CN1985397B - 固体氧化物燃料电池 - Google Patents
固体氧化物燃料电池 Download PDFInfo
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- CN1985397B CN1985397B CN2005800191120A CN200580019112A CN1985397B CN 1985397 B CN1985397 B CN 1985397B CN 2005800191120 A CN2005800191120 A CN 2005800191120A CN 200580019112 A CN200580019112 A CN 200580019112A CN 1985397 B CN1985397 B CN 1985397B
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- layer
- sofc battery
- alloy
- doping
- cerium oxide
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- 239000000446 fuel Substances 0.000 title description 9
- 239000007787 solid Substances 0.000 title 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 230000007704 transition Effects 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000010416 ion conductor Substances 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 36
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- 238000005336 cracking Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 19
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 12
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 12
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052706 scandium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003863 metallic catalyst Substances 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims 10
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 14
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 13
- 229910003271 Ni-Fe Inorganic materials 0.000 abstract description 6
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 229910001566 austenite Inorganic materials 0.000 abstract description 3
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000010363 phase shift Effects 0.000 abstract description 2
- -1 ScYSZ Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 230000001627 detrimental effect Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 81
- 238000005507 spraying Methods 0.000 description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000005755 formation reaction Methods 0.000 description 20
- 238000005266 casting Methods 0.000 description 16
- 238000000465 moulding Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 230000008595 infiltration Effects 0.000 description 14
