JP5126535B2 - 複合体型混合導電体 - Google Patents
複合体型混合導電体 Download PDFInfo
- Publication number
- JP5126535B2 JP5126535B2 JP2008292866A JP2008292866A JP5126535B2 JP 5126535 B2 JP5126535 B2 JP 5126535B2 JP 2008292866 A JP2008292866 A JP 2008292866A JP 2008292866 A JP2008292866 A JP 2008292866A JP 5126535 B2 JP5126535 B2 JP 5126535B2
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- Prior art keywords
- oxygen
- conductive phase
- mixed
- phase
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011533 mixed conductor Substances 0.000 title claims description 57
- 239000002131 composite material Substances 0.000 title claims description 54
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 117
- 239000001301 oxygen Substances 0.000 claims abstract description 112
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 66
- -1 oxygen ion Chemical class 0.000 claims abstract description 44
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000035699 permeability Effects 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 5
- 239000010416 ion conductor Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000011532 electronic conductor Substances 0.000 abstract 1
- 229910000859 α-Fe Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 86
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 52
- 238000000034 method Methods 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 229910000420 cerium oxide Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002407 reforming Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000004697 chelate complex Chemical class 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000629 steam reforming Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229960004543 anhydrous citric acid Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
Classifications
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C04B35/2666—Other ferrites containing nickel, copper or cobalt
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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Description
(1)単相型混合導電体
これは、その物質自体が混合導電性を有するものであり、例としては、La−Sr−Co−Fe、およびLa−Sr−Ga−Fe系ペロブスカイト型酸化物が知られている(文献:Chem.Lett.,(1985)1743、Am.Ceram.Soc.Bull.,74(1995)71、Catal.Today,36(1997)265、SolidState Ionics,129(2000)285、Solid State Ionics,135(2000)631参照)。
(2)複合体型混合導電体
これは、単体としては、酸素イオン導電性または電子導電性のいずれか一方しか示さない物質を複合体とすることにより混合導電性を発現させるものであり、例としてはイオン導電体であるイットリウム安定化ジルコニア(YSZ)と電子伝導体である金属Pdの混合体やガドリニウム添加セリウム酸化物とLa−Sr−Mn系ペロブスカイト型酸化物の混合体等がある。
単相型混合導電体の場合は高い混合導電性が得られる物質系が非常に限られているのに対し、複合体型では幅広い材料が適用対象となりうる。また、複合体型混合導電体では数種類の物質を含有することから、副次的な機能、例えば触媒機能等を付与することも可能となる。
本発明の複合体混合導電体において、酸素イオン導電相は、酸素ガスの酸素イオン化及び酸素イオンの酸素化を促進する触媒を含有しているか、上記触媒が塗布されているか、または上記触媒を含有しかつ上記触媒が表面に塗布されている。ここで、触媒は、RuまたはNi、またはこれらの組み合わせである。
