CN103050724A - Single-cell structure of fuel cell and preparation method thereof - Google Patents
Single-cell structure of fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN103050724A CN103050724A CN2013100291271A CN201310029127A CN103050724A CN 103050724 A CN103050724 A CN 103050724A CN 2013100291271 A CN2013100291271 A CN 2013100291271A CN 201310029127 A CN201310029127 A CN 201310029127A CN 103050724 A CN103050724 A CN 103050724A
- Authority
- CN
- China
- Prior art keywords
- cell
- fuel
- curtain coating
- cell structure
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000446 fuel Substances 0.000 title abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 238000007766 curtain coating Methods 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 8
- 238000010345 tape casting Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 51
- 238000009938 salting Methods 0.000 claims description 46
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 35
- 239000011159 matrix material Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000006424 Flood reaction Methods 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000021323 fish oil Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 stir 1h Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002803 maceration Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 238000010344 co-firing Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 238000000462 isostatic pressing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
Abstract
The invention discloses a single-cell structure of a fuel cell with high structure strength and high electric conductivity, and a preparation method of the single-cell structure of the fuel cell. The single-cell structure of the fuel cell disclosed by the invention is composed of three layers of laminated curtain coating zirconium oxide substrates; the curtain coating substrates at two sides of the single-cell structure have porous structures; the middle curtain coating substrate is used as an electrolyte layer; anode metal salt solution and cathode metal salt solution are respectively dipped into the porous structures of the curtain coating substrates at two sides of the single-cell structure; the single-cell structure of the fuel cell is formed by the following steps of taking zirconium oxide as raw materials, molding and preparing two layers of curtain coating substrates as the electrodes and a layer of electrolyte layer by a tape casting method, and then conducting isostatic pressing on the three layers of curtain coating substrates so as to form a green body with a composite structure so as; then conducting high-temperature co-firing, and dipping the anode metal salt solution and the cathode metal salt solution; baking at 500-1000 DEG C so as to finally form the single-cell structure of the fuel cell. The single-cell structure of the fuel cell can be applied to the technical field of the fuel cell.
Description
Technical field
The present invention relates to a kind of fuel cell, relate in particular to a kind of preparation method of single-cell structure and this single-cell structure of fuel cell.
Background technology
It is negative electrode that traditional Solid Oxide Fuel Cell all has three main parts, anode and the dielectric substrate that is clipped in the middle, and also it is referred to as one of reason of battery just for this.Solid Oxide Fuel Cell has strict requirement to the selection of electrode and electrolyte: sufficiently high electronic conductivity will be arranged (1) anode material so that the transporting and moving of electronics, to play to the electrochemical oxidation of fuel good catalytic action, micro-structural with porous is beneficial to transporting of fuel gas, to under the reducing atmosphere of anode working, keep stable, and with the electrolyte that is close to good thermal matching be arranged; (2) cathode material will have sufficiently high electronic conductivity so that the transporting and moving of electronics, to play to the electrochemical oxidation of oxygen good catalytic action, has the micro-structural of porous so that transporting of oxygen, to under the oxidizing atmosphere of negative electrode work, keep stable, and with the electrolyte that is close to good thermal matching be arranged; (3) the dielectric substrate material requirements has sufficiently high ionic conductivity, but requires simultaneously its electronic conductivity as far as possible low, stablize in the atmosphere of oxidation and reduction, has fine and close micro-structural, and has good thermal matching with adjacent electrode material.The different materials high temperature sintering is to obtaining together the structure of whole solid state Solid Oxide Fuel Cell, but the thermal coefficient of expansion between the adjacent materials does not mate, the phenomenon that electrode just easily alice occurs, comes off in preparation and hot operation process subsequently, this impact is even more serious for the electrode-supported hull cell, can cause the torsional deformation of battery even breaks.Therefore in the evolution of fuel cell, at selection material, regulate the material thermal expansion coefficient aspect and dropped into a large amount of energy, the long-term existence but this problem remains unchanged.The very high electrode material of a lot of electrocatalysis is arranged also since thermal coefficient of expansion do not mate and can not be widely adopted.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, a kind of structural strength is high, conductance is high fuel-cell single-cell structure and the preparation method of this fuel-cell single-cell structure are provided, the method is simple to operate, greatly shortened Production Time, improved operating efficiency, also provided cost savings.