- 238000001764 infiltration Methods 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000007650 screen-printing Methods 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910002484 Ce0.9Gd0.1O1.95 Inorganic materials 0.000 description 3
- 229910000604 Ferrochrome Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003490 calendering Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 1
- 229910002612 Gd-Ce Inorganic materials 0.000 description 1
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- YMVZSICZWDQCMV-UHFFFAOYSA-N [O-2].[Mn+2].[Sr+2].[La+3] Chemical compound [O-2].[Mn+2].[Sr+2].[La+3] YMVZSICZWDQCMV-UHFFFAOYSA-N 0.000 description 1
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
SOFC电池,包括:金属支撑(1),其终止于基本纯净的电子导电氧化物;活性阳极层(2),其由基于氧离子导体的共掺杂氧化锆构成;活性阴极层(5);以及LSM和铁素体的混合物层,其作为到单相LSM的阴极集电器(7)的过渡层(6)。使用金属支撑而不是Ni-YSZ阳极支撑,增加了支撑的机械强度并确保了支撑的氧化还原稳定性。多孔铁素体不锈钢终止于纯净的电子导电氧化物,以阻止倾向于溶解到铁素体不锈钢中而导致从铁素体到奥氏体结构的有害相移的活性阳极中金属之间的反应。
Description
技术领域
本发明涉及包括金属支撑的固体氧化物燃料电池(SOFC)。
背景技术
US 2002/0048 699涉及一种包括铁素体不锈钢基板的固体氧化物燃料电池,所述铁素体不锈钢基板包括多孔区域和束缚该多孔区域的非多孔区域。铁素体不锈钢双极板位于所述基板的多孔区域的一个表面之下,并密封连接到所述基板的多孔区域之上的非多孔区域。第一电极层位于所述基板的多孔区域的另一表面之上,并且电解质层位于第一电极层之上,而第二电极层位于该电解质层之上。这样的固体氧化物燃料电池相对便宜。但是其不够鲁棒(robust)。
发明内容
本发明的目的是提供一种固体氧化物燃料电池,其相对便宜,并且同时比之前已知的固体氧化物燃料电池更加鲁棒。
根据本发明一方面的SOFC电池包括:
金属支撑材料,
活性阳极层,由良好的碳氢化合物裂解(crack)催化剂构成,
电解质层,
活性阴极层,和
到阴极集电器的过渡层,由LSM和铁素体的混合物构成,或者由单相LSM构成,
提供用于阻止所述金属支撑和活性阳极之间扩散的装置,
其中,通过渐变的、终止于基本纯净的电子导电氧化物的金属支撑阻止了金属支撑和活性阳极之间的扩散。
根据本发明另一方面的SOFC电池包括:
金属支撑材料,
活性阳极层,由良好的碳氢化合物裂解催化剂构成,
电解质层,
活性阴极层,和
到阴极集电器的过渡层,由LSM和铁素体的混合物构成,或者由单相LSM构成,
到阴极集电器的过渡层,由LSM和铁素体的混合物构成,或者由单相LSM构成,
提供用于阻止所述金属支撑和活性阳极之间扩散的装置,
其中,由阳极层阻止所述金属支撑和活性阳极之间的扩散,所述阳极层由多孔材料构成,所述多孔材料是在烧结之后渗透的。
使用金属支撑而不是Ni-YSZ(氧化钇稳定氧化锆)阳极支撑,增加了支撑的机械强度并确保了支撑的氧化还原稳定性。
使用金属支撑时的问题是,在烧结(其在相对高的温度进行)期间,来自活性阳极层的电极材料与金属支撑互相扩散,造成例如从铁素体到奥氏体相的有害的支撑相变。
根据本发明,这可以通过以下方法避免,将金属支撑形成为终止于(end in)电子导电氧化物(electron conducting oxide)的渐变(graded)金属陶瓷结构,或者将活性阳极层形成为多孔层,在烧结之后向其中渗透活性阳极材料。
在根据本发明的具体实施方案中,该电池包括:铁素体金属支撑,其由渐变的、终止于基本纯净的电子导电氧化物的层状金属陶瓷结构构成,
活性阳极层,其由良好的碳氢化合物催化剂构成,例如掺杂的氧化铈和Ni-Fe合金的混合物,
电解质层,
活性阴极层,
过渡层,其优选由LSM(LaxSr1-xMnO3)和铁素体的混合物构成,并终止于
阴极集电器,其优选由单相LSM构成。
