CN110391426A - A method of improving cathode of solid oxide fuel cell long-time stability - Google Patents

A method of improving cathode of solid oxide fuel cell long-time stability Download PDF

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CN110391426A
CN110391426A CN201910694317.2A CN201910694317A CN110391426A CN 110391426 A CN110391426 A CN 110391426A CN 201910694317 A CN201910694317 A CN 201910694317A CN 110391426 A CN110391426 A CN 110391426A
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lscf
cathode
solid oxide
oxide fuel
fuel cell
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熊岳平
李栋
金英敏
刘超军
宗鑫
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • 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
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    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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 a kind of methods for improving cathode of solid oxide fuel cell long-time stability, belong to field of solid oxide fuel.The invention solves solid oxide fuel cell cathode performance is gradually decayed during long-term work the problem of.The method of the present invention: LSCF nano material being uniformly mixed with carbon nano-fiber powder, the terpineol solution of ethyl cellulose is added, and is uniformly mixed and is added dehydrated alcohol, magnetic agitation is uniform, obtains cathode slurry；Then cathode slurry is coated on GDC electrolyte sheet using silk screen print method, is sintered to get LSCF cathode skeleton is arrived；Then GDC nitrate solution is impregnated on LSCF cathode skeleton, is then dried, and is sintered, is obtained LSCF-GDC composite cathode.More good long-time stability are shown using LSCF-GDC composite cathode prepared by the method.Present invention is mainly applied to solid oxide fuel cell.

Description

A method of improving cathode of solid oxide fuel cell long-time stability
Technical field
The invention belongs to the technical fields of solid oxide fuel cell；More particularly to a kind of raising solid oxide fuel The method of cell cathode long-time stability.
Background technique
Solid oxide fuel cell is a kind of efficient energy conversion device, does not follow Carnot cycle, can by hydrogen, Chemical energy in natural gas, hydrocarbon compound is converted into electric energy, and energy utilization efficiency is up to 60%, has fuel multiplicity Change, environmental-friendly, features simple structure the advantages that.Wherein cathode is the important component of solid oxide fuel cell, is to occur The important place of oxygen reduction reaction.During cathode reaction, extraneous oxygen enters cathode and absorption dissociation, Zhi Hou first occurs Three phase boundary (O2Cathode-electrolyte) receive electronics generation oxygen reduction reaction generation negative oxygen ion, last negative oxygen ion is through yin Pole, electrolyte conducts reach anode side and participate in anode reaction.In solid oxide fuel cell, air electrode polarization resistance Anti- accounting electrode polarization impedance is up to 70%.The decaying of cathode performance at present is that influence solid oxide fuel cell is commercialized One of key factor.The factor for causing cathode performance to be decayed include but is not limited to mutual between material reunite, the segregation of element, Reacting to each other between material, pollutant etc..
Summary of the invention
The problem of decaying the invention solves cathode performance during existing SOFC long-term work；And provide one kind The method for improving cathode of solid oxide fuel cell long-time stability.
In order to solve the above-mentioned technical problem, the side of cathode of solid oxide fuel cell long-time stability is improved in the present invention Method is realized by following step:
Step 1: LSCF nano material is uniformly mixed with carbon nano-fiber powder, the terpinol of ethyl cellulose is added Solution is uniformly mixed and adds dehydrated alcohol, and magnetic agitation is uniform, obtains cathode slurry；
Step 2: being coated on GDC electrolyte sheet using the cathode slurry that silk screen print method obtains step 1, using fast Fast sintering process is sintered to arrive LSCF cathode skeleton；
Step 3: impregnating GDC nitrate solution on the LSCF cathode skeleton that step 2 obtains, then dry, is sintered, i.e., Obtain LSCF-GDC composite cathode.
It further limits, LSCF nano material described in step 1 is LSCF nanofiber or LSCF nano particle, LSCF The mass ratio of nano material and carbon fiber powder is 1:(20~10).
