JP5260052B2 - 固体酸化物型燃料電池 - Google Patents
固体酸化物型燃料電池 Download PDFInfo
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- JP5260052B2 JP5260052B2 JP2007526203A JP2007526203A JP5260052B2 JP 5260052 B2 JP5260052 B2 JP 5260052B2 JP 2007526203 A JP2007526203 A JP 2007526203A JP 2007526203 A JP2007526203 A JP 2007526203A JP 5260052 B2 JP5260052 B2 JP 5260052B2
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- layer
- fuel cell
- solid oxide
- oxide fuel
- doped
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- 239000000446 fuel Substances 0.000 title claims description 43
- 239000007787 solid Substances 0.000 title claims description 32
- 239000010410 layer Substances 0.000 claims description 148
- 239000000203 mixture Substances 0.000 claims description 54
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 35
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 35
- 229910052727 yttrium Inorganic materials 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 238000005336 cracking Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 230000004888 barrier function Effects 0.000 claims description 12
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 11
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 11
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 229910052706 scandium Inorganic materials 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229910000859 α-Fe Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims 11
- 229910052688 Gadolinium Inorganic materials 0.000 claims 10
- 229910052772 Samarium Inorganic materials 0.000 claims 9
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 229910002546 FeCo Inorganic materials 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000005470 impregnation Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 238000010345 tape casting Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- -1 lanthanoid strontium manganate Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910002484 Ce0.9Gd0.1O1.95 Inorganic materials 0.000 description 3
- 229910000604 Ferrochrome Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 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
- 235000016027 Persea schiedeana Nutrition 0.000 description 1
- 244000261838 Persea schiedeana Species 0.000 description 1
- 241000968352 Scandia <hydrozoan> Species 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
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- H01M4/8605—Porous electrodes
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- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- H01M4/8885—Sintering or firing
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- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
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- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
-
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- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
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- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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Description
金属サポート材料、
良好な炭化水素クラッキング触媒で構成された活性アノード層、
電解質層、
活性カソード層、および
カソード集電板までの、好ましくは、LSMとフェライトの混合物で構成された遷移層、
を有し、
前記金属サポートと前記活性アノードの間の拡散を抑制する手段が提供されることを特徴とする。
実質的に純粋な電子伝導性酸化物で終端する傾斜層状セラミック構造からなるフェライト系金属サポート、
ドープされたセリアとNi−Fe合金との混合物のような、良好な炭化水素触媒からなる活性アノード層、
電解質層、
活性カソード層、
LSM(LaxSr1-xMnO3)とフェライトの混合物から構成されることが好ましい遷移層、および
単一層のLSMで構成されることが好ましいカソード集電板
を有する。
1アノード/金属サポートバリア層が不要となり、単純になる
2安価な処理プロセス−−ダブル含浸層の場合、一つの焼結処理のみが必要となる
3Niなしで焼結処理が実施され、これにより焼結時の粗大化の問題が生じなくなる
4含浸処理によって、高表面積の電極が得られる可能性が高まる