FeCr多孔支撑在所有内和外表面上具有氧化物层,该氧化物层可通过Fe-Cr合金本身在适当气氛中氧化或通过涂敷该合金来形成。该涂层的目的是阻止碳和焦油的沉积。涂层的成分可基于例如Cr2O3,CeO2,LaCrO3,SrTiO3。在任何情况中,基础氧化物应当适当地掺杂。
根据本发明的SOFC电池可在电解质层和活性阴极层之间设有掺杂的氧化铈的反应阻挡层,所述反应阻挡层具有0.1~1μm的厚度。该阻挡层阻止了阳离子从阴极到电解质的扩散。结果可以增加使用寿命。
根据本发明,活性阴极可由以下复合物构成,该复合物一种材料选自氧化钪和氧化钇稳定氧化锆(ScYSZ)或掺杂的氧化铈,一种材料选自LSM,锰酸锶镧(LnSrMn)或氧化钴铁锶镧(LnSrFeCo),(Y1-xCax)Fe1-yCoyO3,(Gd1-xSrx)sFe1-yCoyO3或(Gd1-xCax)sFe1-yCoyO3。这种阴极材料比其他阴极材料表现更好。
根据本发明,电解质层可由共掺杂的氧化锆基氧离子导体构成。这种电解质具有比YSZ更高的氧离子导电性,以及比ScSZ更好的长时间稳定性。作为替换,可使用掺杂的氧化铈。
根据本发明,SOFC电池可包括:铁素体不锈钢支撑;活性复合物阳极层,其由良好的碳氢化合物裂解催化剂(例如Ni合金)和适当的离子导体(例如掺杂的氧化铈或ScYSZ)构成;电解质层;和活性阴极层以及到阴极集电器的过渡层,该过渡层优选地由LSM和铁素体的混合物构成,该阴极集电器优选由单相LSM构成。
在具体实施方案中,金属支撑可由FeCrMx合金构成。Mx是诸如Ni,Ti,Ce,Mn,Mo,W,Co,La,Y或Al的合金元素。浓度保持在相关的奥氏体形成的水平之下。
在另一具体实施方案中,活性阳极可由8YSZ、共掺杂的氧化锆或共掺杂的氧化铈的多孔层构成。可添加0~50%的金属合金。
附图说明
下面参考附图来说明本发明,其中:
图1示出根据本发明的鲁棒的中等温度SOFC电池。
图2示出多种阴极材料的面积电阻率(area specific resistance),包括在根据本发明的SOFC电池中使用的阴极材料。
图3示出具有阳极渗透层的SOFC电池。
图4示出具有阳极渗透层和阻挡层的SOFC电池。
图5示出具有双电极渗透层的SOFC电池。
具体实施方式
图1示出了根据本发明的固体氧化物燃料电池SOFC。该电池包括:金属支撑1,其终止于基本纯净的电子导电氧化物;活性阳极层2,其由掺杂的氧化铈或ScYSZ、Ni-Fe合金构成;电解质层3,其由共掺杂的氧化锆或氧化铈基氧离子导体构成;活性阴极层5;以及LSM和铁素体层的混合物层,其作为到优选由单相LSM或LnSrMnCo构成的阴极集电器7(或多孔金属集电器)的过渡层6。
由七个功能层构成的完整的固体氧化物燃料电池的主干是功能渐变的多孔金属陶瓷结构1,其由多孔铁素体不锈钢和电子导电氧化物构成,所述电子导电氧化物如(Sr1-xLax)sTi1-yNbyO3(LSTN),其中0≤x≤0.4,0.5≤s≤1,0≤y≤1。这种氧化物的另一例子为(La1-xSrx)CrO3 (LSC)。另一例子为Sr(La)Ti(Nb)O3(LSTN)+FSS(例如,Fe22Cr)。通常,可以使用热膨胀系数与金属的热膨胀系数大致匹配的电子导电氧化物(n型或p型导体)。合金表面(内与外)涂有电子导电氧化物层,以便阻止多孔阳极支撑1中碳氢化合物的裂解。由于多孔支撑中碳氢化合物裂解可能会使碳沉淀,导致孔隙堵塞,因此碳氢化合物的裂解应当仅在活性阳极中发生。
使用金属支撑1而不是Ni-YSZ阳极支撑,增加了支撑的机械强度,并确保了该支撑的氧化还原稳定性。多孔铁素体不锈钢1终止于纯净的电子导电氧化物,例如LSC或LSTN(Sr(La)Ti(Nb)O3),以便阻止活性阳极2中金属之间的反应,尤其是Ni或NiO,其易于溶解到铁素体不锈钢中,造成可能有害的从铁素体到奥氏体结构的相移。还可在相反方向发生扩散,因为来自金属支撑的元素可扩散到阳极中。
活性阳极层2是掺杂的氧化铈+ScYSZ+Ni-Fe合金的渐变结构,其仅包含少量百分比的纳米粒度的金属催化剂,该催化剂为良好的碳
氢化合物裂解催化剂。该层的厚度为1~50μm。
活性阳极2由NiO和FeOx或其混合物在ScYSZ和LSTN中的固溶体来制造。这种制品保证了在操作燃料电池中还原之后有少量百分比的纳米粒度的Ni-Fe催化剂。这实现了催化剂的高表面积,并且由于催化剂颗粒彼此保持一定的距离,阻止了催化剂的聚集。少量高表面积的镍和铁能够实现碳氢化合物的转换和裂解的快速动力学,以及氢的高效电化学转换。仅通过使催化剂细微地分散,避免了当使用碳氢化合物作为燃料时碳纳米管的形成。当活性阳极还原时形成细微分散的催化剂。由于阳极仅包含少量百分比的催化剂,因此它将是氧化还原稳定的(由于仅阳极的一小部分显示出氧化还原活性)。氧化还原循环可最终使Ni-Fe催化剂的纳米结构复苏(revive)。阳极2包含大量的氧化铈,其具有催化碳的电化学氧化的能力,碳可作为裂解过程的结果而形成。
电解质层3由共掺杂的氧化锆基氧离子导体(Y,Sc)Sz(氧化钇,氧化钪稳定氧化锆)构成。该类型的电解质具有比YSZ更高的氧离子导电性以及比ScSZ更好的长期稳定性。替代的,可使用掺杂的氧化铈。
