JP2019112657A - Platinum powder and method for producing same and paste using platinum powder - Google Patents
Platinum powder and method for producing same and paste using platinum powder Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 39
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical class N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 2
- -1 oxygen ion Chemical class 0.000 claims description 12
- PDJBCBKQQFANPW-UHFFFAOYSA-L azanide;platinum(2+);dichloride Chemical compound [NH2-].[NH2-].[NH2-].[NH2-].Cl[Pt]Cl PDJBCBKQQFANPW-UHFFFAOYSA-L 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 9
- 150000003057 platinum Chemical class 0.000 claims description 8
- 239000007784 solid electrolyte Substances 0.000 claims description 8
- DZMFOGZJMORTEO-UHFFFAOYSA-L hydrogen carbonate;platinum(2+) Chemical compound [Pt+2].OC([O-])=O.OC([O-])=O DZMFOGZJMORTEO-UHFFFAOYSA-L 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
本発明は、白金粉末およびその製造方法、並びに白金粉末を用いたペーストに関するものである。 The present invention relates to platinum powder, a method of producing the same, and a paste using platinum powder.
酸素センサ等のガスセンサの電極において、高い電極活性を得るため、電極触媒である貴金属と、固体電解質であるイットリア安定化ジルコニアと、酸素等のガスと、の三成分が接触する面（三相界面）を多数形成することが重要である。 In an electrode of a gas sensor such as an oxygen sensor, a surface on which three components of a noble metal as an electrode catalyst, a yttria stabilized zirconia as a solid electrolyte, and a gas such as oxygen contact in order to obtain high electrode activity It is important to form many).
特許文献１には、酸素センサの電極形成方法として、電極材である白金粉末と安定化ジルコニア粉末を所定の比率で混合してさらに溶剤、樹脂を添加してペーストを得、イットリア安定化ジルコニア基材上に該ペーストを塗布、乾燥、焼成して電極を形成する方法が提案されている。
一方、特許文献２には、白金族元素または白金族元素を主体とする合金からなる金属フレークを製造する方法で、金属粒子原料の平均結晶子サイズが１〜５０ｎｍの範囲にある金属フレーク製造方法が開示されている。特許文献３には、形状が棒状で長軸の平均長さは１８．２ｎｍ、そのアスペクト比は５．０７である白金超微粒子及びその製造方法が開示されている。特許文献４には、白金によってその骨格が構成され、かつ厚さ２〜２５ｎｍ、外径３０〜６００ｎｍの単結晶質シート状粒子であって、直径１〜３．５ｎｍの六角形若しくは円形、又は幅１〜３．５ｎｍ、長さ３．５〜１０ｎｍの楕円形若しくは長方形の凹面状ナノホールが、４〜５ｎｍのほぼ等間隔又は１〜５ｎｍの不等間隔で配列した構造を有することを特徴とするシート状白金ナノ粒子とその製造方法が開示されている。特許文献５には、直径２０ｎｍの白金ナノ粒子、直径が２００〜６００ｎｍの白金ナノ繊維とその製造方法が開示されている。特許文献６には、平均粒子径が１ｎｍ〜５０ｎｍの範囲内にある楕円体形状の白金微粒子とその製造方法が開示されている。
In Patent Document 1, as a method of forming an electrode of an oxygen sensor, a platinum powder as an electrode material and a stabilized zirconia powder are mixed in a predetermined ratio, and a solvent and a resin are further added to obtain a paste. A method has been proposed in which the paste is applied onto a material, dried and fired to form an electrode.
On the other hand, Patent Document 2 discloses a method for producing metal flakes composed of an alloy mainly composed of platinum group elements or platinum group elements, wherein the average crystallite size of the metal particle raw material is in the range of 1 to 50 nm. Is disclosed. Patent Document 3 discloses platinum ultrafine particles having a rod-like shape, an average length of a long axis of 18.2 nm, and an aspect ratio of 5.07, and a method for producing the same. Patent Document 4 describes a single crystalline sheet-like particle having a skeleton of platinum and having a thickness of 2 to 25 nm and an outer diameter of 30 to 600 nm, and is hexagonal or circular, or 1 to 3.5 nm in diameter. Characterized in that elliptical or rectangular concave nanoholes having a width of 1 to 3.5 nm and a length of 3.5 to 10 nm are arranged at substantially equal intervals of 4 to 5 nm or at unequal intervals of 1 to 5 nm Discloses sheet-like platinum nanoparticles and a method for producing the same. Patent Document 5 discloses platinum nanoparticles having a diameter of 20 nm, platinum nanofibers having a diameter of 200 to 600 nm, and a method for producing the same. Patent Document 6 discloses ellipsoidal platinum fine particles having an average particle diameter in the range of 1 nm to 50 nm and a method for producing the same.
ガスセンサの電極（電極触媒層）は高い電極活性を有することと、電気抵抗率が低いことと、高い熱的安定性を有することとが要求される。まず、電極活性を高めるには、反応場となる大気と貴金属と固体電解質とが接する三相界面の量を増やす必要がある。三相界面を増やすためには、ガス拡散性を増加させるために電極を多孔化させることが重要となる。電気抵抗率を低減するためには、白金粒子を焼結させることで白金粒子同士のつながりを高めることが重要となる。熱的安定性は、粉末の粒径に関連があり、ナノ粒子などの粒径が小さいものは焼結の進行が大きく、熱的安定性が低い傾向があり、粒径が大きいと熱的安定性が良い傾向が高い。 The electrode (electrode catalyst layer) of the gas sensor is required to have high electrode activity, low electrical resistivity, and high thermal stability. First, in order to enhance the electrode activity, it is necessary to increase the amount of the three-phase interface at which the atmosphere serving as the reaction site, the noble metal, and the solid electrolyte are in contact. In order to increase the three-phase interface, it is important to make the electrode porous in order to increase the gas diffusivity. In order to reduce the electrical resistivity, it is important to enhance the connection between the platinum particles by sintering the platinum particles. Thermal stability is related to the particle size of the powder, and those with small particle size such as nanoparticles tend to have a large degree of sintering progress and thermal stability tend to be low, and large particle sizes cause thermal stability. The tendency is good.
