CN1555105A - Novel plate assembled solid oxide fuel cell - Google Patents
Novel plate assembled solid oxide fuel cell Download PDFInfo
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- CN1555105A CN1555105A CNA2003101211711A CN200310121171A CN1555105A CN 1555105 A CN1555105 A CN 1555105A CN A2003101211711 A CNA2003101211711 A CN A2003101211711A CN 200310121171 A CN200310121171 A CN 200310121171A CN 1555105 A CN1555105 A CN 1555105A
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Abstract
This invention relates to a new type of solid oxide fuel cell, concretely, it relates to very new structured, a panel assembled, detachable, serial and parallel mixed solid oxide fuel cell including multiple single cells connected by a conduction connection unit, which can be detachable. This invention also relates to the said cell preparation method.
Description
Technical field
The present invention relates to a kind of novel solid oxide fuel cell (SOFC), more specifically, the present invention relates to a kind of brand new, panel assembled, detachable, Solid Oxide Fuel Cell (SOFC) that connection in series-parallel mixes, the invention still further relates to described battery preparation method.
Background technology
As a kind of novel energy system of clean and effective, Solid Oxide Fuel Cell is developing rapidly in the recent period, becomes the research focus and emphasis in global energy field.
Mainly developed at present the SOFC battery pack of tubular structure and two kinds of forms of plate armature.Tubular structure SOFC development is morning, also comparative maturity relatively.Monocell is sealed by an end, and the pipe of an end opening constitutes.Monocell forms battery pile by connecting between cathode and anode, and the trial run system can reach the 200kw energy output, has moved nearly ten thousand hours.The tubular structure battery pile cell degree of freedom is big, and is not easy to crack; Adopt porous ceramic as supporter, firm in structure; Without elevated-temperature seal, connect easily.But the male-female die opening is big, and the internal resistance loss is big; The stay pipe weight and volume is big, and energy density is low; Support the thickness of pipe, gaseous diffusion becomes rate determining step by this pipe; Must adopt electrochemical vapour deposition (EVD) (EVD) prepared electrolyte and electrode layer, production cost height.Begin under the situation that commercialization transforms at present SOFC, its energy density is low, complex manufacturing, and the processing cost height becomes the outstanding problem of its development of restriction.
Plate armature SOFC has just caused people's attention recently, and this geometry simply is designed to its making and has widened the field.In the plate armature SOFC battery pile, the battery coupled in series, electric current flows through each thin layer successively, and the path is short, and the internal resistance loss is little, the energy density height; Structure is flexible, and the gas communication mode is many; Constituent element is preparation separately, and technology is easy, various; The electrolyte thin membranization, working temperature reduces (700-800 ℃).
Classic flat-plate type SOFC structure, cell is formed film by anode, electrolyte, negative electrode, and the connector of both sides trough of belt connects the negative electrode and the anode of adjacent cell, and the gas passage of fuel gas and oxic gas is provided respectively in both sides, carries out gas-insulated simultaneously.Adopt the gas passage of dull and stereotyped straight flute form as patent USP5470672, USP4883497 has adopted corrugated structure that gas passage is provided.Follow-on dull and stereotyped SOFC structure as described in patent CN2368165Y, changes the gas passage on the connector into snakelike groove, and it is more even to make that reacting gas flows in battery pile; Patent CN2400908Y has reported the anode film one side introducing nickel porous plate on connecting plate piston ring land and solid electrolyte, to improve hard contact of anode film one side on connecting plate piston ring land and the solid electrolyte, improve the anode-side fuel availability, alleviate the thermal stress and the mechanical stress of battery pile.
Flat structure SOFC, though improved power of battery density effectively, and realized the low-cost production in enormous quantities of cell, also there are a lot of problems in this structure.At first form and to adopt glass or glass ceramic material sintering to form between film and the connector to be connected by anode, electrolyte, negative electrode, to realize sealing and insulation, yet must cause battery system under the periodic duty condition owing to be connected the different thermal coefficient of expansion of storeroom, be subjected to bigger thermal stress effect repeatedly, especially form three-in-one film under the trend of ultra-thinization development at anode, electrolyte, negative electrode, its life-span and reliability problems are more outstanding.Secondly, since between cell and the connector by contact the connection of realization electric current, this structure has high requirement to the evenness of cell diaphragm and connector flat board, for example to being of a size of the yttrium oxide stable zirconium oxide electrolyte of 100 * 100 * 0.15mm, requiring flatness error is ± 5 μ m, and this requirement has improved the difficulty and the cost of processing greatly.In addition, by realizing being connected successively between cell and the connector behind the seal, sealing materials sintering, series connection fully forms overall structure (being called as battery module) between the cell, and the SOFC battery pile is in case by after the sealing-in moulding, just can not dismantle.In this structure, when wherein a slice cell breaks down, can't change, the integral battery door module is scrapped.