具有550℃操作温度的电池的活性阴极5可由以下复合物制造,该复合物一种材料选自可能掺杂有Ce的ScYSZ或掺杂的氧化铈(例如,氧化钆掺杂氧化铈,CGO),一种材料选自(Y1-xCax)Fe1-yCoyO3,(Gd1-xSrx)sFe1-yCoyO3,(Gd1-xCax)sFe1-yCoyO3。另一例子为渐变复合物(Y,Ca)FeCoO3和掺杂氧化锆或氧化铈。这样的阴极5显示了优于LSM和其他阴极材料的性能,参见图2。在A部位上替换为Y和Ca,而不是通常所用的阳离子La和Sr,提高了阴极的性能和稳定性。稳定性提高是由于当使用Y和Ca而不是La和Sr时避免了非导电锆酸盐(La2Zr2O7和SrZrO3)的形成。为了获得足够长的使用寿命,掺杂的氧化铈的反应阻挡层4(阻止阳离子从阴极向ScYSZ电解质扩散)可能是必需的。对于在700℃以上的温度范围操作的燃料电池,可以使用
LSM-YSZ或(Y,Sc)SZ复合物阴极,并且在这种情况下,氧化铈阻挡层4是不需要的。
在活性阴极层5之上,放置由LSM和铁素体的混合物或LSM+(Y,Ca)FeCoO3构成的渐变层6,作为到单相LSM(La(Sr)MnO3)或LSFCo(La1-xSrxFe1-yCoyO3-δ)的阴极集电器7的过渡,因为这具有最高的电子导电性。过渡层6的功能是阻止由于LSM和铁素体之间热膨胀系数的小差异导致的高的局部热应力。当LSM/YSZ用作阴极时可以取消该层。
图2示出了作为面积电阻率(ASR)给出的多种阴极性能的阿列纽斯(Arrhenius)曲线。其显示出GSFCo-铁素体像含有贵金属催化剂的阴极一样好。
作为替换,SOFC可用多孔电极渗透层制造,以忽略金属支撑和活性阳极之间的扩散,参见图3,层11~13。
层11:金属支撑(200~2000μm),FeCrMx合金,具有0~50Vol%的氧化物(例如掺杂的氧化锆,掺杂的氧化铈或其他氧化物,如Al2O3,TiO2,MgO,CaO,Cr2O3或其组合,但不限于这种材料)。添加氧化物起到以下几种作用:1)增强阳极层和金属支撑之间的化学键合;2)调整热膨胀系数;以及3)控制烧结能力和晶粒生长。
层12:用于阳极渗透的多孔层(20~100μm),Sc-Y-Ga-Ce掺杂氧化锆/Sm-Gd-Y或任意Ln元素或CaO掺杂氧化铈,添加有或未添加金属合金(FeCrMx)。在添加金属支撑材料的情况中,层将具有氧离子导电性(掺杂的氧化锆/氧化铈)以及电子导电性(金属)。在掺杂的氧化铈的情况中,层还将具有一些电催化效应。在烧结之后通过渗透电催化成分(Ni,具有或不具有掺杂氧化铈或任何其他电催化剂)来完成阳极。
层13:标准电解质(~10μm)类似于层12的离子导电材料或LaGaO3基电解质。
层14:全电池;具有两种不同选择,如下面图3和5列出的。
图3:普通的阴极喷涂或丝网印刷。
图5:具有阴极的第二多孔层14的渗透。
通过应用渗透获得了以下优点:
1.简单,不需要阳极/金属支撑阻挡层。
2.廉价的处理:在双渗透层的情况下仅需要一次烧结。
3.在不存在Ni的情况下进行烧结,因此烧结期间晶粒长大(coarsening)不是问题。
4.渗透提供了获得具有高表面积的电极的可能性。
5.因为操作温度低于烧结温度,阻止/减弱了电极材料和另一电池材料之间的化学反应。
6.渗透层的复合结构确保了电解质和金属支撑之间良好的机械结合,以及良好的跨越界面的导电性。
以下给出实施例。
实施例1
第一步是用成分为Fe-22%Cr的铁素体不锈钢的浆料流延成型(tape cast)为1mm的厚度。
第二步是在Fe-Cr铁素体钢的上部流延成型由80wt%(Sr0.8La0.2)0.95Ti0.9Nb0.1O3和20wt%Fe-22%Cr浆料构成的复合物,厚度为5~50μm。
第三步是喷涂厚度为5~50μm的(Sr0.8La0.2)0.95Ti0.9Nb0.1O3。
第四步是喷涂活性阳极浆液,厚度为10μm。该浆液的成分为50wt%的Y0.04Sc0.16Zr0.8O2和50wt%的Sr0.84Ni0.05Fe0.1TiO3。
第五步是喷涂成分为Y0.04Sc0.16Zr0.8O2的电解质,厚度为5μm。
第六步是将得到的半电池在9%H2+91%Ar的还原气氛中在1300℃共烧结。
第七步是喷涂由Ce0.9Gd0.1O1.95构成的阻挡层,厚度为0.2μm,然后在700℃烧结。
第八步是涂覆Fe-Cr合金。
第九步是喷涂由50wt%的(Gd0.6Sr0.4)0.99Co0.2Fe0.8O3和50wt%的Y0.04Sc0.16Zr0.8O2构成的阴极,厚度为20μm。
第十步是喷涂50wt%的(La0.85Sr0.15)0.95MnO3和50wt%的(Gd0.8Sr0.4)0.99Co0.2Fe0.8O3,厚度为1~30μm。
第十一步是丝网印刷由(La0.85Sr0.15)0.95MnO3构成的集电器,厚度为50μm。
阴极和阴极集电器在堆叠中现场烧结。
得到的固体氧化物燃料电池是鲁棒的,并且是灵活的,因为碳氢化合物和氢都能够在阳极转换。燃料电池通过裂解转换碳氢化合物,随后电化学氧化裂解产品。空气或纯氧气都可用作氧化剂。
实施例2
第一步是用成分为Fe-22%Cr的铁素体不锈钢的浆料流延成型为1mm的厚度。