The technical scheme that fuel-cell single-cell structure of the present invention adopts is: described fuel-cell single-cell structure is made of the curtain coating zirconium oxide substrate that three laminations are closing, the curtain coating substrate that wherein is positioned at both sides has loose structure, be positioned at the curtain coating substrate in centre position as dielectric substrate, be impregnated with respectively anode metal salting liquid and cathodic metal salting liquid at the loose structure of the described curtain coating substrate that is positioned at both sides.
The described curtain coating substrate that is positioned at both sides contains the ball-type graphite as pore creating material.
The thickness that is positioned at the described curtain coating substrate of both sides is 0.05～1.0mm.
The porosity that is positioned at the described curtain coating substrate of both sides is 20～60%.
The thickness that is positioned at the described curtain coating substrate in centre position is 0.05～0.5mm.
The described curtain coating substrate that is positioned at the centre position contains 0～8 mol% Y
2O
3, 0～20 mol% Gd
2O
3, 0～9 mol% Sc
2O
3, 0～3 mol% Ce
2O
3, the doping total amount is 2～30mol%.
The anode metal salting liquid that floods at the described curtain coating substrate that is positioned at both sides is the soluble-salt solution of nickel, and described cathodic metal salting liquid is dissolved in the solution that forms in the deionized water for nitrate or the solvable chloride of the lanthanum, strontium and the manganese that calculate according to the LSM mol ratio.
Described anode metal salting liquid is the salting liquid of nickel nitrate or nickel chloride or nickelous sulfate, and described cathodic metal salting liquid is the salting liquid of lanthanum nitrate, strontium nitrate and manganese nitrate.
The technical scheme that the preparation method of fuel-cell single-cell structure of the present invention adopts is that the method may further comprise the steps:
(1) preparation of anode and cathodic metal salting liquid: in the volumetric flask of deionized water is housed, add the soluble-salt of nickel, form until completely dissolved the anode metal salting liquid; In the volumetric flask of deionized water is housed, add nitrate or the solvable chloride of lanthanum, strontium and manganese, form until completely dissolved the cathodic metal salting liquid;
(2) preparation of curtain coating substrate: adopt the tape casting moulding to prepare the two-layer ball-type graphite that contains as curtain coating substrate and one deck laminar flow of electrolyte epitaxial substrate of pore creating material, cut out three laminar flow epitaxial substrates for subsequent use by the battery specification;
(3) green compact preparation: stacked good three laminar flow epitaxial substrates in the step (2), wherein the intermediate layer is the laminar flow of electrolyte epitaxial substrate, makes monocell matrix green compact by isostatic compaction;
(4) green compact are fired: the monocell green compact after the moulding are placed in the stove burn altogether, ignition temperature is 1200～1600 ℃, and temperature retention time 0.5～5h makes the fuel-cell single-cell matrix;
(5) the monocell matrix is detected: place the fuel-cell single-cell matrix fuchsin solution to detect, whether the dielectric substrate that mediates with detection has cracking, pore, if having, then is judged to be substandard products; Otherwise, be judged to be certified products;
(6) impregnation process: adopt impregnation method that anode that step (1) makes and cathodic metal salting liquid utilize the primary coat formula respectively anode and the negative electrode of the monocell matrix processed through step (5) to be carried out impregnation process, dipping once floods after drying again, through 5～10 dippings, finish impregnation process;
(7) baking is processed at last: the fuel-cell single-cell matrix of processing through step (6) is toasted, namely get the fuel-cell single-cell structure after the dried maceration extract to be baked.
Also comprise pinkish red Liquid Residue step in described step (5), this step is: after having finished pinkish red detection, the pinkish red Liquid Residue that will be attached in combustion furnace on the fuel-cell single-cell matrix dryouies.
The anode metal salting liquid that makes in the described step (1) and cathodic metal salting liquid are the solution of 1mol/L.
In the described step (2), when preparation is positioned at the curtain coating substrate of both sides, with base material zirconia powder and 0～10wt% dispersant, 3～20wt% binding agent, 1～15wt% plasticizer, deionized water mixing and ball milling proportionally, ball milling 24h forms discharging behind the stable slurry, the ball-type graphite that then will account for zirconia powder quality 15～40% joins in the slurry, stirs 1h, and slurry and ball-type graphite are mixed, then carry out the deaeration curtain coating, make needed zirconia curtain coating substrate.