ガドリニウム添加セリウム酸化物を構成する金属の塩と、スピネル型Fe複合酸化物を構成する金属の塩と、酸素ガスの酸素イオン化及び酸素イオンの酸素化を促進する触媒と、キレート錯体と、キレート重合剤とを混合して高分子化し、この高分子化した混合相を炭化し、この炭化した混合相の炭素を酸化脱離して上記金属の酸化物を作製し、この酸化物を粉砕し、この粉砕した酸化物を加圧焼成して作製する。
前記触媒は、加圧焼成後に塗布しても良い。ガドリニウム添加セリウム酸化物を構成する金属の塩は、好ましくは、Ce(NO3)3・6H2O及びGd(NO3)3・5H2O、またはCe(NO3)3・6H2O及びGd(OH)3であり、スピネル型Fe複合酸化物相を構成する金属の塩は、Fe(NO3)3・9H2O、Co(NO3)2・6H2O、Ni(NO3)2・6H2O、または、Mn(NO3)2・6H2Oのいずれか1つ、またはこれらの組み合わせであり、触媒はRuまたはNi、またはこれらの組み合わせであり、キレート錯体は無水クエン酸であり、キレート重合剤はエチレングリコールである。
プラセオジム添加セリウム酸化物を構成する金属の塩と、スピネル型Fe複合酸化物を構成する金属の塩と、酸素ガスの酸素イオン化及び酸素イオンの酸素化を促進する触媒と、キレート錯体と、キレート重合剤とを混合して高分子化し、この高分子化した混合相を炭化し、この炭化した混合相の炭素を酸化脱離して上記金属の酸化物を作製し、この酸化物を粉砕し、粉砕した酸化物を加圧焼成して作製する。
前記触媒は、加圧焼成後に塗布しても良い。プラセオジム添加セリウム酸化物を構成する金属の塩は、好ましくは、Ce(NO3)3・6H2O及びPr(NO3)3・5H2O、またはCe(NO3)3・6H2O及びPr(OH)3であり、スピネル型Fe複合酸化物相を構成する金属の塩は、Fe(NO3)3・9H2O、Co(NO3)2・6H2O、Ni(NO3)2・6H2O、または、Mn(NO3)2・6H2Oのいずれか1つ、またはこれらの組み合わせであり、触媒はRuまたはNi、またはこれらの組み合わせであり、キレート錯体は無水クエン酸であり、キレート重合剤はエチレングリコールである。
本発明の作製方法は、液相混合法、別名、Pechini法、あるいは錯体重合法を使用することを特徴としている。この方法によれば、単なる液体状態の混合ではなく、種々の金属元素を重合体の中に閉じ込めることによる原子レベルでの混合状態を得て、引き続く焼成において均一な組成を有する試料を作製することができる。単に硝酸塩や塩化物を水に溶かしただけでは、液体の状態では原子レベルで混合されるが、蒸発に伴い各塩が粒として析出してしまう。液相混合法では錯体(ポリマー)の中に金属元素が閉じ込められるので、液相から固相になっても均一な混合状態が保たれる。本発明では、イオン導電体と電子伝導体を均一にかつ微細に混合する必要があるため、液相混合法を使用する。また、その均一混合性が良いために、一般に、両相が予期しない副次的な反応を引き起こすものであるが、本発明の、ガドリニウム添加セリウム酸化物(組成式:Ce1−xGdxO2−x/2)相とスピネル型Fe複合酸化物(組成式:MFe2O4、ただし、M=Mn,Fe,Co又はNi)相、または、プラセオジム添加セリウム酸化物(組成式:Ce1−xPrxO2−x/2)相とスピネル型Fe複合酸化物相では、このような好ましくない副次的な反応が極めて少ない。
図1において、白い部分が酸素イオン導電相のGDC、黒い部分が電子導電相のCFOである(微少領域組成解析装置により確認した)。GDC、CFOともに0.2〜0.5μmの結晶粒径となっていることがわかる。また、図2において顕著にみられるように、粒子の粒界領域に、約50nmの幅をもつ粒界相の存在が確認される。通常の複合体型混合導電体ではこのような粒界相の生成が混合導電性を阻害するが、本試料においては、この部分は各々10nm程度の超微細なGDCとCFOの混合状態となっていることが確認された。
x=16.7,31.4,64.6vol%の三種類の試料の粉末X線回折像を示している。図において、○はCexGd1−xO2固溶体に起因する回折ピークであり、▼はCoFe2O4(Feスピネル酸化物)に起因する回折ピークである。粉末X線回折の結果から、GDCはCexGd1−xO2固溶体であり、CFOはCoFe2O4(Feスピネル酸化物)であることが確認された。
なお、1000℃で長時間、空気からの酸素分離またはメタンの部分酸化に使用した後に、GdFeO3ペロブスカイト型酸化物の微弱な回折ピークが観測されたが、酸素分離またはメタンの部分酸化能力に変化がないことから、この酸化物は混合導電性を阻害しない。
電気的特性は、一定酸素分圧中、一定温度中に試料を固定し、試料から電極を引き出して4端子法で測定した。試料の電気特性は、酸素分圧が1〜10−6atmの範囲においてはp型ホール伝導が優勢であり、また、酸素分圧が10−6atm以下の範囲においてはn型電子伝導が優勢である混合導電体であることが確認された。
図から明らかなように、本発明のGDC−CFO複合体型混合導電体の酸素透過特性は、従来のものと同等もしくはそれ以上の酸素透過特性を示している。
また、触媒としてNiおよびRuを含有させ、表面にNi触媒を塗布したもの(24CFO−Niおよび24CFO−Ru)はさらに高い酸素透過特性を示した。これに加えて特筆すべきことは、24CFO−Ru試料において、キャリアガスをAr−H2とした場合、酸素透過速度が1.26μmol・cm−2・s−1と、単相型混合導電体に匹敵する酸素透過特性を示した点である。この24CFO−Ru試料は、Ar−H2下での酸素透過実験中も化学的・機械的に安定であった。以上のことから、本発明のGDC−CFO複合体は新規な高性能混合導電体・酸素透過膜であることがわかる。
なお、図5において、比較に用いた25GCCとは、酸素イオン導電相GDCに、組成式(Gd1−xCax)CoO3で表される電子導電相GCCを体積比で25%混合した複合型混合導電体である。また、25LSMとは、酸素イオン導電相GDCに、組成式(La1−xSrx)MnO3で表される電子導電相LSMを体積比で25%混合した複合型混合導電体である。
図7は本発明の複合体型混合導電体の酸素透過係数の、電子導電相の酸素イオン導電相に対する体積組成依存性を示す図である。測定に用いた試料は、酸素イオン導電相がGDC、電子導電相がMnFe2O4である。横軸は、MnFe2O4相のGDC相に対する体積分率xを示し、縦軸は酸素透過係数を示す。測定温度は800℃、900℃及び1000℃である。