第二步是在Fe-Cr铁素体钢的上部流延成型由80wt%(Sr0.8La0.2)0.95Ti0.9Nb0.1O3和20wt%Fe-22%Cr浆料构成的复合物,厚度为5~50μm。
第三步是喷涂厚度为5~30μm的(Sr0.8La0.2)0.95Ti0.9Nb0.1O03。
第四步是喷涂活性阳极浆液,厚度为10μm。该浆液的成分为50wt%的Y0.04Sc0.16Zr0.8O2-δ和50wt%的Sr0.84Ni0.05Fe0.1TiO3。
第五步是喷涂成分为Y0.04Sc0.16Zr0.8O2-δ的电解质,厚度为5μm。
第六步是将得到的半电池在9%H2+91%Ar的还原气氛中在1300℃共烧结。
第七步是喷涂由Ce0.9Gd0.1O1.95构成的阻挡层,厚度为0.2μm,然后在700℃烧结。
第八步是涂覆Fe-Cr合金。
第九步是喷涂由50wt%的(Gd0.6Sr0.4)0.99Co0.2Fe0.8O3-δ和50wt%的CGO10构成的阴极,厚度为20μm。
第十步是喷涂50wt%的(La0.85Sr0.15)0.95MnO3和50wt%的(Gd0.6Sr0.4)0.99Co0.2Fe0.8O3,厚度为1~30μm。
第十一步是丝网印刷由(La0.85Sr0.15)0.95MnO3构成的集电器,厚度为50μm。阴极在堆叠中现场烧结。
得到的固体氧化物燃料电池是鲁棒的,并且是灵活的,因为碳氢化合物和氢都能够在阳极转换。燃料电池通过裂解转换碳氢化合物,随后电化学氧化裂解产品。空气或纯氧气都可用作氧化剂。
实施例3
第一步是用成分为Fe-22%Cr的铁素体不锈钢的浆料流延成型为1mm的厚度。
第二步是在Fe-Cr铁素体钢的上部流延成型由80wt%(Sr0.8La0.2)0.95Ti0.9Nb0.1O3和20wt%Fe-22%Cr浆料构成的复合物,厚度为5~50μm。
第三步是喷涂厚度为1~30μm的(Sr0.8La0.2)0.95Ti0.9Nb0.1O3。
第四步是喷涂活性阳极浆液,厚度为10μm。该浆液的成分为50wt%的Y0.04Sc0.16Zr0.8O2-δ和50wt%的Sr0.84Ni0.05Fe0.1TiO3。
第五步是喷涂成分为Y0.04Sc0.16Zr0.8O2-δ的电解质,厚度为5μm。
第六步是喷涂由Ce0.9Gd0.1O1.95构成的阻挡层,厚度为0.5μm。
第七步是将得到的半电池在9%H2+91%Ar的还原气氛中在1350℃共烧结。
第八步是涂覆Fe-Cr合金。
第九步是喷涂由50wt%的(Gd0.6Ca0.4)0.99Co0.2Fe0.8O3和50wt%的
CGO10构成的阴极,厚度为20μm。
第十步是喷涂50wt%的(La0.85Sr0.15)0.95MnO3和50wt%的(Gd0.6Sr0.4)0.99Co0.2Fe0.8O3,厚度为1~30μm。
第十一步是丝网印刷由(La0.85Sr0.15)0.95MnO3构成的集电器,厚度为50μm。阴极在堆叠中现场烧结。
得到的固体氧化物燃料电池是鲁棒的,并且是灵活的,因为碳氢化合物和氢都能够在阳极转换。燃料电池通过裂解转换碳氢化合物,随后电化学氧化裂解产品。空气或纯氧气都可用作氧化剂。
实施例4
第一步是用成分为Fe-22%Cr的铁素体不锈钢的浆料流延成型为1mm的厚度。
第二步是在Fe-Cr铁素体钢的上部流延成型由80wt%(Sr0.8La0.2)0.95Ti0.9Nb0.1O3和20wt%Fe-22%Cr浆料构成的复合物,厚度为5~50μm。
第三步是喷涂厚度为1~30μm的(Sr0.8La0.2)0.95Ti0.9Nb0.1O3。
第四步是喷涂活性阳极浆液,厚度为10μm。该浆液的成分为50wt%的Y0.04Sc0.16Zr0.8O2-δ和50wt%的Sr0.84Ni0.05Fe0.1TiO3。
第五步是喷涂成分为Y0.04Sc0.16Zr0.8O2-δ的电解质,厚度为5μm。
第六步是将得到的半电池在9%H2+91%Ar的还原气氛中在1350℃共烧结。
第七步是喷涂由50wt%的LSM和50wt%的Y0.04Sc0.16Zr0.8O2-δ构成的阴极,厚度为20μm。
第八步是丝网印刷由(La0.85Sr0.15)0.95MnO3构成的集电器,厚度为50μm。阴极在堆叠中现场烧结。
得到的固体氧化物燃料电池是鲁棒的,并且是灵活的,因为碳氢化合物和氢都能够在阳极转换。燃料电池通过裂解转换碳氢化合物,随后电化学氧化裂解产品。空气或纯氧气都可用作氧化剂。
实施例5
第一步是用成分为Fe-22%Cr的铁素体不锈钢的浆料流延成型为1mm的厚度。
第二步是在Fe-Cr铁素体钢的上部流延成型由80wt%(Sr0.8La0.2)0.95Ti0.9Nb0.1O3和20wt%Fe-22%Cr浆料构成的复合物,厚度为5~50μm。
第三步是喷涂厚度为1~30μm的(Sr0.8La0.2)0.95Ti0.9Nb0.1O3。
第四步是喷涂活性阳极浆液,厚度为10μm。该浆液的成分为50wt%的Y0.04Sc0.16Zr0.8O2-δ和50wt%的Sr0.84Ni0.05Fe0.1TiO3。
第五步是喷涂成分为Y0.04Sc0.16Zr0.8O2-δ的电解质,厚度为5μm。
