CN107879742A - A kind of ceramic material titanium tantalum silicon-carbon for solid-oxide fuel cell connector - Google Patents

A kind of ceramic material titanium tantalum silicon-carbon for solid-oxide fuel cell connector Download PDF

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CN107879742A
CN107879742A CN201711120713.1A CN201711120713A CN107879742A CN 107879742 A CN107879742 A CN 107879742A CN 201711120713 A CN201711120713 A CN 201711120713A CN 107879742 A CN107879742 A CN 107879742A
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tantalum silicon
carbon
titanium tantalum
ceramic material
sic
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郑莉莉
李美栓
李希超
钱余海
徐敬军
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Qingdao University
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Qingdao University
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Abstract

The invention belongs to energy project and technical field, is specifically a kind of new ceramic material titanium tantalum silicon-carbon for being used for SOFC (SOFCs) connector.Its chemical formula is (Ti1‑xTax)3SiC2(x=0.005 0.5).The ceramic material antioxygenic property and conductive capability are better than present commercial alloy Crofer22 APU；Thermal coefficient of expansion is (9.2 ± 0.5) × 10‑6K‑1, zirconium oxide (YSZ) thermal coefficient of expansion 10.5 × 10 with SOFCs electrolyte stabilized with yttrium oxide‑6K‑1It is close；Creep-resistant property is high, and heat endurance is good, easy processing.It is that volatile contaminant will not be produced in SOFCs working environments the characteristics of the ceramic material maximum compared with alloy metallic interconnection materials, avoids Poisoning cathode and deteriorate Performance data.Thus, such ceramic joining body material can solve the volatilization problems of alloy connector when in use, and huge practical application foreground is possessed on SOFCs.

Description

A kind of ceramic material titanium tantalum silicon-carbon for solid-oxide fuel cell connector
Technical field
The invention belongs to energy project and technical field, and in particular to one kind is used for SOFC (SOFCs) the new ceramic material titanium tantalum silicon-carbon of connector.
Background technology
SOFC is due to high low with cost of electricity-generating etc. excellent with usable carbon-containing fuel, generating efficiency Point, have broad application prospects in the field such as distributed power station and electrical source of power.But its metallic interconnection materials is SOFCs development One of bottleneck.SOFCs metallic interconnection materials are the Lanthanum Chromite of Lanthanum Chromite or doping before the nineties, but this connector All kinds of corrupt practices creep in for material tool：It is required that battery is operated in more than 1000 DEG C, aerial sintering character is poor, and heat conductivility is bad, Forming difficulty, easily form Lacking oxygen, low-temperature conductive performance difference etc..After the nineties, dropped to SOFCs operating temperature 600-800 DEG C, alloy can be used as metallic interconnection materials, predominantly chromium-base alloy, nickel-base alloy and ferrous alloy, and these materials have Its own the advantages of.But also there are fatal defects：
1. the compound volatilization problems of chromium.In order that metallic interconnection materials have certain antioxygenic property under working environment And electric conductivity, alloy metallic interconnection materials will contain certain chromium, to generate oxidation chromium oxide film.And chromium oxide is in working environment The lower compound that can form volatile chromium, these compounds meeting Poisoning cathode, declines the output performance of battery, finally accelerates The aging of pile.
2. thermal coefficient of expansion mismatch problem.Electrolyte YSZ thermal coefficient of expansion is 10.5 × 10-6K-1, and Cr2O3Formed Thermal coefficient of expansion is higher in alloy, and the thermal coefficient of expansion of Fe based alloys is 11.5 × 10-6K-1-20×10-6K-1, Ni based alloys heat The coefficient of expansion is 14 × 10-6K-1-19×10-6K-1.Thermal coefficient of expansion, which mismatches, to cause pile to be produced during heating-cooling Larger thermal stress, cause battery component fragmentation.