Above-mentioned LSCF nanofiber can be prepared by method of electrostatic spinning, specifically be carried out in the steps below:
Step 1: weighing lanthanum nitrate, strontium nitrate, cobalt nitrate, ferric nitrate according to the ratio of molar ratio 8:2:2:8, be then added Into n,N dimethylformamide, magnetic agitation adds polyvinylpyrrolidone (PVP), magnetic agitation is extremely to being completely dissolved PVP is completely dissolved, and obtains the electrostatic spinning liquid in sticky, transparent state, wherein the quality of inorganic salts in electrostatic spinning liquid Score is 15%~25%, and the mass fraction of polyvinylpyrrolidone is 8%~10%；
Step 2: step 1 acquisition electrostatic spinning liquid being injected into medical plastic syringe, syringe needle is that polish No. 8 are stainless Syringe is fixed as a row using copper wire by steel needle head, and using nickel screen as acceptor, carries out electrostatic spinning, the item of electrostatic spinning Part are as follows: humidity 20%~30%, 25 DEG C~30 DEG C of temperature, voltage 15kV~20kV, the reception distance 15cm between syringe needle and nickel screen ~20cm；
Step 3: the resulting non-woven fabrics of electrostatic spinning is dried in 80 DEG C~100 DEG C air dry ovens, postposition In Muffle furnace, 300 DEG C, constant temperature 2h are warming up to the heating rate of 2~5 DEG C/min, later with the heating speed of 2~5 DEG C/min Degree is warming up to 800 DEG C~900 DEG C, constant temperature 2h, after cooled to room temperature, obtains LSCF nanofiber.
LSCF nano particle will be obtained after the LSCF nanofiber ball milling of above method preparation, specific method is: by LSCF Nanofiber is mixed with zirconia ball and is placed in ball grinder, using dehydrated alcohol as dispersing agent, ball milling 3h in the ball mill, finally Suspension after ball milling is placed in air dry oven and is dried to get LSCF nano particle is arrived.
It further limits, the mass percentage of the terpineol solution of ethyl cellulose is 3%~5% in step 1； The mass ratio of the terpineol solution of LSCF nano material powder and ethyl cellulose is 6:4.
It further limits, sintering process is as follows in step 2: being warming up to 800 with 10 DEG C/min~15 DEG C/min rate DEG C~900 DEG C, it is down to room temperature naturally after keeping the temperature 1min~5min.
It further limits, the operation of silk screen print method described in step 2 is as follows: with punch in Scotch adhesive tape Circular hole is got in centre, is then covered on GDC electrolyte sheet and makes the center of circle of hole and the central point weight of GDC electrolyte sheet Close, cathode slurry be coated at electrolyte center, is struck off with scraper plate, it is to be coated on slurry it is slightly dry after throw off adhesive tape.
Further limit, sintering process is as follows in step 3: with the heating rate of 2~5 DEG C/min be warming up to 750 DEG C~ 800 DEG C, constant temperature 1h~2h is down to room temperature naturally later.
It further limits, GDC nitrate solution configures in the steps below in step 3: by cerous nitrate and gadolinium nitrate It is dissolved in the mixed solution of deionized water and dehydrated alcohol, glycine is added until completely dissolved, be uniformly mixed and obtain GDC nitre Acid salt solution, wherein the molar ratio of cerous nitrate and gadolinium nitrate is 8:2, and the volume ratio of deionized water and dehydrated alcohol is 4:3, Ce4+ Concentration be 0.15mol/L~0.20mol/L, the concentration of glycine is 0.3mol/L~0.4mol/L.
The present invention is to effectively improve the hole of composite cathode by the way that carbon fiber is added in cathode slurry as pore creating material Gap rate, and then improve the best LSCF/GDC mass ratio of LSCF-GDC composite cathode under each microscopic appearance.Best LSCF/GDC On the one hand the raising of mass ratio increases the three phase boundary of LSCF-GDC composite cathode, on the other hand make the compound yin of LSCF-GDC LSCF intracell is by a greater degree of compression in the course of work of pole, to effectively improve LSCF-GDC composite cathode Long-time stability.
The method of the present invention is easy to operate.