At the problem that exists in the above-mentioned flat structure, people have carried out a large amount of trial work.As USP4883497 and CN2368165Y, make air-flow more even, but can not system deal with problems that complex structure has caused processing difficulties simultaneously, cost rises, and when adopting the ceramic material connector, or even is difficult to moulding and processing.Though CN2400908Y has been alleviated the part SOFC internal stress, can not eliminate thermal stress on the whole at all.
In sum, press for the SOFC of a kind of brand new of development at present, on the basis that keeps good characteristics such as plate SOFC high power density, low cost, easy processing, solve the problem of its built-in thermal stress, improve its sealing-in difficulty, optimize, simplify device architecture, reduce cost of manufacture, improve reliability of operation.
Summary of the invention
At problems of the prior art, the object of the present invention is to provide a kind of novel solid oxide fuel cell (SOFC), more specifically, the present invention relates to a kind of brand-new type, panel assembled, detachable, Solid Oxide Fuel Cell that connection in series-parallel mixes and preparation method thereof.
In first aspect present invention, solid-oxide fuel cell stack is provided, comprise a plurality of cells that connect by conduction connecting structure, wherein, described conduction connecting structure is dismountable conduction connecting structure.
In second aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned first aspect is provided, wherein, described conduction connecting structure is that machinery is tightly connected, and is preferably the pressure syndeton.
In third aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned second aspect is provided, wherein, described cell adopts plate armature.
In fourth aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned second aspect is provided, comprise that cell 1, elasticity are electrically connected the laminated construction repeatedly of material 2, gasket seal 3, bipolar sheets 4, metal pneumatic panel 5.
In fifth aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned second aspect is provided, wherein, described conduction connecting structure comprises that the elasticity electric current connects material 2, sealing gasket 3 and bipolar sheets 4, when compressing, elasticity is electrically connected material 2 and passes sealing gasket 3, and its one side links to each other with a electrode in the cell 1, and another side links to each other with bipolar sheets 4.
In sixth aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned the 5th aspect is provided, wherein, it is to be agglomerated into the certain thickness wire at random that described elasticity electric current connects material 2, diameter wiry for example is 0.2-1mm, or porous metals felt, metal Sponge or have the bending metals thin slice of elastic construction.
In seventh aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned the 6th aspect is provided, wherein, it is to be selected from nickel, copper or stainless metal in anode one side that described elasticity electric current connects material 2, in negative electrode one side is the Fe-Cr alloy silk of heat-resisting oxidation-resistance or nickel wire, the copper wire that has oxidation resistant coating, the metal or alloy silk that for example scribbles lanthanum manganate, chromic acid lanthanum, zirconia ceramics is intertwined at random, or above-mentioned material porous metals felt, the metal Sponge made.
In eighth aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned the 5th aspect is provided, wherein, described sealing gasket (3) anode one side be gold, silver, nickel, copper, stainless steel, etc. material make paillon foil or carbon paper, negative electrode one side be gold, silver, etc. material make paillon foil, or apply tinsels such as oxidation resistant coating nickel, copper, stainless steel, or adopt sheeting such as mica paper.
In ninth aspect present invention, a kind of solid-oxide fuel cell stack according to above-mentioned the 5th aspect is provided, wherein, described bipolar sheets 4 is preferably laminar metal.Preferred low bulk, heat-resisting, anti-oxidant ferritic alloyed steel (Fe-Cr alloy) are in negative electrode one side oxidation resistant coating such as preferred surface coating lanthanum manganate, chromic acid lanthanum also.
Description of drawings
The SOFC battery pile schematic diagram of accompanying drawing 1 brand new
Accompanying drawing 2 SOFC cell structural representations
Accompanying drawing 3 SOFC cell cutaway views
The SOFC battery pile generalized section of accompanying drawing 4 brand news
Embodiment
Below more specifically introduce the present invention in conjunction with the accompanying drawings with non-limited way.
Battery pile structure
Battery pile of the present invention preferably adopts flat laminated construction, but also can adopt other arrangement, as long as connect by dismountable conduction connecting structure between the cell.Can series, parallel or connection in series-parallel mixing connected mode between each cell.