In the described step (2), when preparation is positioned at middle dielectric substrate, 0～8mol% Y will mix
2O
3, 0～20mol% Gd
2O
3, 0～9mol% Sc
2O
3, 0～3mol% Ce
2O
3The doping total amount is proportionally mixing and ball milling of the zirconia powder of 2～30mol% and 0～10wt% dispersant, 3～20wt% binding agent, 1～15wt% plasticizer, deionized water, discharging deaeration curtain coating behind the ball milling 24h formation stable slurry, curtain coating thickness 0.05～0.5mm makes needed dielectric substrate.
In described step (3), the process of described isostatic compaction is: the three laminar flow epitaxial substrates that stack are inserted in the warm water pressurize 60s under the pressure of 5～50MPa.
Described dispersant is fish oil or castor oil or triethanolamine, and described binding agent is PVB, polyester or PVA, and described plasticizer is DBP, DOP, glycerine or polyethylene glycol.
Baking temperature in the described step (7) is set as 500～1000 ℃.
The invention has the beneficial effects as follows: because the curtain coating substrate as anode and negative electrode that is in both sides among the present invention all adopts the zirconia base material to make with the dielectric substrate that mediates, form the fuel cell matrix by high temperature co-firing three layers of zirconium oxide substrate are stacked, solved that the different materials coefficient of expansion does not mate and the warpage that occurs and the problem such as come off; Contain ball-type graphite at the curtain coating substrate as electrode that is positioned at both sides, this ball-type graphite is as pore creating material, the loose structure that forms in two electrodes can hold accumulate utmost point metal salt solution well, through overbaking rear catalyst and porous layer good adhesion is arranged, adopt simultaneously zirconia as base material, and zirconic intensity is higher, and this has improved the intensity of fuel cell largelyr; And the thickness of the dielectric substrate that mediates only has 0.05～0.5mm, and thinner dielectric substrate has greatly improved the guiding rate of battery, and its battery performance is also higher.
Because the preparation method of the fuel-cell single-cell structure among the present invention is in the preparation cell process, only need to prepare respectively three layers of zirconia curtain coating substrate, then cut out by the specification of battery, final layer stacks pressing and forming, flood respectively anode metal salting liquid and cathodic metal salting liquid being positioned on the curtain coating substrate as electrode of both sides, namely obtain the fuel-cell single-cell structure through being total to burning, so, the inventive method step is simple, simple to operate, can greatly shorten the operating time, and save a large amount of costs, also indirectly reduce simultaneously staff's labour intensity.
Description of drawings
Fig. 1 is the tangent plane structural representation of fuel-cell single-cell structure of the present invention.
Embodiment
As shown in Figure 1, the present invention is made of the curtain coating zirconium oxide substrate that three laminations are closing, the curtain coating substrate that wherein is positioned at both sides has loose structure, be positioned at the curtain coating substrate in centre position as dielectric substrate, be impregnated with respectively anode metal salting liquid and cathodic metal salting liquid at the loose structure of the described curtain coating substrate that is positioned at both sides.
The described curtain coating substrate that is positioned at both sides contains the ball-type graphite as pore creating material.The thickness that is positioned at the described curtain coating substrate of both sides is 0.05～1.0mm.The porosity that is positioned at the described curtain coating substrate of both sides is 20～60%.The thickness that is positioned at the described curtain coating substrate in intermediate layer is 0.05～0.5mm.This layer contains 0～8mol% Y
2O
3, 0～20mol% Gd
2O
3, 0～9mol% Sc
2O
3, 0～3mol% Ce
2O
3, the doping total amount is 2～30mol%.The anode metal salting liquid that floods at the described curtain coating substrate that is positioned at both sides is the soluble-salt solution of nickel, and described cathodic metal salting liquid is dissolved in the solution that forms in the deionized water for nitrate or the solvable chloride of the lanthanum, strontium and the manganese that calculate according to the LSM mol ratio.In the present embodiment, described anode metal salting liquid is the salting liquid of nickel nitrate or nickel chloride or nickelous sulfate, and described cathodic metal salting liquid is the salting liquid of lanthanum nitrate, strontium nitrate and manganese nitrate.