More good long-time stability are shown using LSCF-GDC composite cathode prepared by the method for the present invention, through pore-creating Nanofiber LSCF-GDC composite cathode afterwards is in 100mA/cm2Constant current polarizes during 144h, rate of decay 0.08mV/ H is shown relative to the nanofiber LSCF-GDC composite cathode (rate of decay is 0.3mV/h in polarization process) of non-pore-creating More good long-time stability.
Detailed description of the invention
Fig. 1 is the SEM figure of the nanofiber in embodiment 1 using method of electrostatic spinning preparation；
Fig. 2 is the ac impedance spectroscopy that the nanofibrous structures LSCF-GDC composite cathode of pore creating material is not added in embodiment 1；
Fig. 3 is the ac impedance spectroscopy that the nanofibrous structures LSCF-GDC composite cathode of pore creating material is added in embodiment 1；
Fig. 4 is multiple for the nanofibrous structures LSCF-GDC for being not added with pore creating material in 750 DEG C of constant current polarization process in embodiment 1 Close the U-t curve of cathode；
Fig. 5 is that the nanofibrous structures LSCF-GDC of addition pore creating material in 750 DEG C of constant current polarization process in embodiment 1 is compound The U-t curve of cathode；
Fig. 6 is the compound yin of nanofibrous structures LSCF-GDC for being not added with pore creating material in embodiment 1 and adding pore creating material The EDS of pole schemes, and wherein a is the EDS being not added with before the nanofibrous structures LSCF-GDC composite cathode polarization of pore creating material, and b is not EDS after adding the nanofibrous structures LSCF-GDC composite cathode polarization of pore creating material, c are the nanofiber knot for adding pore creating material EDS before the polarization of structure LSCF-GDC composite cathode, d are the nanofibrous structures LSCF-GDC composite cathode polarization for adding pore creating material EDS afterwards；
Fig. 7 is the ac impedance spectroscopy that the nanoparticle structure LSCF-GDC composite cathode of pore creating material is not added in embodiment 2；
Fig. 8 is the ac impedance spectroscopy that the nanoparticle structure LSCF-GDC composite cathode of pore creating material is added in embodiment 2；
Fig. 9 is multiple for the nanoparticle structure LSCF-GDC for being not added with pore creating material in 750 DEG C of constant current polarization process in embodiment 2 Close the U-t curve of cathode；
Figure 10 is that the nanoparticle structure LSCF-GDC of addition pore creating material in 750 DEG C of constant current polarization process in embodiment 2 is multiple Close the U-t curve of cathode.
Specific embodiment
Embodiment 1: the La that the present embodiment uses0.8Sr0.2Co0.2Fe0.8O3-δ(LSCF) nanofiber can pass through electrostatic spinning Method preparation, specifically carry out in the steps below:
Step 1: by 2.6937g lanthanum nitrate, 0.3292g strontium nitrate, 0.4527g cobalt nitrate, 2.5129g ferric nitrate, then It being added in 30mL n,N dimethylformamide, magnetic agitation adds 3.0g polyvinylpyrrolidone (PVP) to being completely dissolved, Magnetic agitation is completely dissolved to PVP, obtains the electrostatic spinning liquid in sticky, transparent state；
Step 2: step 1 acquisition electrostatic spinning liquid being injected into the medical plastic syringe of 5mL, syringe needle is 8 polished Number stainless steel syringe needle, is fixed as a row for syringe using copper wire, and using nickel screen as acceptor, carries out electrostatic spinning, Static Spinning The condition of silk are as follows: humidity 30%, temperature are 25 DEG C, voltage 20kV, and the reception distance between syringe needle and nickel screen is 18cm；
Step 3: 8h is dried in 80 DEG C of air dry ovens in the resulting non-woven fabrics of electrostatic spinning, be placed on Muffle In furnace, 300 DEG C are warming up to the heating rate of 2 DEG C/min, constant temperature 2h is warming up to 900 later with the heating rate of 2 DEG C/min DEG C, constant temperature 2h after cooled to room temperature, obtains LSCF nanofiber, and SEM figure is as shown in Figure 1, it will thus be seen that LSCF material Material shows as apparent fibre structure, and fibre diameter is in 280nm or so, and nanometer rods are evenly distributed, soap-free emulsion polymeization phenomenon.