3. creep-resistant property is insufficient.Alloy connector creep test shows that the creep-resistant property of alloy metallic interconnection materials is not Foot.If Crofer22APU is under 800 DEG C of 10MPa pressure, creep failure occurs in 240 hours；Under 800 DEG C of 8MPa pressure, Creep failure occurs in 1200 hours；Under 650 DEG C of 21.7MPa pressure, creep failure occurs in 2800 hours.
Therefore, the solid-oxide fuel cell connector material of the excellent performance of Development of Novel has highly important reality With change meaning.
The content of the invention
For volatilization problems of the metal connector present in prior art in SOFCs working environments, mesh of the invention Be a kind of SOFC ceramic joining body material-(Ti is provided1-xTax)3SiC2System, have on SOFCs There is big practical application foreground, the industrialization process of SOFC can be promoted.The new ceramic material is not four The simple sintering of kind former powder, but by hot pressing after, form a kind of phase constituent, be a kind of single-phase.It is any in 4 kinds of element powders It is a kind of individually element all without the synthesis monophase materialses performance.Ti was studied before forms TiC, this material with C element Antioxygenic property it is poor, severe oxidation can occur at work, matrix is fully oxidized to oxide, resistance mistake after a period of time Greatly, electric conductivity requirement is not reached；With Ti, Si and C-shaped are into Ti3SiC2Material, after the material oxidation, oxidation that its surface is formed Film is thicker, and electric conductivity is poor, does not reach electric conductivity requirement；Synthetically prepared Ta is designed with Ta, Si and C3SiC2Material, still This kind of material can not be synthesized, reason is：The mixing dephasign such as TiC, SiC is formed, single-phase composition can not be formed.
Present invention, also belong to first using this kind of monophase materialses titanium tantalum silicon-carbon as solid-oxide fuel cell connector Example.
The present invention adopts the technical scheme that：
One kind is used for the new ceramic material titanium tantalum silicon-carbon of SOFC (SOFCs) connector, the company Junctor material is titanium tantalum silicon-carbon ceramics, and this ceramic material is the ceramic phase material that titanium silicon-carbon carries out tantalum doping vario-property, wherein：Titanium tantalum Silicon-carbon chemical formula is (Ti1-xTax)3SiC2。
Further, the chemical formula (Ti1-xTax)3SiC2In, x=0.005-0.5.
Further, the chemical formula (Ti1-xTax)3SiC2In, x=0.05.
Further, the consistency of the titanium tantalum silicon carbon material is higher than 98%.
Further, the titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2Oxygen in 600~800 DEG C of temperature ranges It is 1.03 × 10 to change speed constant-14g2·cm-4·s-1-7.33×10-14g2·cm-4·s-1, thermal coefficient of expansion is 9.2 × 10- 6K-1.The characteristics of the most prominent is will not to produce volatile products at work.
Further, the titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2It is air in SOFCs negative electrode working environments Environment, it is 800 DEG C to control oxidizing temperature, and it is TiO that oxidization time obtains oxidation product after being 500 hours2+SiO2Oxide-film, surface Smooth, the oxide layer of oxide-film is single layer structure, oxide thickness≤3 μm.
Further, the titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2Under SOFCs negative electrode working environments, oxygen is controlled It is 800 DEG C to change temperature, and after aoxidizing 100 hours, the area specific resistance of material is 19 ± 3m Ω cm2。
The preparation process of titanium tantalum silicon-carbon ceramic material is as follows：
(1) Ti, Ta, Si are used, C element powder is synthetic material；
(2) each material is prepared according to stoichiometric proportion in chemical formula；
(3) the raw material powder prepared, which is put into agate jar, to be mixed, and with agate ball ball milling, the time is 5-24 hours, after dry in the air It is dry to take out sieving for standby；
(4) with 1-10MPa pressure cold moudlings in graphite jig, synthesized in case being put into hot pressing in hot pressing furnace.