The preparation method of described fuel-cell single-cell structure may further comprise the steps:
(1) preparation of anode and cathodic metal salting liquid: in the volumetric flask of deionized water is housed, add the soluble-salt of nickel, form until completely dissolved the anode metal salting liquid; In the volumetric flask of deionized water is housed, add nitrate or the solvable chloride of lanthanum, strontium and manganese, form until completely dissolved the cathodic metal salting liquid;
(2) preparation of curtain coating substrate: adopt the tape casting moulding to prepare the two-layer ball-type graphite that contains as curtain coating substrate and one deck laminar flow of electrolyte epitaxial substrate of pore creating material, cut out three laminar flow epitaxial substrates for subsequent use by the battery specification;
(3) green compact preparation: stacked good three laminar flow epitaxial substrates in the step (2), wherein the intermediate layer is the laminar flow of electrolyte epitaxial substrate, makes monocell matrix green compact by isostatic compaction; In this course, the three laminar flow epitaxial substrates that stack are inserted in the warm water, pressurize 60s under the pressure of 5～50MPa, pressure is got 7MPa in the present embodiment;
(4) green compact are fired: the monocell green compact after the moulding are placed in the stove burn altogether, ignition temperature is 1200～1600 ℃, and insulation 0.5～5h makes the fuel-cell single-cell matrix;
(5) the monocell matrix is detected: place the fuel-cell single-cell matrix fuchsin solution to detect, whether the dielectric substrate that mediates with detection has cracking, pore, if having, then is judged to be substandard products; Otherwise, be judged to be certified products; After having finished pinkish red detection, the pinkish red Liquid Residue that will be attached in combustion furnace on the fuel-cell single-cell matrix dryouies;
(6) impregnation process: adopt impregnation method that anode that step (1) makes and cathodic metal salting liquid utilize the primary coat formula respectively anode and the negative electrode of the monocell matrix processed through step (5) to be carried out impregnation process, dipping once floods after drying again, through 5～10 dippings, finish impregnation process;
(7) baking is processed at last: the fuel-cell single-cell matrix of processing through step (6) is toasted, both got the fuel-cell single-cell structure after the dried maceration extract to be baked; Its baking temperature is set as 500～1000 ℃, and in the present embodiment, baking temperature is set as 800 ℃.
The anode metal salting liquid that makes in the described step (1) and cathodic metal salting liquid are the solution of 1mol/L.In the described step (2), when preparation is positioned at the curtain coating substrate of both sides, with base material zirconia powder and 0～10wt% dispersant, 3～20wt% binding agent, 1～15wt% plasticizer, deionized water mixing and ball milling proportionally, ball milling 24h forms discharging behind the stable slurry, the ball-type graphite that then will account for zirconia powder quality 15～40% joins in the slurry, stirs 1h, and slurry and ball-type graphite are mixed, then carry out the deaeration curtain coating, make needed zirconia curtain coating substrate.In the described step (2), when preparation is positioned at middle dielectric substrate, 0～8mol% Y will mix
2O
3, 0～20mol% Gd
2O
3, 0～9 mol% Sc
2O
3, 0～3mol% Ce
2O
3The doping total amount is proportionally mixing and ball milling of the zirconia powder of 2～30mol% and 0～10wt% dispersant, 3～20wt% binding agent, 1～15wt% plasticizer, deionized water, discharging deaeration curtain coating behind the ball milling 24h formation stable slurry, curtain coating thickness 0.05～1.0mm makes needed dielectric substrate.
In the process of above-mentioned preparation three laminar flow epitaxial substrates, described dispersant is fish oil or castor oil or triethanolamine, and described binding agent is PVB, polyester or PVA, and described plasticizer is DBP, DOP, glycerine or polyethylene glycol.
The present invention is further illustrated with specific embodiment for the below.
1, the preparation zirconium oxide substrate, with zirconia and 2wt% dispersant---fish oil and castor oil, 8wt% binding agent---PVB, 4wt% plasticizer---DBP, deionized water is mixing and ball milling proportionally, ball milling 24h forms discharging behind the stable slurry, the ball-type graphite that then will account for zirconia powder quality 30% joins in the slurry, stir 1h, slurry and ball-type graphite are mixed, then carry out the deaeration curtain coating, make needed zirconium oxide substrate, need in the process to guarantee mixing of ball-type graphite and slurry, otherwise the curtain coating process can cause the defectives such as layering and cracking.