第六步是将得到的半电池在9%H2+91%Ar的还原气氛中在1350℃共烧结。
第七步是喷涂由50wt%的LSM和50wt%的Y0.04Sc0.16Zr0.8O2-δ构成的阴极,厚度为20μm。
第八步是丝网印刷由(La0.85Sr0.15)0.95MnO3构成的集电器,厚度为50μm。
阴极在堆叠中现场烧结。
得到的固体氧化物燃料电池是鲁棒的,并且是灵活的,因为碳氢化合物和氢都能够在阳极转换。燃料电池通过裂解转换碳氢化合物,随后电化学氧化裂解产品。空气或纯氧气都可用作氧化剂。
实施例6
通过流延成型Fe22Cr合金(+少量组分,如Mn)粉末悬浮液来制造厚度在200~2000μm范围的支撑片,参见图3。在干燥支撑11后,通过喷涂法沉积用于阳极渗透的层(层12,50μm)和最终的电解质层(层13,10μm)。这两层的成分都为Zr0.78Sc0.20Y0.02O2-δ。制造用于喷涂的悬浮液,使得渗透层12具有至少40%的孔隙率,平均孔隙尺寸为3μm,并且在烧结后电解质为致密的。随后将样品冲压成期望的尺寸,并在受控的还原条件下烧结所谓的半电池。Ni-,Ce-,Gd-硝酸盐的溶液通过真空浸入而渗透到多孔氧化锆层12中。得到的阳极具有40%Ni和60%(Gd0.1Ce0.9)O2-δ的体积浓度。在干燥和清洁电解质表面之后,通过喷涂法沉积(Gd0.6Sr0.4)0.99(Co0.2Fe0.8)O3-δ阴极(层14,40μm)。
实施例7
通过流延成型Fe22Cr合金(带有少量附加组分)粉末悬浮液来制造厚度在200~2000μm范围的支撑片,参见图3。在干燥支撑11后,通过丝网印刷包括体积比为1∶1的Zr0.78Sc0.20Y0.02O2-δ和FeCr合金的混合物的墨水,来沉积用于阳极渗透的层(层12,50μm)。向渗透层添加金属确保了金属支撑和渗透层之间的良好结合。最后,通过喷涂法沉积电解质层(层13,10~15μm)。如实施例6所述完成电池。
实施例8
通过流延成型与2~10Vol%的Zr0.94Y0.06O2-δ混和的Fe22Cr合金(带有少量组分)粉末悬浮液来制造厚度在200~2000μm范围的支撑片,参见图3。如实施例7所述完成电池。
实施例9
通过流延成型Fe22Cr合金(带有少量附加组分)粉末悬浮液来制造厚度在200~2000μm范围的支撑片,参见图3。由一个或多个包括电解质材料和金属合金(FeCrMx)混合物的薄片制造渐变渗透层。通过流延成型粉末悬浮液制造厚度为30~70μm的薄片,其具有变化的颗粒尺寸和由此所产生的孔隙尺寸。通过压延和压制,层压金属支撑片和1~4个渗透层片来制造电池结构。所得到的渗透层在成分方面渐变,孔隙尺寸和颗粒尺寸在5~10μm范围变化,相对金属支撑在电解质界面处降至~1μm。如实施例6所述完成电池。
实施例10
如实施例9,但是添加孔隙形成剂来控制渗透层和金属支撑的最终孔隙率。
实施例11
如实施例10,但是添加烧结添加剂(15)来控制层的收缩。其例子包括(但不限于)Al2O3,MgO,CaO,SrO,CoOx,MnOx,B2O3,CuOx,ZnO2,VOx,Cr2O3,FeOx,NiO,MoOx,WO3,Ga2O3或其组合。
实施例12
制造如前面实施例中所述的半电池。通过旋涂Gd-Ce硝酸盐溶液在电解质表面上沉积阴极/电解质阻挡层14(图4)(0.5μm)。在700℃烧结阻挡层之后,将Ni-(Gd0.1Ce0.9)O2-δ阳极渗透到层12中,如实施例6所述。在干燥和清洁电解质表面之后,通过丝网印刷沉积
(La0.6Sr0.4)0.99(Co0.2Fe0.8)O3-δ阴极(层15,40μm)。
实施例13
通过压延Fe22Cr合金浆料来制造约800μm厚的支撑片,图3中的层11。在干燥支撑之后,通过丝网印刷来沉积用于阳极渗透的层(层12)和电解质层。这两层的成分都为(Sm0.1Ce0.9)O2-δ。制造用于丝网印刷的墨水使得渗透层具有>50%的孔隙率,平均孔隙尺寸为1~2μm,并且电解质是致密的。随后将样品冲压成期望的尺寸,并且在受控的还原条件下烧结所谓的半电池。
制备Ni硝酸盐的溶液并且通过浸渍渗透到多孔(Sm0.1Ce0.9)O2-δ层(层12)中。在干燥和清洁电解质表面之后,通过喷涂法沉积(La0.6Sr0.4)0.99(Co0.2Fe0.8)O3-δ阴极(层14)。
实施例14
通过流延成型含有5vol%(Gd0.1Ce0.9)O2-δ的Fe22Cr合金粉末悬浮液来制造约500μm厚的支撑片,以增强与渗透层的结合,参见图3。通过喷涂法来沉积用于阳极渗透的层(30μm)和最终的电解质层(10μm)。这两层的成分都为(Gd0.1Ce0.9)O2-δ。在烧结之后,通过真空浸入来将Ni,Gd和Ce的硝酸盐渗透到多孔氧化铈层中。在干燥和清洁电解质表面之后,通过丝网印刷沉积LSCF阴极。
实施例15
如实施例8所述制造支撑。通过喷涂法来沉积用于阳极渗透的层(30μm)和(Gd0.1Ce0.9)O2-δ电解质层(10μm),所述用于阳极渗透的层包括Fe-Cr合金粉末和(Gd0.1Ce0.9)O2-δ,体积比为1∶1。如实施例6所述完成电池。
实施例16