In a scheme of the present invention, the SOFC battery pile of brand new of the present invention adopts flat laminated construction, comprise that cell 1, elasticity are electrically connected various parts such as material 2, gasket seal 3, metal bipolar sheet 4, metal pneumatic panel 5, its structure example as shown in Figure 1.
Cell
In battery pile of the present invention, can adopt various cells, as long as its structure and type are suitable for forming fuel cell pack with dismountable conduction connecting structure of the present invention.
In a concrete execution mode, cell 1 is for example formed by ceramic upper support frame 6, ceramic lower support frame 7, glass-ceramic seal materials 8 and by 4 parts such as three-in-one thin slice 9 that anode, electrolyte, negative electrode are formed, as shown in Figure 2.Cell 1 can adopt plate armature.But, should be appreciated that, can also adopt the cell of other structures and type in the present invention, and be not limited to cell shown in Figure 2.Some that below describe the cell can be used for battery pile of the present invention are example more specifically.
Form film 9 by anode, electrolyte, negative electrode in the cell 1 in the SOFC structure of the present invention, it can be the three-in-one film of electrolyte-supported, it also can be the three-in-one film of anode-supported, or the three-in-one film of cathode support, the three-in-one film that preferred electrolyte supports and the three-in-one film of anode-supported.Electrolyte can be selected fully stabilized zirconia for use, the electrolyte of doped cerium oxide or other new developments, preferred yttrium oxide stable zirconium oxide electrolyte.Anode material can be selected precious metal material for use, for example platinum, gold, silver etc., nickel/zirconia cermet, the anode material of copper/zirconia cermet or other new developments, preferred nickel/zirconia cermet and copper/zirconia cermet.Cathode material can be selected precious metal material for use, for example platinum, gold, silver etc., the cathode material of doped with manganese strontium acid lanthanum or other new developments, preferred doped with manganese strontium acid lanthanum.The shape of this thin slice can be the geometric figure that planar can form any regular that Mi Dui arranges, and for example triangle, rhombus, rectangle, square, just hexagonal etc. are taken all factors into consideration the simplification of processing technology, preferred square.In order to reduce the cell internal resistance, the thickness of diaphragm should be low as far as possible, should be below 1mm, and the thickness of optimization is below the 500 μ m, more the thickness of You Huaing is below the 200 μ m.
Carriage up and down 6 and 7 in the cell 1 in the SOFC structure of the present invention is a kind of structural details, as shown in Figure 3, mainly play a supportive role, portion forms the cavity of reacting gas within it, reaction gas can free rapid diffusion, avoid the resistance of gas when directly flowing between plate groove, snake type groove or corrugation groove, improved the utilance of reacting gas.As structural detail, its hot expansibility that has certain mechanical property and be complementary of major requirement with electrolyte, and do not have the requirement of electric conductivity.Can adopt the ceramic material carriage, aluminium oxide ceramics for example, Zirconia reinforced alumina ceramic (ZTA), partial stabilization zirconium oxide ceramic (PSZ), cubic stabilization zirconium oxide ceramic (TZP) and fully stabilized zirconia pottery.Preferred Zirconia reinforced alumina ceramic (ZTA), partial stabilization zirconium oxide ceramic (PSZ), cubic stabilization zirconium oxide ceramic (TZP) and fully stabilized zirconia pottery (YSZ).The geometry of carriage can be the geometric figure that planar can form any regular that Mi Dui arranges, for example triangle, rhombus, rectangle, square, just hexagonal etc.Take all factors into consideration the simplification of processing technology, preferred square.And be complementary with three-in-one diaphragm shapes, preferred thickness is 3-5mm, and the degree of depth of frame further groove part is 1-2mm, and the wall width is 3-8mm.
Glass ceramics seal, sealing materials 8 main electrolyte and carriage 6 and 7 of connecting in the cell 1 in the SOFC structure of the present invention, because carriage preferentially adopts ceramic materials such as ZTA, PSZ, TZP, YSZ, preferred electrolyte YSZ has very close even corresponding to hot expansibility with cell, therefore select the glass ceramics seal, sealing materials for use, preferably its thermal coefficient of expansion and YSZ electrolyte is approaching or consistent.The preferred thickness of seal, sealing materials is 0.1-0.5mm.
Conduction connecting structure
Conduction connecting structure of the present invention is that machinery is tightly connected, and is preferably the pressure syndeton.For example, described conduction connecting structure can comprise that the elasticity electric current connects material 2, gasket seal 3 and bipolar sheets 4, and described conduction connecting structure constitutes conduction under pressure and connects between cell.Following example has more specifically been described the present invention and has been conducted electricity each parts that connects.