2, preparation intermediate electrolyte layer, 5mol% Y will mix
2O
3, 10mol% Gd
2O
3, 5mol%l Sc
2O
3, 2mol% Ce
2O
3Zirconia powder and 2wt% dispersant---DBP, deionized water be mixing and ball milling proportionally for fish oil and castor oil, 8wt% binding agent---PVB, 4wt% plasticizer---, discharging deaeration curtain coating behind the ball milling 24h formation stable slurry, curtain coating thickness 0.09mm, because the curtain coating Thickness Ratio is thinner, so will strictly control edge of a knife height and evenness, guarantee operating steadily of casting machine.
3, the preparation of anode and cathodic metal salting liquid is mixed with the solution for standby of 1mol/L in volumetric flask, will calculate according to the required mol ratio of LSM in the cathodic metal salting liquid.
4, the isostatic compaction of curtain coating substrate stacks the curtain coating substrate of cutting out neatly, puts into the static pressure such as warm water after vacuumizing, pressurize 60s under the pressure of 7MPa.
5, the base substrate after the moulding carries out high temperature co-firing, burns altogether 1400 ℃ of temperature, will control the speed of binder removal in the sintering process, to guarantee can not to produce layering between the substrate or defective appears in the intermediate electrolyte layer.
6, the battery matrix after sintering is finished will use fuchsin solution to detect, and whether detect the intermediate electrolyte layer has the defectives such as cracking, pore, to guarantee the availability of battery.
After 7 detections are finished, burn at a certain temperature pinkish red residual solution, flood, adopt primary coat formula dipping, dipping once carries out the dipping second time afterwards again after drying, generally flood the instructions for use that can satisfy battery for 5-10 time, and the total immersion stain is 8 times in the present embodiment, carry out 800 ℃ of bakings after the two sides is all flooded and finished, form the fuel-cell single-cell that needs.
The present invention can be applicable to the fuel cell technology field.
Claims (16)
1. fuel-cell single-cell structure, it is characterized in that: described fuel-cell single-cell structure is made of the curtain coating zirconium oxide substrate that three laminations are closing, the curtain coating substrate that wherein is positioned at both sides has loose structure, be positioned at the curtain coating substrate in centre position as dielectric substrate, be impregnated with respectively anode metal salting liquid and cathodic metal salting liquid at the loose structure of the described curtain coating substrate that is positioned at both sides.
2. fuel-cell single-cell structure according to claim 1 is characterized in that: the described curtain coating substrate that is positioned at both sides contains the ball-type graphite as pore creating material.
3. fuel-cell single-cell structure according to claim 2, it is characterized in that: the thickness that is positioned at the described curtain coating substrate of both sides is 0.05～1.0mm.
4. fuel-cell single-cell structure according to claim 3, it is characterized in that: the porosity that is positioned at the described curtain coating substrate of both sides is 20～60%.
5. fuel-cell single-cell structure according to claim 1, it is characterized in that: the thickness that is positioned at the described curtain coating substrate in centre position is 0.05～0.5mm.
6. fuel-cell single-cell structure according to claim 5, it is characterized in that: the described curtain coating substrate that is positioned at the centre position contains 0～8 mol% Y
2O
3, 0～20 mol% Gd
2O
3, 0～9 mol% Sc
2O
3, 0～3 mol% Ce
2O
3, the doping total amount is 2～30mol%.
7. according to claim 1 to 6 each described fuel-cell single-cell structures, it is characterized in that: the anode metal salting liquid that floods at the described curtain coating substrate that is positioned at both sides is the soluble-salt solution of nickel, and described cathodic metal salting liquid is dissolved in the solution that forms in the deionized water for nitrate or the solvable chloride of the lanthanum, strontium and the manganese that calculate according to the LSM mol ratio.
8. fuel-cell single-cell structure according to claim 7, it is characterized in that: described anode metal salting liquid is the salting liquid of nickel nitrate or nickel chloride or nickelous sulfate, described cathodic metal salting liquid is the salting liquid of lanthanum nitrate, strontium nitrate and manganese nitrate.