如实施例6所述制造支撑(图3中的层11)。在干燥该支撑之后,
通过喷涂法沉积用于电极渗透的层(层12,70μm)、Zr0.78Sc0.20Y0.02O2-δ 电解质层(层13,10μm)、以及最终的另一用于电极渗透的层(层14,30μm)。两个渗透层的成分都为Zr0.78Sc0.20Y0.02O2-δ与40vol%的FeCr粉末,具有~60%孔隙率的大致孔隙率。
随后将样品冲压成期望的尺寸,并在受控的还原条件下烧结样品。遮蔽层14,并通过真空浸入将Ni-,Ce-,Gd-硝酸盐的溶液渗透到多孔层12中。得到的阳极将具有体积浓度为40%的Ni和60%的(Gd0.1Ce0.9)O2-δ 。在干燥之后,去除层14上的遮蔽物,遮蔽层12并在硝酸盐溶液中通过真空浸入来渗透活性阴极材料(得到的阴极成分):
(Gd0.6Sr0.4)0.99(Co0.2Fe0.8)O3-δ。
实施例17
如实施例6所述制造电池结构。通过压力渗透纳米尺寸的NiO和(Gd0.1Ce0.9)O2-δ的悬浮液来制造阳极层。
实施例18
如实施例7,但是特征在于使用烧结添加剂(选自(但不限于)实施例12中给出的列表中的一种或多种),其使得能够在低于1100℃的温度在氧化条件下适当烧结各种成分。
Claims (25)
1.SOFC电池,其包括:
金属支撑材料,
活性阳极层,由良好的碳氢化合物裂解催化剂构成,
电解质层,
活性阴极层,和
到阴极集电器的过渡层,所述过渡层由LSM和铁素体的混合物构成,或者由单相LSM构成,以及
提供用于阻止所述金属支撑和活性阳极之间扩散的装置,
其特征在于,通过渐变的、终止于基本纯净的电子导电氧化物的金属支撑阻止了金属支撑和活性阳极之间的扩散。
2.根据权利要求1的SOFC电池,其特征在于,所述金属支撑由FeCrMx类型的金属合金构成,Mx为Ni,Ti,Ce,Mn,Mo,W,Co,La,Y或Al。
3.根据权利要求1的SOFC电池,其特征在于,所述活性阳极层由良好的碳氢化合物裂解催化剂构成。
4.根据权利要求1的SOFC电池,其特征在于,在电解质层和活性阴极层之间具有掺杂的氧化铈的反应阻挡层。
5.根据权利要求4的SOFC电池,其特征在于,所述反应阻挡层具有0.1至1μm的厚度。
6.根据权利要求1的SOFC电池,其特征在于,所述活性阴极层由以下复合物构成,该复合物一种材料选自ScYSZ和掺杂的氧化铈,另一种材料选自LSM,LnSrMn,LnSrFeCo(Y1-xCax)Fe1-yCoyO3,(Gd1-xSrx)Fe1-yCoyO3和(Gd1-xCax)sFe1-yCoyO3。
7.根据权利要求1的SOFC电池,其特征在于,所述电解质层由共掺杂的氧化锆或共掺杂的氧化铈基氧离子导体构成。
8.根据权利要求7的SOFC电池,其特征在于,所述电解质层具有0.1至20μm的厚度。
9.根据权利要求1的SOFC电池,其特征在于,活性阳极(2)具有1至50μm的厚度。
10.根据权利要求1的SOFC电池,其特征在于,过渡层(6)由单相LSM构成。
11.根据权利要求1的SOFC电池,其特征在于,多孔Fe-Cr Mx金属支撑的内和外表面具有涂层。
12.根据权利要求1的SOFC电池,其特征在于,所述金属支撑由含Fe-Cr的合金与0至50%金属氧化物的添加剂制造。
13.根据权利要求1的SOFC电池,其特征在于,所述活性阴极层由掺杂的氧化锆或氧化铈与(La,Gd,Sr)(Fe,Co)O3-δ的混合物构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
14.SOFC电池,其包括:
金属支撑材料,
活性阳极层,由良好的碳氢化合物裂解催化剂构成,
电解质层,
活性阴极层,和
到阴极集电器的过渡层,所述过渡层由LSM和铁素体的混合物构成,或者由单相LSM构成,以及
提供用于阻止所述金属支撑和活性阳极之间扩散的装置,
其特征在于,由阳极层阻止所述金属支撑和活性阳极之间的扩散,所述阳极层由多孔材料构成,所述多孔材料是在烧结之后渗透的。
15.根据权利要求14的SOFC电池,其特征在于,添加到支撑材料中的金属氧化物从由掺杂的氧化锆、掺杂的氧化铈、Al2O3、TiO2、MgO、CaO、Cr2O3、FeOx或其组合构成的组中选择。
16.根据权利要求14的SOFC电池,其特征在于,所述活性阳极层由掺杂的氧化锆或掺杂的氧化铈构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
17.根据权利要求16的SOFC电池,其特征在于,所述活性阳极层由混合有金属合金的掺杂的氧化锆或氧化铈构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
18.根据权利要求14的SOFC电池,其特征在于,所述电解质由掺杂的氧化锆或掺杂的氧化铈构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca或其任意组合。
19.根据权利要求14的SOFC电池,其特征在于,所述活性阳极由带有金属催化剂的掺杂的氧化锆或掺杂的氧化铈的多孔层构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
