate is weighed by the second mass ratio；By the La-Ce-Pr carbon weighed
Hydrochlorate is added in deionized water；The deionized water formation suspension is stirred, and dust technology is added into the suspension, so that
Suspended things dissolving in the suspension, forms the first solution；The bloodstone material weighed is added into first solution
In；First solution is stirred for suspended shape；First solution is evaporated, block is formed；Described piece is sintered at the second temperature
The duration of body second；After the block after cooling sintering, it is the second powdered composite to grind the block；With described
Second composite is used as the intermediate layer material.
6. method as claimed in claim 5, it is characterised in that first mass ratio is 13:7；First temperature is 700
℃；A length of 2 hours when described first.
7. method as claimed in claim 5, it is characterised in that second mass ratio is 2:3；The concentration of the dust technology is
0.5mol/L；The second temperature is 750 DEG C；A length of 2 hours when described second.
8. method as claimed in claim 5, it is characterised in that when the intermediate layer material is the powdered bloodstone material
During material：
The preparation method of the cathode material is：By 1:1 volume ratio, mix and abrasive flour shape the bloodstone material and
Lanthanum-strontium cobalt iron oxide, forms the cathode material；
The preparation method of the anode material is：By 1:1 volume ratio, mix and abrasive flour shape the bloodstone material and
Nickel cobalt aluminium oxidate for lithium, forms the anode material.
9. method as claimed in claim 5, it is characterised in that when the intermediate layer material is first composite or institute
When stating the second composite：
The preparation method of the cathode material and the anode material is：Nickel cobalt aluminium lithium oxide powder is added by the first proportioning
Enter into glycerinated alcoholic solution, stir the alcoholic solution and obtain black slurry；The black slurry is coated to foam
Nickel surface, and drying is coated with the nickel foam of the black slurry at a temperature of the 3rd；Institute is used as using the nickel foam of drying
State cathode material and the anode material.
10. method as claimed in claim 9, it is characterised in that first proportioning adds for every milliliter of alcoholic solution
0.4g nickel cobalt aluminium lithium oxide powders；The alcoholic solution contains the glycerine of 10% volume fraction；3rd temperature is 300
℃。
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| CN107768690B (en) * | 2017-08-29 | 2021-05-07 | 湖北大学 | Semiconductor film electrolyte type fuel cell and its making method |
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| CN101320814B (en) * | 2008-06-25 | 2012-08-29 | 施秀英 | Electrolyte material of low temperature oxide fuel battery and preparation method thereof |
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