9. the preparation method of a fuel-cell single-cell structure as claimed in claim 8 is characterized in that, the method may further comprise the steps:
(1) preparation of anode and cathodic metal salting liquid: in the volumetric flask of deionized water is housed, add the soluble-salt of nickel, form until completely dissolved the anode metal salting liquid; In the volumetric flask of deionized water is housed, add nitrate or the solvable chloride of lanthanum, strontium and manganese, form until completely dissolved the cathodic metal salting liquid;
(2) preparation of curtain coating substrate: adopt the tape casting moulding to prepare the two-layer ball-type graphite that contains as curtain coating substrate and one deck laminar flow of electrolyte epitaxial substrate of pore creating material, cut out three laminar flow epitaxial substrates for subsequent use by the battery specification;
(3) green compact preparation: stacked good three laminar flow epitaxial substrates in the step (2), wherein the intermediate layer is the laminar flow of electrolyte epitaxial substrate, makes monocell matrix green compact by isostatic compaction;
(4) green compact are fired: the monocell green compact after the moulding are placed in the stove burn altogether, ignition temperature is 1200～1600 ℃, and insulation 0.5～5h makes the fuel-cell single-cell matrix;
(5) the monocell matrix is detected: place the fuel-cell single-cell matrix fuchsin solution to detect, whether the dielectric substrate that mediates with detection has cracking, pore, if having, then is judged to be substandard products; Otherwise, be judged to be certified products;
(6) impregnation process: adopt impregnation method that anode that step (1) makes and cathodic metal salting liquid utilize the primary coat formula respectively anode and the negative electrode of the monocell matrix processed through step (5) to be carried out impregnation process, dipping once floods after drying again, through 5～10 dippings, finish impregnation process;
(7) baking is processed at last: the fuel-cell single-cell matrix of processing through step (6) is toasted, namely get the fuel-cell single-cell structure after the dried maceration extract to be baked.
10. the preparation method of fuel-cell single-cell structure according to claim 9, it is characterized in that, in described step (5), also comprise pinkish red Liquid Residue step, this step is: after having finished pinkish red detection, the pinkish red Liquid Residue that will be attached in combustion furnace on the fuel-cell single-cell matrix dryouies.
11. the preparation method of fuel-cell single-cell structure according to claim 10 is characterized in that: the anode metal salting liquid that makes in the described step (1) and cathodic metal salting liquid are the solution of 1mol/L.
12. the preparation method of fuel-cell single-cell structure according to claim 10, it is characterized in that: in the described step (2), when preparation is positioned at the curtain coating substrate of both sides, with base material zirconia powder and 0～10wt% dispersant, 3～20wt% binding agent, 1～15wt% plasticizer, deionized water is mixing and ball milling proportionally, ball milling 24h forms discharging behind the stable slurry, the ball-type graphite that then will account for zirconia powder quality 15～40% joins in the slurry, stir 1h, slurry and ball-type graphite are mixed, then carry out the deaeration curtain coating, make needed zirconia curtain coating substrate.
13. the preparation method of fuel-cell single-cell structure according to claim 10 is characterized in that: in the described step (2), when preparation is positioned at middle dielectric substrate, 0～8mol% Y will mix
2O
3, 0～20mol% Gd
2O
3, 0～9mol% Sc
2O
3, 0～3mol% Ce
2O
3The doping total amount is proportionally mixing and ball milling of the zirconia powder of 2～30mol% and 0～10wt% dispersant, 3～20wt% binding agent, 1～15wt% plasticizer, deionized water, discharging deaeration curtain coating behind the ball milling 24h formation stable slurry, curtain coating thickness 0.05～0.5mm makes needed dielectric substrate.
14. the preparation method of fuel-cell single-cell structure according to claim 10, it is characterized in that, in described step (3), the process of described isostatic compaction is: the three laminar flow epitaxial substrates that stack are inserted in the warm water pressurize 60s under the pressure of 5～50MPa.
15. according to claim 12 or the preparation method of 13 described fuel-cell single-cell structures, it is characterized in that: described dispersant is fish oil or castor oil or triethanolamine, described binding agent is PVB, polyester or PVA, and described plasticizer is DBP, DOP, glycerine or polyethylene glycol.