Elasticity electric current in the SOFC structure of the present invention connects material 2 and is arranged in the carriage up and down 6 of cell 1 and 7 inside, and main effect is to play electric current between electrode (negative electrode or anode) and the bipolar sheets at cell to be communicated with effect.When battery pile was assembled, each constituent element closely was connected one, and it is compacted that elasticity is electrically connected material 2, and one side links to each other with a electrode in the cell 1, and another side links to each other with bipolar sheets 4, and metallic gasket 3 is just in time passed in its position.The elasticity electric current connects material 2 as a kind of flexible transition, and corresponding strain can take place along with the STRESS VARIATION between carriage and the bipolar sheets, effectively alleviates internal stress.Requirement to its material property is good high-temperature electrical conductance, non-oxidizability, and low price.The face shaping of electric current connection wire rod and arrangement requirement do not influence reacting gas and freely spread.
The structure that elasticity is electrically connected material 2 adopts thin wire, and diameter is 0.2-1mm, is agglomerated into certain thickness at random, or Network Weaving becomes certain thickness, for example porous metals felt, metal Sponge etc. have fixed size and shape, and pressured contracting is connected to form electric conductor.When assembling, battery pile directly is put into carriage up and down 6 in the cell 1 and 7 inside.
Elasticity is electrically connected material 2 and can adopts nickel wire, copper wire, stainless steel metal wire to be intertwined at random in anode one side, or above-mentioned material porous metals felt, the metal Sponge made or bending metals thin slice etc., perhaps the charcoal felt made of carbon fiber with elastic construction; Negative electrode one side adopts the Fe-Cr alloy silk of heat-resisting oxidation-resistance, or have nickel wire, the copper wire of oxidation resistant coating, the metal or alloy silk that for example scribbles lanthanum manganate, chromic acid lanthanum, zirconia ceramics is intertwined at random, or porous metals felt of making of above-mentioned material, metal Sponge etc.
Gasket seal 3 in the SOFC structure of the present invention mainly plays gas mechanical seal effect between the carriage 6,7 of cell and metal bipolar sheet 4, and formation flexibly connects.When battery pile was assembled, each constituent element was compacted, relied on the elasticity of gasket seal to form sealing when closely connecting.Gasket seal anode one side preferable material be gold, silver, nickel, copper, stainless steel, etc. material make paillon foil or carbon paper etc., negative electrode one side preferable material be gold, silver, etc. material make paillon foil, or apply tinsels such as oxidation resistant coating nickel, copper, stainless steel, or adopt sheeting such as mica paper.The geometry and the cell of tinsel are complementary, and preferred thickness is 0.1-0.5mm.
Metal pneumatic panel 5 in the SOFC structure of the present invention mainly plays to form respectively fuel gas and oxic gas passage, and material can be selected the heat resisting low expansion alloy material for use.
Specify the battery pile that how to prepare brand-new structure below by example.
Embodiment 1:
Three-in-one preparation: can adopt Chinese patent application number is that the flow casting molding method of report in 02129594.8 prepares yittrium oxide fully stabilized zirconia (YSZ) electrolyte membrane, be of a size of 50 * 50 * 0.15mm, concrete preparation method is as follows: adopting the YSZ nano-powder is raw material, require the YSZ nanopowder should have following feature: TEM observation primary particle granularity 15～50nm down, N
2Absorption specific surface 10～70m
2/ g; Centrifugal sedimentation test offspring concentrates on more than 85% between 0.10～0.60 μ m micron, and presents the main peak value in 0.3～0.4 μ m place; Down the observation particle is spherical in shape basically for TEM, can be in water stable suspersion more than 24 hours; Present a cube crystalline phase in the X-ray diffraction.Above-mentioned nano-powder (being example with the YSZ nanopowder here) and The suitable solvent, dispersant, binding agent and plasticiser are mixed, form the mud of even viscosity behind the ball milling.By 100 microns sieve apertures, under 0.2atm, carry out the emptying gas disposal, it is higher relatively to form solid content, and viscosity is suitable, good film-forming property, the mud of stable suspersion.Mixing mud being cast on the conveyer belt of a motion, is thin slice with thin scraper with its strickling.Usually scraper gap is 2: 1 with the biscuit thickness ratio of final drying.The viscosity of dry back biscuit thickness and mud, curtain coating speed, scraper gap setting and relation is arranged through the height of scraper rear slurry.Behind the mud casting film-forming, put into drying box and get rid of solvent.Adopt casting technique moulding electrolytic thin-membrane base substrate, the base substrate relative density is more than 60%, and profile is smooth evenly can stablize placement, not the modification cracking.