5作動温度が焼結温度よりも低いため、電極材料と他のセル材料の間の化学反応が抑制/防止される
6含浸層の複合構造によって、電解質と金属サポートとの間に、良好な機械的結合および良好な界面伝導性が提供される。
Claims (19)
- 金属サポート材料、
活性アノード層、
電解質層、
活性カソード層、および
前記活性カソード層とカソード集電板の間の遷移層、
を有し、
前記遷移層は、LSMとフェライトの混合物、またはLSMと(Y , Ca)FeCoCo 3 の混合物で構成され、前記カソード集電板に向かって傾斜された組成を有し、
前記金属サポート材料と前記活性アノード層の間の拡散を抑制する手段が提供され、
前記活性アノード層は、多孔質材料および炭化水素クラッキング触媒からなり、前記金属サポート材料と前記多孔質材料とが焼結により形成された後に、前記多孔質材料に前記炭化水素クラッキング触媒が含浸され、これにより、前記金属サポート材料と前記活性アノード層の間の拡散が抑制されることを特徴とする固体酸化物型燃料電池。 - 前記金属サポート材料は、FeCrMxで表される種類の金属合金で構成され、Mxは、Ni、Ti、Ce、Mn、Mo、W、Co、La、YまたはAlであることを特徴とする請求項1に記載の固体酸化物型燃料電池。
- 前記活性アノード層は、ドープされたセリアとNi−Fe合金の混合物で構成されることを特徴とする請求項1に記載の固体酸化物型燃料電池。
- 前記電解質層と前記活性カソード層の間に、ドープされたセリアの反応バリア層が設置されることを特徴とする請求項1乃至3のいずれか一つに記載の固体酸化物型燃料電池。
- 前記活性カソード層は、ScYSZおよびドープ化セリアの中から選択される一つの材料と、LSM、LnSrMn、LnSrFeCo、(Y1-xCax)Fe1-yCoyCo3、(Gd1-xSrx)Fe1-yCoyO3、および(Gd1-xCax)sFe1-yCoyO3の中から選択される一つの材料との複合材で構成されることを特徴とする請求項1乃至4のいずれか一つに記載の固体酸化物型燃料電池。
- 前記電解質層は、酸素イオン伝導体をベースとした、共ドープされたジルコニアまたは共ドープされたセリアで構成されることを特徴とする請求項1乃至4のいずれか一つに記載の固体酸化物型燃料電池。
- 多孔質Fe−Cr−Mx製の前記金属サポート材料の内表面および外表面には、コーティング層があることを特徴とする請求項1乃至6のいずれか一つに記載の固体酸化物型燃料電池。
- 前記金属サポート材料は、0乃至50%の金属酸化物が添加されたFe−Cr含有合金で構成されることを特徴とする請求項1に記載の固体酸化物型燃料電池。
- 前記金属サポート材料には、ドープされたジルコニア、ドープされたセリア、Al2O3、TiO2、MgO、CaO、Cr2O3、FeOxまたはこれらの組み合わせからなる群から選択される金属酸化物が添加されることを特徴とする請求項1に記載の固体酸化物型燃料電池。
- 前記活性アノード層の多孔質材料は、ドープされたジルコニアまたはドープされたセリアで構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、またはこれらの組み合わせからなる群から選定されることを特徴とする請求項1に記載の固体酸化物型燃料電池。 - 前記活性アノード層の多孔質材料は、ドープされたジルコニアまたはセリアで構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、または金属合金と混合されたこれらの組み合わせからなる群から選定されることを特徴とする請求項10に記載の固体酸化物型燃料電池。 - 前記活性アノード層は、ドープされたジルコニアまたはドープされたセリアの多孔質層で構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、または金属触媒とこれらの組み合わせからなる群から選定されることを特徴とする請求項1乃至11のいずれか一つに記載の固体酸化物型燃料電池。 - 前記活性カソード層は、ドープされたジルコニアまたはセリアの混合物から構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、またはこれらと、(La,Gd,Sr)(Fe,Co)O3-δとの組み合わせからなる群から選定されることを特徴とする請求項1乃至12のいずれか一つに記載の固体酸化物型燃料電池。 - 前記活性カソード層は、多孔質層で構成され、
該多孔質層の中に、焼結後に、活性カソードが含浸されることを特徴とする請求項1乃至13のいずれか一つに記載の固体酸化物型燃料電池。 - 前記活性アノード層の多孔質材料は、ドープされたジルコニアまたはドープされたセリアで構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはLn元素、またはこれらの組み合わせからなる群から選定されることを特徴とする請求項14に記載の固体酸化物型燃料電池。 - 前記活性アノード層の多孔質材料は、ドープされたジルコニアまたはドープされたセリアで構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、または金属合金と混合されたこれらの組み合わせからなる群から選定されることを特徴とする請求項15に記載の固体酸化物型燃料電池。 - 前記電解質層は、ドープされたジルコニアまたはセリアで構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、またはこれらの組み合わせからなる群から選定されることを特徴とする請求項14に記載の固体酸化物型燃料電池。 - 前記活性アノード層は、ドープされたジルコニアまたはドープされたセリアで構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、または金属触媒とこれらの組み合わせからなる群から選定されることを特徴とする請求項14に記載の固体酸化物型燃料電池。 - 前記活性カソード層は、ドープされたジルコニアまたはドープされたセリアの混合物で構成され、
ドーパントは、Sc、Y、Ce、Ga、Sm、Gd、Caおよび/もしくはいずれかのLn元素、またはこれらと(LaGdSr)(FeCo)O3-δの組み合わせからなる群から選定されることを特徴とする請求項14に記載の固体酸化物型燃料電池。
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CA2569866A1 (en) | 2005-12-22 |
CA2569866C (en) | 2011-05-17 |
US20070269701A1 (en) | 2007-11-22 |
RU2399996C1 (ru) | 2010-09-20 |
NO20070151L (no) | 2007-03-08 |
CN1985397B (zh) | 2012-07-04 |
JP2012069533A (ja) | 2012-04-05 |
KR100909120B1 (ko) | 2009-07-23 |
US7745031B2 (en) | 2010-06-29 |
WO2005122300A3 (en) | 2006-03-02 |
RU2356132C2 (ru) | 2009-05-20 |
RU2006144071A (ru) | 2008-07-20 |
AU2005253203A1 (en) | 2005-12-22 |
AU2005253203B2 (en) | 2009-05-28 |
RU2008152447A (ru) | 2010-07-10 |
EP1784888A2 (en) | 2007-05-16 |
KR20080105182A (ko) | 2008-12-03 |
JP2008502113A (ja) | 2008-01-24 |
EP2259373A1 (en) | 2010-12-08 |
WO2005122300A2 (en) | 2005-12-22 |
KR20070038511A (ko) | 2007-04-10 |
CN102013507A (zh) | 2011-04-13 |
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