16. the preparation method of fuel-cell single-cell structure according to claim 9 is characterized in that: the baking temperature in the described step (7) is set as 500～1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100291271A CN103050724A (en) | 2013-01-25 | 2013-01-25 | Single-cell structure of fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100291271A CN103050724A (en) | 2013-01-25 | 2013-01-25 | Single-cell structure of fuel cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103050724A true CN103050724A (en) | 2013-04-17 |
Family
ID=48063286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100291271A Pending CN103050724A (en) | 2013-01-25 | 2013-01-25 | Single-cell structure of fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103050724A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103490076A (en) * | 2013-10-21 | 2014-01-01 | 哈尔滨工业大学 | Method for preparing acicular metal Ni on inner surface of porous substrate at high temperature |
| CN104879778A (en) * | 2015-05-08 | 2015-09-02 | 桂林市淦隆环保科技有限公司 | Automatic recognition method for controlling intelligent combustor to ignite utilizing conductivity of alcohol-based fuel |
| CN107611461A (en) * | 2017-09-30 | 2018-01-19 | 福州大学 | A kind of preparation method of SOFC |
| CN109888308A (en) * | 2019-04-09 | 2019-06-14 | 深圳市致远动力科技有限公司 | It is a kind of using electrolyte layer as fuel cell of matrix and preparation method thereof |
| CN109980238A (en) * | 2019-04-09 | 2019-07-05 | 深圳市致远动力科技有限公司 | A kind of production method and fuel cell of film electrode structure |
| CN110010908A (en) * | 2019-04-09 | 2019-07-12 | 深圳市致远动力科技有限公司 | A kind of fuel cell and battery pile |
| CN110655403A (en) * | 2018-06-28 | 2020-01-07 | 东莞信柏结构陶瓷股份有限公司 | Ceramic structural part filler, ceramic structural part filler, preparation method and application thereof |
| CN111129560A (en) * | 2019-12-27 | 2020-05-08 | 国联汽车动力电池研究院有限责任公司 | Oxide solid electrolyte sheet and preparation method and application thereof |
| CN111384421A (en) * | 2020-03-17 | 2020-07-07 | 江西赛瓷材料有限公司 | Five-layer structure single cell, preparation method thereof and prepared product |
| CN111416138A (en) * | 2020-03-12 | 2020-07-14 | 西安交通大学 | Proton ceramic membrane fuel cell and preparation method thereof |
| CN116666713A (en) * | 2023-06-06 | 2023-08-29 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Tubular solid oxide fuel cell manufacturing method based on casting and lamination technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101577341A (en) * | 2009-06-10 | 2009-11-11 | 中国矿业大学(北京) | Method for preparing solid oxide fuel cell and entire cell thereof at low temperature |
| CN101978537A (en) * | 2008-03-18 | 2011-02-16 | 丹麦科技大学 | An all ceramics solid oxide fuel cell |
| CN203150657U (en) * | 2013-01-25 | 2013-08-21 | 珠海市香之君电子有限公司 | Monocell structure of fuel cell |
-
2013
- 2013-01-25 CN CN2013100291271A patent/CN103050724A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978537A (en) * | 2008-03-18 | 2011-02-16 | 丹麦科技大学 | An all ceramics solid oxide fuel cell |
| CN101577341A (en) * | 2009-06-10 | 2009-11-11 | 中国矿业大学(北京) | Method for preparing solid oxide fuel cell and entire cell thereof at low temperature |
| CN203150657U (en) * | 2013-01-25 | 2013-08-21 | 珠海市香之君电子有限公司 | Monocell structure of fuel cell |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103490076A (en) * | 2013-10-21 | 2014-01-01 | 哈尔滨工业大学 | Method for preparing acicular metal Ni on inner surface of porous substrate at high temperature |
| CN103490076B (en) * | 2013-10-21 | 2015-06-03 | 哈尔滨工业大学 | Method for preparing acicular metal Ni on inner surface of porous substrate at high temperature |
| CN104879778A (en) * | 2015-05-08 | 2015-09-02 | 桂林市淦隆环保科技有限公司 | Automatic recognition method for controlling intelligent combustor to ignite utilizing conductivity of alcohol-based fuel |
| CN107611461A (en) * | 2017-09-30 | 2018-01-19 | 福州大学 | A kind of preparation method of SOFC |
| CN110655403B (en) * | 2018-06-28 | 2022-01-21 | 东莞信柏结构陶瓷股份有限公司 | Ceramic structural member filler, preparation method and application thereof |