The sintering process of electrolytic thin-membrane base substrate divided for three steps carried out: 200～400 ℃ low thermophase, 800～1100 ℃ middle thermophase, 1300～1450 ℃ hot stage.The heating rate of strict control different phase.Low thermophase: room temperature～200 ℃, heating-up time 1-2 hour; Between 200～400 ℃, every 50 ℃ of constant temperature 1-3 hours, during heating rate be controlled at and raise in 1-2 hour 50 ℃.At low temperature between the middle thermophase, control heating rate be the 2-5 degree/minute.In thermophase: at interval 50 ℃ constant temperature 1-3 hour, during heating rate control 20-30 degree/hour.In middle temperature between the hot stage, control heating rate be the 30-50 degree/hour.Hot stage constant temperature 1-48 hour.It is transparent, smooth, smooth to obtain electrolytic thin-membrane at last.
It is 40 μ m that a side on this diaphragm adopts casting molding processes to prepare thickness, is of a size of the NiO/YSZ porous anode material of 40 * 40mm, 1350 ℃ of sintering 2 hours; It is 40 μ m that opposite side on this diaphragm adopts silk-screen printing technique to prepare thickness, is of a size of manganese strontium acid lanthanum (LSM) porous cathode material of 40 * 40mm, and 1250 ℃ of sintering obtain three-in-one diaphragm after 2 hours.
The carriage preparation: adopt the gel casting process to prepare the YSZ carriage, the folk prescription frame is of a size of 50 * 50mm, and the edge width is 4mm, and thickness is 5mm, and vent openings place depth of groove is 2mm.Overall dimension is 100 * 100mm.
Sealing-in assembly preparation: can adopt Chinese patent application number is that the glass ceramics seal, sealing materials of 02147179.7 invention prepares the sealing-in assembly, earlier powder is made slurry, adopt the flow casting molding method to prepare base substrate again, punch forming square frame behind the static pressure such as process, folk prescription frame overall dimension is 50 * 50mm, the edge width is 3mm, and thickness is 0.3mm.Concrete preparation method is as follows:
The seal, sealing materials preparation: according to the various raw materials of raw material proportioning weighing, add the ethanolic solution of 200 gram agate balls and 150ml 95%, put into the 250ml agate jar, the ball mill mix grinding is 24 hours during with planet, takes out oven dry.The powder of predry is placed in the corundum crucible, place chamber type electric resistance furnace or induction furnace or LASER HEATING stove to be rapidly heated, air atmosphere is to 1300～1500 ℃ of fusion temperatures, constant temperature 2 hours, compound is melt into flowable state, take out fast, pour cooling fast in the cold water rapidly into, form the fritter grog.After the block grog that will obtain is put into agate jar, added agate ball, dry grinded 4 hours.The ethanolic solution that adds 120ml 95% continued mix grinding 24 hours, and after the oven dry, behind 200 mesh sieves, it is stand-by to make seal, sealing materials excessively.
Flow casting molding base substrate film:, join 20ml and contain in the water of dispersant ball milling 24h with the seal, sealing materials that 100g prepares in example 1.Add the PVA solution of 9.5wt%, the alcoholysis degree of PVA is 50%, adds propylene glycol and PVP, wherein, the binding agent gross mass is 6.20g, and the quality of PVP is 20% of a binding agent gross mass, and the quality of propylene glycol is 1/2 of PVA, 1, the quality of ammediol is 100% of a propylene glycol, continues ball milling 24h.With the slurries filtration that obtains, vacuum degassing, curtain coating then, air dry 8h.
Compress film Deng static pressure: the seal, sealing materials membrane blank that will in example 2, prepare, lie on the smooth metallic plate, in the rubber bag of packing into, after vacuumizing mouth is shut.The static pressure press such as put into, rubber bag is taken out in voltage stabilizing after 1 minute, remove packing, obtains the base substrate thin slice.Plant the shape of requirement according to Fig. 1, on corresponding model press, strike out the shape of behavior requirement,
The cell assembling: the YSZ carriage vent grooves that will be of a size of 100 * 100mm places ground floor down, with 4 chip sizes is that 50 * 50 * 3mm sealing-in blank lies in wherein and to be the second layer, continuation placement 4 chip sizes are that the three-in-one diaphragm of negative electrode, electrolyte, anode of the sintering of 50 * 50mm is the 3rd layer, repeating to place 4 chip sizes is that 50 * 50 * 3mm sealing-in blank is the 4th layer on three-in-one diaphragm, places the YSZ carriage vent grooves that a slice is of a size of 100 * 100mm again and is layer 5 up.Above-mentioned five are placed on the supporting plate, put into high temperature furnace and are heated to 1150 ℃ of sintering 0.5 hour, obtain the cell that links together with carriage after slowly cooling off with stove.