図からわかるように、x=5%から実用可能な酸素透過係数を有しており、1000℃のグラフに見られるようにx=40%を越えると酸素透過係数が急激に小さくなる。従って、電子導電相の酸素イオン導電相に対する好ましい体積組成は5%〜40%の範囲である。
図9は本発明の複合体型混合導電体によるメタン部分酸化特性を示し、(a)はメタン部分酸化中のCH4、H2及びCOの濃度変化を示す図であり、横軸はメタン部分酸化時間を示しており、左の縦軸はCH4、H2及びCOの濃度を示し、右の縦軸は酸素透過速度jO2を示す。なお、メタン部分酸化は図中に示しているように、温度を800℃から1000℃まで段階的に上昇させて行った。図9(b)は上記のメタン部分酸化中におけるH2/CO濃度比及びH2、COの選択率(Selectivity)を示す図である。左の縦軸はH2/CO濃度比を示し、右の縦軸は選択率を示す。
また、本実施例は上図から明らかなように、800〜1000℃において約1時間連続して動作させたが、動作中及び動作後において特性の劣化が見られず、また、相の分解やクラックも発生しなかった。このことから、本発明の複合体型混合導電体は、化学的・熱的にも十分な安定性を有しており、劣化が生じない複合体型混合導電体である。
2:ソーダガラスのリング
3:セラミック板
4:透過酸素測定部
5:大気圧印加部
6:金リング
7:試料
8:アルミナ管
9:熱電対
10:アルミナ管
Claims (3)
- 酸素イオン導電相及び電子導電相の各相が相互に混合されてなり、
上記酸素イオン導電相がガドリニウム添加セリウム酸化物(組成式:Ce1-x Gd xO2-x/2、ただし0<x<0.5)からなり、
上記電子導電相がスピネル型Fe複合酸化物(組成式:MFe2O4、ただし、M=Mn,Fe,Co又はNi)からなり、
上記電子導電相の上記酸素イオン導電相に対する体積組成が、5%から40%までの範囲であり、
上記酸素イオン導電相及び上記電子導電相が、それぞれ0.2μmから0.5μmまでの範囲の微粒径を有し均一に混合されていて、上記各相がそれぞれ導電ネットワークを形成しており、
各々10nm程度の超微細な酸素イオン導電相及び電子導電相の混合状態となる粒界相が粒界領域に形成されている、複合体型混合導電体。 - 前記酸素イオン導電相は、酸素ガスの酸素イオン化及び酸素イオンの酸素化を促進する触媒を含有しているか、上記触媒が塗布されているか、または上記触媒を含有しかつ上記触媒が表面に塗布されている、請求項1に記載の複合体型混合導電体。
- 前記触媒は、RuまたはNi、またはこれらの組み合わせである、請求項2に記載の複合体型混合導電体。
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US6332964B1 (en) * | 1996-12-31 | 2001-12-25 | Praxair Technology, Inc. | Multi-phase solid ion and electron conducting membrane with low volume percentage electron conducting phase and methods for fabricating |
JP2000260436A (ja) * | 1999-03-10 | 2000-09-22 | Tokyo Gas Co Ltd | 低温活性電極を有する支持膜式固体電解質型燃料電池および該燃料電池に使用する空気極の作製方法 |
US6471921B1 (en) * | 1999-05-19 | 2002-10-29 | Eltron Research, Inc. | Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing |
JP2002333424A (ja) * | 2001-05-08 | 2002-11-22 | Ibiden Co Ltd | 酸素センサー |
CA2450679C (en) * | 2001-06-29 | 2010-08-31 | Nextech Materials, Ltd. | Nano-composite electrodes and method of making the same |
JP3975184B2 (ja) * | 2003-08-07 | 2007-09-12 | Tdk株式会社 | 複合体型混合導電体の製造方法 |
JP4712310B2 (ja) * | 2004-03-30 | 2011-06-29 | Tdk株式会社 | 複合体型混合導電体の製造方法 |
-
2003
- 2003-04-08 WO PCT/JP2003/004435 patent/WO2003084894A1/ja active Application Filing
- 2003-04-08 JP JP2003582095A patent/JP4277200B2/ja not_active Expired - Lifetime
- 2003-04-08 US US10/510,343 patent/US7223358B2/en not_active Expired - Lifetime
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2007
- 2007-04-13 US US11/783,946 patent/US7479242B2/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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US7479242B2 (en) | 2009-01-20 |
JP4277200B2 (ja) | 2009-06-10 |
US7223358B2 (en) | 2007-05-29 |
WO2003084894A1 (fr) | 2003-10-16 |
JPWO2003084894A1 (ja) | 2005-08-11 |
US20070252114A1 (en) | 2007-11-01 |
US20050142053A1 (en) | 2005-06-30 |
JP2009087944A (ja) | 2009-04-23 |
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