20.根据权利要求14的SOFC电池,其特征在于,所述活性阴极层由多孔层构成,在烧结之后向其中渗透活性阴极。
21.根据权利要求20的SOFC电池,其特征在于,所述活性阴极层由掺杂的氧化锆或掺杂的氧化铈构成,其中掺杂物是Sr,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
22.根据权利要求21的SOFC电池,其特征在于,所述活性阴极层由混合有金属合金的掺杂的氧化锆或掺杂的氧化铈构成,其中掺杂物是Sr,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
23.根据权利要求20的SOFC电池,其特征在于,所述电解质由掺杂的氧化锆或氧化铈构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca或其任意组合。
24.根据权利要求20的SOFC电池,其特征在于,所述活性阳极由带有金属催化剂的掺杂的氧化锆或掺杂的氧化铈的多孔层构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
25.根据权利要求20的SOFC电池,其特征在于,所述活性阴极由掺杂的氧化锆或掺杂的氧化铈与(La,Gd,Sr)(Fe,Co)O3-δ的混合物构成,其中掺杂物是Sc,Y,Ce,Ga,Sm,Gd,Ca,任意Ln元素或其组合。
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- 2005-06-09 WO PCT/DK2005/000379 patent/WO2005122300A2/en active Application Filing
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- 2005-06-09 JP JP2007526203A patent/JP5260052B2/ja not_active Expired - Fee Related
- 2005-06-09 CN CN2010105435139A patent/CN102013507A/zh active Pending
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- 2005-06-09 KR KR1020077000633A patent/KR100909120B1/ko not_active IP Right Cessation
- 2005-06-09 US US11/570,320 patent/US7745031B2/en not_active Expired - Fee Related
- 2005-06-09 KR KR1020087028315A patent/KR20080105182A/ko not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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RU2356132C2 (ru) | 2009-05-20 |
RU2399996C1 (ru) | 2010-09-20 |
US7745031B2 (en) | 2010-06-29 |
KR20070038511A (ko) | 2007-04-10 |
RU2006144071A (ru) | 2008-07-20 |
RU2008152447A (ru) | 2010-07-10 |
KR100909120B1 (ko) | 2009-07-23 |
US20070269701A1 (en) | 2007-11-22 |
JP5260052B2 (ja) | 2013-08-14 |
JP2012069533A (ja) | 2012-04-05 |
JP2008502113A (ja) | 2008-01-24 |
EP2259373A1 (en) | 2010-12-08 |
NO20070151L (no) | 2007-03-08 |
KR20080105182A (ko) | 2008-12-03 |
EP1784888A2 (en) | 2007-05-16 |
AU2005253203A1 (en) | 2005-12-22 |
CN102013507A (zh) | 2011-04-13 |
CN1985397A (zh) | 2007-06-20 |
WO2005122300A3 (en) | 2006-03-02 |
WO2005122300A2 (en) | 2005-12-22 |
CA2569866C (en) | 2011-05-17 |
AU2005253203B2 (en) | 2009-05-28 |
CA2569866A1 (en) | 2005-12-22 |
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