Repeat above-mentioned technology, the many groups of preparation cell.
Bipolar sheets preparation: can adopt Chinese patent application number is low bulk, heat-resisting, the anti-oxidant Alfer steel of 02155409.9 invention, preparation size is 100 * 100mm, thickness be the 0.8mm metal connector as bipolar sheets, side spraying LSM coating wherein again, thickness is 40 μ m.Concrete preparation method is as follows for bipolar sheets: adopt conventional smelting technique to obtain molten steel, pour into alloy pig, and make the sample of test desired shape, size by the pressure processing method of routine, thereby prepare and have the alloy material that its composition falls into following compositing range, by weight, this alloy material comprises: Cr 15～30wt%, Ni 0.1～1wt%, Al 0.1～1wt%, Si 0.1～1.5wt%, Zr 0.1～1wt%, C＜0.05wt%, P＜0.03wt%, the Fe of S＜0.01wt and surplus.
Assembled battery heap: the bipolar sheets for preparing (is of a size of 100 * 100 * 0.8mm) and places ground floor; Place gasket seal, be of a size of 100 * 100mm Ni matter paillon foil square frame, the edge width is 3mm, and thickness is that 0.2mm is the second layer; Placing 4 porous Ni matter felts is the 3rd layer, is of a size of 40 * 40 * 4mm, is electrically connected material as elasticity; Placing the cell that has assembled is the 4th layer; Placing felt that 4 ferritic alloyed steels make, to be electrically connected material as elasticity be layer 5, is of a size of 40 * 40 * 4mm; Placing the goldleaf gasket seal is layer 5, is of a size of 100 * 100mm square frame, and the edge width is 3mm, and thickness is 0.2mm; The bipolar sheets that scribbles the LSM oxidation resistant coating (is of a size of 100 * 100 * 0.8mm) and places layer 6 down; Subsequently continue to repeat above-mentioned 2 to 6 layers operation, form the battery pile that comprises 5 cells successively.Upper and lower is with four bolted, and the ferritic alloyed steel that will have the input and output gas passage is at last made support and tightened together, and forms the integral battery door heap, after detecting through air-tightness, can carry out the stack performance experiment.
Embodiment 2:
With the Ni matter gasket seal of anode among the embodiment 1 and bipolar sheets one side be electrically connected material Ni matter porous felt as elasticity and be replaced by Cu matter gasket seal and Cu matter porous felt respectively, the constant assembling integral battery door heap of other assemblies.
Embodiment 3:
With the Ni matter gasket seal of anode among the embodiment 1 and bipolar sheets one side be electrically connected material Ni matter porous felt as elasticity and be replaced by carbon paper respectively and be electrically connected material as gasket seal and charcoal fibrofelt as elasticity, the constant assembling integral battery door heap of other assemblies.
Embodiment 4:
With the goldleaf gasket seal of negative electrode among the embodiment 1 and bipolar sheets one side be electrically connected material ferritic alloyed steel porous felt as elasticity and be replaced by mica paper respectively as gasket seal with scribble Ni matter or the Cu matter porous felt of one deck LSM, the constant assembling integral battery door heap of other assemblies.
Embodiment 5:
With the goldleaf gasket seal of negative electrode among the embodiment 1 and bipolar sheets one side be electrically connected material ferritic alloyed steel porous felt as elasticity and be replaced by mica paper respectively as gasket seal with scribble the Ni matter or the Cu matter porous felt of one deck chromic acid lanthanum, the constant assembling integral battery door heap of other assemblies.
Embodiment 6:
YSZ carriage among the embodiment 1 is replaced by the TZP material makes carriage and prepare cell, then the assembled battery heap.
Embodiment 7:
The three-in-one diaphragm structure of the YSZ electrolyte-supported among the embodiment 1 is replaced by the electrode and the three-in-one diaphragm structure of electrolyte of anode-supported, preparation cell, assembled battery heap then.