The method of cathode of solid oxide fuel cell long-time stability is improved in this implementation to be realized by following step :
Step 1: 0.1283gLSCF nanofiber is uniformly mixed with 0.0093g carbon nano-fiber powder, it is added The terpineol solution for the ethyl cellulose that 0.0824g mass percentage is 3% is uniformly mixed and adds the anhydrous second of 0.3347g Alcohol, magnetic agitation 8h obtain uniform, sticky cathode slurry；
Step 2: being coated using silk screen print method, the Scotch glue that the punch for being 10mm with diameter is produced in 3M company The circular hole that diameter is 10mm is got with centre, is then covered on GDC electrolyte disk and makes the center of circle and the GDC of hole (Gd0.2Ce0.8O1.9) electrolyte sheet centre point be overlapped, cathode slurry is coated at electrolyte center, is struck off with scraper plate, it is to be coated Adhesive tape is thrown off after the slurry being covered with is slightly dry, 900 DEG C is warming up to the rate of 10 DEG C/min, keeps the temperature 1min, i.e., in GDC electrolyte circle On piece obtains the LSCF cathode skeleton that diameter is 10mm；
Matched Step 3: being dissolved in 6.078g cerous nitrate and 1.579g gadolinium nitrate by 40mL deionized water and 30mL dehydrated alcohol In the mixed solution set, 1.9706g glycine is added until completely dissolved, is uniformly mixed and obtains GDC (Gd0.2Ce0.8O1.9) nitre Acid salt solution, then being dripped GDC nitrate solution using micro syringe makes it on the LSCF cathode skeleton that step 2 obtains Infiltration is put into air dry oven dries later to cathode skeletal internal, then in Muffle furnace 800 DEG C of sintering 1h to get arriving LSCF-GDC composite cathode.
Using following experimental verification invention effects:
In the present embodiment prepared by monocell: platinum cream is coated on to the other side of GDC electrolyte using silk screen print method, and with The heating rate of 5 DEG C/min is warming up to 1000 DEG C of constant temperature 1h；The platinum filament that diameter is 0.3mm is wrapped in GDC electrolyte sheet edge, And enclosed with platinum slurry coating one, 1000 DEG C of constant temperature 1h are warming up to the heating rate of 5 DEG C/min.
Monocell prepared by the above method is placed in tube furnace, is tested using CHI650D electrochemical workstation different Polarization impedance of the LSCF-GDC composite cathode of LSCF/GDC mass ratio under the conditions of 750 DEG C, polarization impedance are composed such as Fig. 2,3 institutes Show.It can be seen that the LSCF-GDC composite cathode for being not added with carbon fiber pore creating material is reached when LSCF/GDC mass ratio is 1:0.76 To Minimum Polarization impedance；The LSCF-GDC composite cathode for adding carbon fiber pore creating material is reached when LSCF/GDC mass ratio is 1:1.01 To Minimum Polarization impedance.The corresponding polarization impedance of the two is respectively 0.06 Ω cm2With 0.045 Ω cm2。
Long term stability tests: using Corrtest electrochemical workstation to the LSCF-GDC composite cathode of addition pore creating material (under the conditions of best LSCF/GDC mass ratio) applies current density 100mA/cm2Constant current polarization, polarization time 144h, test The U-t curve of composite cathode in polarization process.Group as a comparison, similarly test is not added with the compound yin of LSCF-GDC of pore creating material U-t curve in pole (under the conditions of best LSCF/GDC mass ratio) polarization process, as shown in Figure 4,5.It can be seen that addition pore-creating The LSCF-GDC composite cathode of agent has slower rate of decay relative to the composite cathode for being not added with pore creating material, and the two declines The rate of deceleration is respectively 0.08mV/h and 0.3mV/h, illustrates that the addition of pore creating material effectively improves LSCF-GDC composite cathode Long-time stability.EDS power spectrum characterization is carried out to the LSCF-GDC composite cathode of polarization front and back, the results showed that be not added with pore creating material LSCF-GDC composite cathode shows the Sr element segregation of higher degree after constant current polarizes, as shown in Figure 6.