Further, technique is used by hot pressing synthesis：Control hot pressing pressure 15-70MPa, hot pressing temperature 1300- 1650 DEG C, soaking time 5-70 minutes；Reaction atmosphere is the Ar gas of flowing
Chemically reacted during this is synthetically prepared, Ti first and Ta and C reaction generation (Ti, Ta) C intermediate compounds, Then (Ti, Ta) C reacts with having melted the Si being in a liquid state, and it is (Ti that generation, which has chemical formula,1-xTax)3SiC2Monophase materialses.This High temperature hot pressing preparation method, has that preparation technology is simple, the advantages of synthesizing high purity high dense degree material.
Using agate jar ball milling, sieving in preparation technology, it is easy to powdered rubber being ground into the less form of granularity, Grind size is thinner, is easy to be well mixed, at the material helps to synthesizing high purity high dense, while overcome processing charges it is high, The defects of grain coarsening causes mechanical property to be deteriorated.
Using hot pressing synthesis and preparation process, under certain temperature and pressure effect, each component of raw material can be promoted mutual Reaction, promotes the generation of monophase materialses, and its microstructure shows as that crystallite dimension fine uniform, crystal boundary are pure, and macro manifestations are With excellent mechanical property and creep-resistant property, so as to get monophase materialses consistency reach certain performance indications.
Raw material components corresponding to each element in the application react to each other, and generate single-phase, can improve the comprehensive of material Can, x span ensure that to obtain monophase materialses in chemical formula, and the acquisition of monophase materialses is that this material has each side excellent The guarantee of performance.A large amount of wastes of raw material can be effectively overcome simultaneously, avoid impurities phase excessive in product from influenceing the use of material Performance.
The ceramic material has performance preferable than alloy metallic interconnection materials, such as：
(1) inoxidizability and conductive capability.It can so ensure that it has good stability, matrix material as connector Material is not by severe oxidation, and the electric conductivity of material is good after oxidation reaction；
(2) heat endurance is good.The heat decomposition temperature of this kind of monophase materialses is more than 1550 DEG C, and inoxidizability is good, so It can guarantee that material phase interior denaturation, recurring structure will not fail under arms.
(3) creep-resistant property is high.High creep-resistant property, creep failure can be reduced, reduce SOFC Thermal stress between each component.
(4) easy processing.Good processing characteristics, the processing cost of metallic interconnection materials can be reduced.
Beneficial effects of the present invention are：
1. the thermal coefficient of expansion of titanium tantalum silicon carbon material of the present invention is close with SOFCs electrolyte YSZ's, so as to reduce electricity Heap caused thermal stress in use.(Ti1-xTax)3SiC2(x=0.005-0.5) thermal coefficient of expansion be (9.2 ± 0.5)×10-6K-1；And the thermal coefficient of expansion of alloy metallic interconnection materials is generally 11.5 × 10-6K-1-20×10-6K-1。
2. antioxygenic property of the titanium tantalum silicon carbon material of the present invention under SOFCs working environments compares commercial alloy Crofer22APU's is good, better than other in lapping-in gold metallic interconnection materials.At 800 DEG C, (Ti0.95Ta0.05)3SiC2Oxidation speed Rate constant is 7.33 × 10-14g2·cm-4·s-1, Crofer22APU oxidation rate constant is 1.71 × 10-13g2·cm-4· s-1, the oxidation rate constant of SUS430 stainless steels (the Japanese trade mark) is 7 × 10-13g2·cm-4·s-1；Haynes242 is Ni-based heavy The oxidation rate constant of shallow lake hardened high temperature alloy (U.S.'s trade mark) is 2 × 10-13g2·cm-4·s-1；The Ni-based precipitation of Rene41 alloys The oxidation rate constant of hardened high temperature alloy (U.S.'s trade mark) is 7 × 10-13g2·cm--4·s-1。
3. electric conductivity of the titanium tantalum silicon carbon material of the present invention under SOFCs working environments is good.(Ti0.95Ta0.05)3SiC2 In air 800 DEG C oxidation 100 hours after, 800 DEG C of area specific resistance is 19 ± 3m Ω cm under cathode environment2。
4. titanium tantalum silicon carbon material of the present invention has high consistency, the hair that gas leaks during can avoiding under arms It is raw.