Embodiment 8:
The three-in-one diaphragm structure of the YSZ electrolyte-supported among the embodiment 1 is replaced by the electrode and the three-in-one diaphragm structure of electrolyte of anode-supported, the carriage of the YSZ material among the embodiment 1 is replaced by the TZP material makes carriage and prepare cell, then the assembled battery heap.
The advantage of SOFC battery pile structure of the present invention:
1. the integrative-structure of cell is to realize connecting behind sintering by the glass ceramics seal, sealing materials between the similar or similar material.Because do not have the not thermal expansion between the same material phenomenon that do not match, not only the difficulty of sealing technology has reduced, and its reliability improved, and guaranteed the safety and the working life of battery pile, can realize repeatedly starting repeatedly and working of battery pile.
2. the connection in series-parallel mixed structure of battery pile has overcome the connected mode that can only be connected in series in the former planar cells heap, even this frame mode was after a slice monocell lost efficacy or broke ring, the integral battery door heap still can work on, fundamentally overcome in plate armature, as long as a slice battery breaks down, just must put in order the phenomenon that heap is scrapped.
3. realized that by gasket seal flexible sealing is connected between carriage and the bipolar sheets, really realized the panel assembled battery pile, one-piece assemblies can be dismantled at any time, detects, changes, and do not influence other assemblies and integral battery door performance.
4. realize being electrically connected between cell by bipolar sheets with the elastic bonding material system, can further alleviate the various internal stresss of battery pile under the periodic duty condition.
5. SOFC structure of the present invention is not owing to exist hard connection between cell diaphragm and the bipolar sheets, therefore the evenness to cell diaphragm and bipolar sheets requires to reduce significantly, so just the technology to the preparation film requires to have reduced, and helps realizing low-cost, large-scale industrial production.
6. bipolar sheets has adopted writing board shape, no longer needs the groove of processed complex, greatly reduces the manufacture difficulty of bipolar sheets, helps realizing low-cost, large-scale industrial production.
7. there is not groove class passage in the reaction gas chamber that forms between carriage and the bipolar sheets, helps gas fast free diffusion, has overcome the inhomogeneities of current density, and temperature inhomogeneous improved the gas utilization ratio.
8. because this plane framework formula design of the present invention can not improve under the prerequisite that three-in-one processing film requires to electrolyte, just can obtain the plate SOFC battery pile of big planar dimension, help the manufacturing of small size, high-power battery heap.
The simplification of SOFC battery pile element shapes, the unification of each assembly function, the reduction that the assembly material combination property requires, the avoidance of rigid connection between the assembly, the foundation of modular construction, not only mean and to realize that low cost, industrialized mode produce each assembly material, and promoted the raising of battery pile reliability, be beneficial to the trouble free service of battery pile and have the longer life-span.All these will transform for the commercialization of SOFC battery pile and lay the foundation.
Claims (9)
1. solid-oxide fuel cell stack comprises a plurality of cells that connect by conduction connecting structure, and wherein, described conduction connecting structure is dismountable conduction connecting structure.
2. the solid-oxide fuel cell stack of claim 1, wherein, described conduction connecting structure is that machinery is tightly connected, and is preferably the pressure syndeton.
3. the solid-oxide fuel cell stack of claim 2, wherein, described cell adopts plate armature.
4. the solid-oxide fuel cell stack of claim 2 comprises that cell (1), elasticity are electrically connected the laminated construction repeatedly of material (2), gasket seal (3), bipolar sheets (4), metal pneumatic panel (5).
5. the solid-oxide fuel cell stack of claim 2, wherein, described conduction connecting structure comprises that the elasticity electric current connects material (2), sealing gasket (3) and bipolar sheets (4), when compressing, elasticity is electrically connected material (2) and passes sealing gasket (3), and its one side links to each other with a electrode in the cell (1), and another side links to each other with bipolar sheets (4).
6. the solid-oxide fuel cell stack of claim 5, wherein, it is to be agglomerated into the certain thickness wire at random that described elasticity electric current connects material (2), and diameter wiry for example is 0.2-1mm, or porous metals felt, metal Sponge or have the bending metals thin slice of elastic construction.
7. the solid-oxide fuel cell stack of claim 6, wherein, it is to be selected from nickel, copper or stainless metal in anode one side that described elasticity electric current connects material (2), in negative electrode one side is the Fe-Cr alloy silk of heat-resisting oxidation-resistance or nickel wire, the copper wire that has oxidation resistant coating, the metal or alloy silk that for example scribbles lanthanum manganate, chromic acid lanthanum, zirconia ceramics is intertwined at random, or above-mentioned material porous metals felt, the metal Sponge made.