Embodiment 2: the present embodiment place different from embodiment 1 is: replacing LSCF nanometers using LSCF nano particle Fiber.LSCF nanometer grain preparation method is that the LSCF nanofiber of 1 method of embodiment preparation and zirconia ball are placed in ball milling In tank, using ethyl alcohol as dispersing agent, ball milling 3h is carried out in high energy ball mill, is dried to obtain later in air dry oven LSCF nano particle.Other steps and parameter are same as Example 1.
The test method of the present embodiment is same as Example 1.Fig. 7 is non-pore-creating under the conditions of different LSCF/GDC mass ratioes The polarization impedance of nano particle LSCF-GDC composite cathode is composed, and pore creating material is added under the conditions of Fig. 8 difference LSCF/GDC mass ratio The polarization impedance of nano particle LSCF-GDC composite cathode is composed.As can be seen that the former is when LSCF/GDC mass ratio is 1:0.18 Reach 0.12 Ω cm of Minimum Polarization impedance2, the latter LSCF/GDC mass ratio be 1:0.61 when reach Minimum Polarization impedance 0.08 Ωcm2。
Fig. 9,10 are respectively non-pore-creating, addition pore creating material nano particle LSCF-GDC composite cathode (optimum quality ratio Under the conditions of) U-t curve in constant current polarization process.As can be seen that the latter has more good long-time stability.The two declines The rate of deceleration is respectively 1.71mV/h and 0.31mV/h.Illustrate that the addition of pore creating material can effectively promote LSCF-GDC composite cathode Long-time stability.

Claims (10)

1. a kind of method for improving cathode of solid oxide fuel cell long-time stability, it is characterised in that the raising solid oxygen The method of compound fuel battery negative pole long-time stability is realized by following step:
Step 1: LSCF nano material is uniformly mixed with carbon nano-fiber powder, the terpineol solution of ethyl cellulose is added, It is uniformly mixed and adds dehydrated alcohol, magnetic agitation is uniform, obtains cathode slurry；
Step 2: being coated on GDC electrolyte sheet using the cathode slurry that silk screen print method obtains step 1, burnt using quick Connection is sintered to arrive LSCF cathode skeleton；
Step 3: impregnating GDC nitrate solution on the LSCF cathode skeleton that step 2 obtains, then dry, sintering is to get to admittedly Oxide body fuel battery negative pole.
2. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 1, special Sign is that LSCF nano material described in step 1 is LSCF nanofiber or LSCF nano particle, LSCF nano material and carbon fiber The mass ratio for tieing up powder is 1:(20~10).
3. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 2, special Sign is that LSCF nanofiber is prepared using method of electrostatic spinning, specifically carries out in the steps below:
Step 1: weighing lanthanum nitrate, strontium nitrate, cobalt nitrate, ferric nitrate according to the ratio of molar ratio 8:2:2:8, be then added to N, N In dimethylformamide, magnetic agitation adds polyvinylpyrrolidone (PVP) to being completely dissolved, and magnetic agitation is complete to PVP Dissolution obtains the electrostatic spinning liquid in sticky, transparent state, wherein the mass fraction of inorganic salts is in electrostatic spinning liquid 15%~25%, the mass fraction of polyvinylpyrrolidone is 8%~10%；
Step 2: step 1 acquisition electrostatic spinning liquid being injected into medical plastic syringe, syringe needle is No. 8 stainless pins polished Syringe is fixed as a row using copper wire by head, and using nickel screen as acceptor, carries out electrostatic spinning, the condition of electrostatic spinning are as follows: Humidity is 20%~30%, and temperature is 25 DEG C~30 DEG C, and voltage is 15kV~20kV, and the reception distance between syringe needle and nickel screen is 15cm~20cm；
Step 3: the resulting non-woven fabrics of electrostatic spinning is dried in 80 DEG C~100 DEG C air dry ovens, be placed on horse Not in furnace, 300 DEG C, constant temperature 2h are warming up to the heating rate of 2~5 DEG C/min, later with the heating rate liter of 2~5 DEG C/min Temperature after cooled to room temperature, obtains LSCF nanofiber to 800 DEG C~900 DEG C, constant temperature 2h.
4. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 2, special Sign be that LSCF nano particle is by following operation preparations: by claim 3 the method preparation LSCF nanofiber with Zirconia ball mixing is placed in ball grinder, and using dehydrated alcohol as dispersing agent, ball milling 3h in the ball mill finally will be after ball milling Suspension, which is placed in air dry oven, dries to get LSCF nano particle is arrived.
5. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 1, special Sign is that the mass percentage of the terpineol solution of ethyl cellulose in step 1 is 3%~5%.
6. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 5, special Sign is that the mass ratio of the terpineol solution of LSCF nano material powder and ethyl cellulose is 6:4.
7. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 1, special Sign is in step 2 that sintering process is as follows: being warming up to 800 DEG C~900 DEG C with 10 DEG C/min~15 DEG C/min rate, heat preservation Naturally room temperature is down to after 1min~5min.
8. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 1, special Sign is that the operation of silk screen print method described in step 2 is as follows: getting round hole among Scotch adhesive tape with punch Then hole is covered on GDC electrolyte sheet and makes the center of circle of hole and the central point of GDC electrolyte sheet to be overlapped, by cathode slurry Be coated at electrolyte center, struck off with scraper plate, it is to be coated on slurry it is slightly dry after throw off adhesive tape.
9. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 1, special Sign is in step 3 that sintering process is as follows: 750 DEG C~800 DEG C are warming up to the heating rate of 2~5 DEG C/min, constant temperature 1h~ 2h is down to room temperature naturally later.
10. a kind of method for improving cathode of solid oxide fuel cell long-time stability according to claim 1, special Sign be in step 3 that GDC nitrate solution configures in the steps below: by cerous nitrate and gadolinium nitrate be dissolved in deionized water and In the mixed solution of dehydrated alcohol, glycine is added until completely dissolved, is uniformly mixed and obtains GDC nitrate solution, wherein The molar ratio of cerous nitrate and gadolinium nitrate is 8:2, and the volume ratio of deionized water and dehydrated alcohol is 4:3, Ce4+Concentration be 0.15mol/L~0.20mol/L, the concentration of glycine are 0.3mol/L~0.4mol/L.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768737A (en) * 2021-01-20 2021-05-07 中国科学院上海应用物理研究所 Preparation method of ultrathin dense electrolyte of solid oxide battery and ultrathin dense electrolyte obtained by preparation method
CN113363505A (en) * 2021-05-28 2021-09-07 山东工业陶瓷研究设计院有限公司 LSCF-GDC core-shell structure cathode and preparation method thereof
CN116960420A (en) * 2023-07-05 2023-10-27 中国矿业大学 Preparation method of reversible solid oxide battery with double-layer straight hole structure

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768737A (en) * 2021-01-20 2021-05-07 中国科学院上海应用物理研究所 Preparation method of ultrathin dense electrolyte of solid oxide battery and ultrathin dense electrolyte obtained by preparation method
CN112768737B (en) * 2021-01-20 2022-06-21 中国科学院上海应用物理研究所 Preparation method of ultrathin dense electrolyte of solid oxide battery and ultrathin dense electrolyte obtained by preparation method
CN113363505A (en) * 2021-05-28 2021-09-07 山东工业陶瓷研究设计院有限公司 LSCF-GDC core-shell structure cathode and preparation method thereof
CN116960420A (en) * 2023-07-05 2023-10-27 中国矿业大学 Preparation method of reversible solid oxide battery with double-layer straight hole structure
CN116960420B (en) * 2023-07-05 2024-02-06 中国矿业大学 Preparation method of reversible solid oxide battery with double-layer straight hole structure

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