5. titanium tantalum silicon carbon material of the present invention has high thermal conductivity, thermal conductivity 27.5Wm-1·K-1.High thermal conductivity Utilization rate of the fuel cell system to waste heat can be put forward.
6. titanium tantalum silicon carbon material of the present invention has high modulus of elasticity.Below 1050 DEG C of temperature, the in-fighting of material is basic It will not increase.
Brief description of the drawings
The block titanium tantalum silicon carbon material (Ti that Fig. 1 sinters to obtain by hot pressing synthesis preparation method0.95Ta0.05)3SiC2's XRD results.
Fig. 2 is the titanium tantalum silicon carbon block material (Ti of synthesis0.95Ta0.05)3SiC2Surface of polished SEM back scattering pictures.
Fig. 3 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2Aoxidized in SOFCs negative electrode working environments at a temperature of 800 DEG C Weightening is with the variation relation of oxidization time, Crofer22APU and (Ti0.95Nb0.05)3SiC2Oxidation kinetics data be also placed in Material as a comparison in figure.
Fig. 4 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2In SOFCs negative electrodes working environment, 800 DEG C aoxidize 500 hours The XRD results of surface species phase afterwards.
Fig. 5 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2In SOFCs negative electrodes working environment, 800 DEG C aoxidize 500 hours Surface topography afterwards.
Fig. 6 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2In SOFCs negative electrodes working environment, 800 DEG C aoxidize 500 hours Cross Section Morphology afterwards.
Fig. 7 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2800 DEG C of oxidations 100 are small under SOFCs negative electrode working environments Shi Hou, the area specific resistance at a temperature of 800 DEG C of SOFCs negative electrodes working environment.
Embodiment
Material of the present invention is further discussed below below by embodiment.
Embodiment 1.
As the x=0.05 in chemical formula, choice experiment material is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2, it is made Standby process is as follows：
Using Ti, Ta, Si, C element powder is synthetic material, and above-mentioned material powder is according to 2.85:0.15:1:2 proportioning is matched somebody with somebody Former powder is put, the raw material powder prepared, which is put into ball grinder, to be mixed, and Ball-milling Time is 10 hours, takes out sieving；In graphite jig With 5MPa pressure cold moudlings, it is put into hot pressing in hot pressing furnace and synthesizes.In the present invention, technique is used by hot pressing synthesizes： Under 30MPa pressure, 60 minutes are incubated at 1650 DEG C, reaction atmosphere is the Ar gas of flowing.
Fig. 1 is the densification (Ti sintered out0.95Ta0.05)3SiC2The XRD results of block.
Fig. 2 is the titanium tantalum silicon carbon material (Ti for synthesis0.95Ta0.05)3SiC2Surface of polished SEM back scattering pictures.It can see Go out, synthesized material is fine and close, measures consistency as 99.5%.
From the massive material of densified sintering product 10 × 10 × 2mm is cut with wire cutting method3Block sample, Ran Houyong 600#, 800#, 1000# are finally polished with 2000#SiC sand paper, are then polished with granularity W=1.5 antiscuffing paste, are finally used alcohol It is cleaned by ultrasonic, in case doing oxidation experiment.
Oxidation experiment condition is：Atmosphere is to simulate SOFCs cathode environments i.e. air ambient, 800 DEG C of oxidizing temperature.
Fig. 3 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2Aoxidized in SOFCs negative electrode working environments at a temperature of 800 DEG C The variation relation to increase weight with oxidization time, in order to contrast Crofer22APU and (Ti0.95Nb0.05)3SiC2Oxidation kinetics number According to being also placed in figure.It can be seen that titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2It is anti-oxidant at 800 DEG C in atmosphere Performance is better than Crofer22APU and (Ti0.95Nb0.05)3SiC2's.