8. the solid-oxide fuel cell stack of claim 5, wherein, described sealing gasket (3) anode one side be gold, silver, nickel, copper, stainless steel, etc. material make paillon foil or carbon paper, negative electrode one side be gold, silver, etc. material make paillon foil, or apply tinsels such as oxidation resistant coating nickel, copper, stainless steel, or adopt sheeting such as mica paper.
9. the solid-oxide fuel cell stack of claim 5, wherein, described bipolar sheets (4) is preferably laminar metal.Preferred low bulk, heat-resisting, anti-oxidant ferritic alloyed steel (Fe-Cr alloy) are in negative electrode one side oxidation resistant coating such as preferred surface coating lanthanum manganate, chromic acid lanthanum also.
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| CNB2003101211711A CN1252844C (en) | 2003-12-22 | 2003-12-22 | Novel plate assembled solid oxide fuel cell |
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| CNB2003101211711A CN1252844C (en) | 2003-12-22 | 2003-12-22 | Novel plate assembled solid oxide fuel cell |
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| CN1555105A true CN1555105A (en) | 2004-12-15 |
| CN1252844C CN1252844C (en) | 2006-04-19 |
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| CNB2003101211711A Expired - Fee Related CN1252844C (en) | 2003-12-22 | 2003-12-22 | Novel plate assembled solid oxide fuel cell |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1315223C (en) * | 2005-04-05 | 2007-05-09 | 中国矿业大学（北京校区） | High reliability long life solid oxide fuel battery and process for preparation |
| CN1319202C (en) * | 2005-04-05 | 2007-05-30 | 中国矿业大学（北京校区） | Method for connecting ceramal in solid oxide fuel battery |
| CN100449846C (en) * | 2007-03-08 | 2009-01-07 | 上海交通大学 | Removable flat-plate middle temperature solid oxide fuel cell stack |
| CN101401246B (en) * | 2006-03-10 | 2011-10-19 | 丰田自动车株式会社 | Fuel cell, fuel cell stack, and method of producing the fuel cell stack |
| CN101764236B (en) * | 2010-01-12 | 2012-07-25 | 中国石油大学(华东) | Flat fuel cell flexible seal device and brazing technology thereof |
| WO2017162213A1 (en) * | 2016-03-25 | 2017-09-28 | 安徽巨大电池技术有限公司 | Battery pack and assembly method therefor |
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| CN112310454A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院宁波材料技术与工程研究所 | Integration method of solid oxide fuel cell stack based on symmetrical double-cathode structure |
| CN113948748A (en) * | 2021-10-14 | 2022-01-18 | 广东省科学院新材料研究所 | Connecting plate and solid oxide fuel cell/electrolytic cell stack |
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| CN1315223C (en) * | 2005-04-05 | 2007-05-09 | 中国矿业大学（北京校区） | High reliability long life solid oxide fuel battery and process for preparation |
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| CN101401246B (en) * | 2006-03-10 | 2011-10-19 | 丰田自动车株式会社 | Fuel cell, fuel cell stack, and method of producing the fuel cell stack |
| CN100449846C (en) * | 2007-03-08 | 2009-01-07 | 上海交通大学 | Removable flat-plate middle temperature solid oxide fuel cell stack |
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| CN107230796B (en) * | 2016-03-25 | 2023-10-27 | 安徽巨大电池技术有限公司 | Battery pack and method of assembling the same |
| CN107346804A (en) * | 2016-05-06 | 2017-11-14 | 安徽巨大电池技术有限公司 | Battery pack |
| CN107346804B (en) * | 2016-05-06 | 2024-03-12 | 安徽巨大电池技术有限公司 | Battery pack |
| CN110071304A (en) * | 2019-04-23 | 2019-07-30 | 深圳市雄韬电源科技股份有限公司 | Fuel cell and preparation method thereof |
| CN112310454A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院宁波材料技术与工程研究所 | Integration method of solid oxide fuel cell stack based on symmetrical double-cathode structure |
| CN112310454B (en) * | 2019-07-31 | 2022-09-20 | 中国科学院宁波材料技术与工程研究所 | Integration method of solid oxide fuel cell stack based on symmetrical double-cathode structure |
| CN113948748A (en) * | 2021-10-14 | 2022-01-18 | 广东省科学院新材料研究所 | Connecting plate and solid oxide fuel cell/electrolytic cell stack |
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