| CN110655403A (en) * | 2018-06-28 | 2020-01-07 | 东莞信柏结构陶瓷股份有限公司 | Ceramic structural part filler, ceramic structural part filler, preparation method and application thereof |
| CN110010908A (en) * | 2019-04-09 | 2019-07-12 | 深圳市致远动力科技有限公司 | A kind of fuel cell and battery pile |
| CN109980238A (en) * | 2019-04-09 | 2019-07-05 | 深圳市致远动力科技有限公司 | A kind of production method and fuel cell of film electrode structure |
| CN109888308A (en) * | 2019-04-09 | 2019-06-14 | 深圳市致远动力科技有限公司 | It is a kind of using electrolyte layer as fuel cell of matrix and preparation method thereof |
| CN109980238B (en) * | 2019-04-09 | 2022-05-17 | 深圳市格罗夫科技有限公司 | Manufacturing method of membrane electrode structure and fuel cell |
| CN111129560A (en) * | 2019-12-27 | 2020-05-08 | 国联汽车动力电池研究院有限责任公司 | Oxide solid electrolyte sheet and preparation method and application thereof |
| CN111416138A (en) * | 2020-03-12 | 2020-07-14 | 西安交通大学 | Proton ceramic membrane fuel cell and preparation method thereof |
| CN111384421A (en) * | 2020-03-17 | 2020-07-07 | 江西赛瓷材料有限公司 | Five-layer structure single cell, preparation method thereof and prepared product |
| CN116666713A (en) * | 2023-06-06 | 2023-08-29 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Tubular solid oxide fuel cell manufacturing method based on casting and lamination technology |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103050724A (en) | Single-cell structure of fuel cell and preparation method thereof | |
| US10431841B2 (en) | Method for manufacturing solid oxide fuel cell | |
| CN100456544C (en) | Anode-supported solid electrolyte composite membrane for solid oxide fuel cell and preparation method thereof | |
| KR100648144B1 (en) | High performance anode supported solid oxide fuel cell | |
| CN103928693B (en) | The metal of SOFC supports half-cell and preparation method thereof | |
| CN103236548B (en) | Preparation method of multihole anode support of solid oxide fuel cell | |
| Shen et al. | Co-sintering anode and Y2O3 stabilized ZrO2 thin electrolyte film for solid oxide fuel cell fabricated by co-tape casting | |
| Myung et al. | Fabrication and characterization of planar-type SOFC unit cells using the tape-casting/lamination/co-firing method | |
| JP5097865B1 (en) | Fuel cell | |
| CN109867521B (en) | A method for secondary modification and densification of oxide ceramic films | |
| CN101577340A (en) | Method for preparing cathode-supported tubular solid oxide fuel cells | |
| CN107785598B (en) | Half-cell symmetrical solid oxide fuel cell | |
| CN113381041B (en) | Electrode-supported solid oxide fuel cell and preparation method thereof | |
| CN103151548A (en) | Al2O3-YSZ electrolyte membrane solid oxide fuel cell and preparation method thereof | |
| CN107195938A (en) | A kind of simple SOFC preparation method | |
| JP5242840B1 (en) | Fuel cell | |
| CN101222050A (en) | Anti-carbon deposition anode film material and preparation method thereof | |
| CN116826130A (en) | A kind of preparation method of solid oxide fuel cell | |
| CN109585914A (en) | The preparation method of oxide solid electrolyte sheet and the solid state battery prepared using this method | |
| CN104037425B (en) | A kind of intermediate temperature SOFC flat board anode support type monocell anode construction and preparation method thereof | |
| CN203150657U (en) | Monocell structure of fuel cell | |
| JP2011142042A (en) | Power generation cell for solid oxide fuel battery and its manufacturing method | |
| JP4864171B1 (en) | Solid oxide fuel cell | |
| CN101308930A (en) | A kind of preparation method of methane direct oxidation anode | |
| CN117229057A (en) | Simple and convenient LaGaO preparation 3 Method for preparing electrolyte sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 519000, 3 floor, No. 311 Warwick Road, Guangdong, Zhuhai, two or three Applicant after: ZHUHAI XIANGZHIJUN TECHNOLOGY CO., LTD. Address before: 519015 Development Building, 1154 East Jiuzhou Road, Guangdong, Zhuhai 7 Applicant before: Luckyman Electronic Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130417 |