Fig. 4 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2In SOFCs negative electrodes working environment, 800 DEG C aoxidize 500 hours The XRD results of surface species phase afterwards.It can be seen that oxidation product is TiO2.Except this, the diffraction maximum of matrix is very strong, it can be determined that The oxide-film of Surface Creation is very thin.
Fig. 5 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2In SOFCs negative electrodes working environment, 800 DEG C aoxidize 500 hours Surface topography afterwards.It can be seen that the oxide-film of Surface Creation is smooth, no bulk peeling phenomenon.
Fig. 6 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2In SOFCs negative electrodes working environment, 800 DEG C aoxidize 500 hours Cross Section Morphology afterwards.The material is very thin in 800 DEG C of oxide-films generated after aoxidizing 500 hours, less than 3 μm.Oxide layer is individual layer Structure, oxide-film and matrix are well combined, and interface is without cracking phenomena.With reference to XRD results, sweep result from line and may determine that, oxygen Change the rutile TiO that film is crystalline state2With amorphous Si O2。
Fig. 7 is titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2800 DEG C of oxidations 100 are small under SOFCs negative electrode working environments Shi Hou, the area specific resistance at a temperature of 800 DEG C of SOFCs negative electrodes working environment.It can be seen that the material aoxidizes 100 at 800 DEG C Area specific resistance after hour at 800 DEG C is 19 ± 3m Ω cm2。
In the present embodiment, (Ti0.95Ta0.05)3SiC2It is 7.33 × 10 in 800 DEG C of oxidation rate constants-14g2·cm-4· s-1, thermal coefficient of expansion is 9.2 × 10-6K-1；After 800 DEG C of oxidations 100 hours, at 800 DEG C the area specific resistance of sample for 19 ± 3mΩ·cm2, the metallic interconnection materials available for SOFC.
Embodiment 2.
As the x=0.005 in chemical formula, choice experiment material is titanium tantalum silicon carbon material (Ti0.995Ta0.005)3SiC2, its Preparation process is as follows：
Using Ti, Ta, Si, C element powder is synthetic material, and above-mentioned material powder is according to 2.985:0.015:1:2 proportioning Former powder is configured, the raw material powder prepared, which is put into ball grinder, to be mixed, and Ball-milling Time is 10 hours, takes out sieving；In graphite jig In with 3MPa pressure cold moudlings, be put into hot pressing in hot pressing furnace and synthesize.In the present invention, technique is used by hot pressing synthesizes： Under 20MPa pressure, 40 minutes are incubated at 1600 DEG C, reaction atmosphere is the Ar gas of flowing.The consistency of synthesized material is 98.6%.It is in 800 DEG C of oxidation kinetics constants：9.86×10-14g2·cm-4·s-1。
Embodiment 3.
As the x=0.5 in chemical formula, choice experiment material is titanium tantalum silicon carbon material (Ti0.5Ta0.5)3SiC2, it is prepared Process is as follows：
Using Ti, Ta, Si, C element powder is synthetic material, and above-mentioned material powder is according to 1.5:1.5:1:2 proportioning configuration Former powder, the raw material powder prepared, which is put into ball grinder, to be mixed, and Ball-milling Time is 24 hours, takes out sieving；In graphite jig with 10MPa pressure cold moudlings, it is put into hot pressing in hot pressing furnace and synthesizes.In the present invention, technique is used by hot pressing synthesizes： Under 70MPa pressure, 30 minutes are incubated at 1650 DEG C, is then incubated 60 minutes at 1400 DEG C, reaction atmosphere is the Ar gas of flowing.Institute The consistency of synthetic material is 98.1%.It is in 800 DEG C of oxidation kinetics constants：1.25×10-13g2·cm-4·s-1。
Described above is not limitation of the present invention, it should be pointed out that：Come for those skilled in the art Say, on the premise of essential scope of the present invention is not departed from, some variations, modifications, additions or substitutions can also be made, these improvement Protection scope of the present invention is also should be regarded as with modification.

Claims (9)

  1. A kind of 1. ceramic material titanium tantalum silicon-carbon for solid-oxide fuel cell connector, it is characterised in that the connection Body material is titanium tantalum silicon-carbon ceramics, and this ceramic material is the ceramic phase material that titanium silicon-carbon carries out tantalum doping vario-property, wherein：Titanium tantalum silicon Carbon geochemistry formula is (Ti1-xTax)3SiC2。
  2. 2. the ceramic material titanium tantalum silicon-carbon according to claim 1 for solid-oxide fuel cell connector, it is special Sign is, the chemical formula (Ti1-xTax)3SiC2In, x=0.005-0.5.
  3. 3. the ceramic material titanium tantalum silicon-carbon according to claim 1 for solid-oxide fuel cell connector, it is special Sign is, the chemical formula (Ti1-xTax)3SiC2In, x=0.05.
  4. 4. according to any described ceramic material titanium tantalum silicon for solid-oxide fuel cell connector of claim 1-3 Carbon, it is characterised in that the consistency of the titanium tantalum silicon carbon material is higher than 98%.
  5. 5. the ceramic material titanium tantalum silicon-carbon according to claim 3 for solid-oxide fuel cell connector, it is special Sign is, the titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2Oxidation rate constant in 600~800 DEG C of temperature ranges is 1.03×10-14g2·cm-4·s-1-7.33×10-14g2·cm-4·s-1, thermal coefficient of expansion is 9.2 × 10-6K-1。
  6. 6. the ceramic material titanium tantalum silicon-carbon according to claim 3 for solid-oxide fuel cell connector, it is special Sign is, the titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2It is air ambient in SOFCs negative electrode working environments, control oxidation Temperature is 800 DEG C, and it is TiO that oxidization time obtains oxidation product after being 500 hours2+SiO2Oxide-film, surfacing, oxide-film Oxide layer is single layer structure, oxide thickness≤3 μm.
  7. 7. the ceramic material titanium tantalum silicon-carbon according to claim 3 for solid-oxide fuel cell connector, it is special Sign is, the titanium tantalum silicon carbon material (Ti0.95Ta0.05)3SiC2Under SOFCs negative electrode working environments, the oxidizing temperature is controlled to be 800 DEG C, after aoxidizing 100 hours, the area specific resistance of material is 19 ± 3m Ω cm2。
  8. 8. according to any described ceramic material titanium tantalum silicon for solid-oxide fuel cell connector of claim 1-3 Carbon, it is characterised in that the preparation process of titanium tantalum silicon-carbon ceramic material is as follows：
    (1) Ti, Ta, Si are used, C element powder is synthetic material；
    (2) each material is prepared according to stoichiometric proportion in chemical formula；
    (3) the raw material powder prepared is put into agate jar to be mixed with alcohol, with agate ball Ball-milling Time 5-24 hours, after dry Take out sieving for standby；
    (4) with 1-10MPa pressure cold moudlings in graphite jig, synthesized in case being put into hot pressing in hot pressing furnace.
  9. 9. the ceramic material titanium tantalum silicon-carbon according to claim 8 for solid-oxide fuel cell connector, it is special Sign is that technique is used by hot pressing synthesizes：Control hot pressing pressure 15-70MPa, 1300-1650 DEG C of hot pressing temperature, during insulation Between 5-70 minutes；Reaction atmosphere is the Ar gas of flowing.
CN201711120713.1A 2017-11-14 2017-11-14 A kind of ceramic material titanium tantalum silicon-carbon for solid-oxide fuel cell connector Pending CN107879742A (en)

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JP2007134107A (en) * 2005-11-09 2007-05-31 Toyota Motor Corp Separator for fuel cell, its manufacturing method and fuel cell
CN102117907A (en) * 2009-12-31 2011-07-06 中国科学院金属研究所 Solid oxide fuel cell connector material used in fuel cell
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