本発明はこうした問題を鑑みなされたもので、電気抵抗率を確保しつつ、電極活性を向上させる白金粉末およびその白金粉末の製造方法を提供することを目的としている。 The present invention has been made in view of these problems, and it is an object of the present invention to provide a platinum powder that improves the electrode activity while securing the electrical resistivity, and a method for producing the platinum powder.
本発明者らは、上記の目的を達成すべく鋭意検討した結果、粉末形状を棒状とすると、ペースト塗付時の印刷方向に白金粒子が整列しやすい一方、深さ方向には粒子形状が非球面形状だから充填率が低下して、抵抗率を所定の値に確保しつつ、充填性が低下して焼成膜中に気孔形成されやすく、三相界面の量が増加すること、を着想し、テトラアンミン白金（II）テトラクロロ白金（II）やテトラアンミン白金炭酸水素塩などのテトラアンミン白金を有する固体を熱分解することで棒状白金粉末を作製できることを見出した。そして、その白金粉末をイットリア安定化ジルコニア粒子とバインダと溶剤を混合してペーストとすると、電極作製時に電極界面抵抗を低減させることと、抵抗率が所定の値に確保できることとを見出した。 As a result of intensive studies to achieve the above object, the present inventors set the powder shape to a rod shape, and while the platinum particles are easily aligned in the printing direction at the time of paste application, the particle shape is not uniform in the depth direction. Since it is a spherical shape, it is conceived that the filling rate is lowered and the filling property is lowered and pores are easily formed in the fired film while securing the resistivity to a predetermined value, and the amount of the three phase interface is increased. It has been found that a rod-like platinum powder can be produced by thermally decomposing a solid having tetraammineplatinum such as tetraammineplatinum (II), tetrachloroplatinum (II), tetraammineplatinum hydrogencarbonate and the like. Then, when the platinum powder was mixed with yttria-stabilized zirconia particles, a binder and a solvent to form a paste, it was found that the electrode interface resistance can be reduced at the time of electrode preparation and that the resistivity can be maintained at a predetermined value.
本発明は、粒子の短径が０．５μｍ〜９μｍであり、該粒子の外観における長径（Ａ）と短径（Ｂ）との比Ａ／Ｂが２〜１４であることを特徴とする白金または白金合金粉末である。 The present invention is characterized in that the minor diameter of the particle is 0.5 μm to 9 μm, and the ratio A / B of the major diameter (A) to the minor diameter (B) in the appearance of the particle is 2 to 14 Or platinum alloy powder.
上記の構成において、該粒子の粒子形状が棒状であるようにしてもよい。 In the above configuration, the particle shape of the particles may be rod-like.
また、本発明にかかるペーストは、上記粉末と、酸素イオン電導性を有する固体電解質と、樹脂と、溶剤とを含むペーストである。 Moreover, the paste concerning this invention is a paste containing the said powder, the solid electrolyte which has oxygen ion conductivity, resin, and a solvent.
上記の構成において、固体電解質がイットリア安定化ジルコニアであるようにしてもよい。 In the above configuration, the solid electrolyte may be yttria stabilized zirconia.
また、本発明の白金粉末の製造方法は、テトラアンミン白金塩を５００℃未満の温度域で熱分解することを特徴とする。上記製造方法において、テトラアンミン白金塩が、テトラアンミン白金（II）テトラクロロ白金（II）又はテトラアンミン白金炭酸水素塩であるようにしてもよい。また、上記製造方法において、塩化白金酸にテトラアンミン白金ジクロライドを混合撹拌し、濾過することにより前記テトラアンミン白金（II）テトラクロロ白金（II）を得る工程又はテトラアンミン白金ジクロライドに重炭酸アンモニウムを混合し濾過することにより前記テトラアンミン白金炭酸水素塩を得る工程を更に含んでもよい。 Furthermore, the method for producing platinum powder of the present invention is characterized in that the tetraammine platinum salt is thermally decomposed in a temperature range of less than 500 ° C. In the above manufacturing method, the tetraammine platinum salt may be tetraammine platinum (II) tetrachloroplatinum (II) or tetraammine platinum hydrogen carbonate. In the above production method, chloroplatinic acid is mixed and stirred with tetraammineplatinum dichloride, and filtered to obtain the above-mentioned tetraammineplatinum (II) tetrachloroplatinum (II), or by mixing ammonium bicarbonate with tetraammineplatinum dichloride for filtration. The method may further include the step of obtaining the tetraammine platinum hydrogen carbonate by conducting the reaction.
本発明に従うと、高い電極活性を有し、抵抗が低く、高い熱的安定性を有する白金粉末およびその白金粉末の製造方法ならびにペーストを提供することができる。 According to the present invention, it is possible to provide a platinum powder having high electrode activity, low resistance, and high thermal stability, a method for producing the platinum powder, and a paste.
以下、本発明の白金粉末およびその製造方法、並びに白金粉末を用いたペーストについて、さらに詳細に説明する。 Hereinafter, the platinum powder of the present invention, the method for producing the same, and the paste using the platinum powder will be described in more detail.
本件発明の白金粉末は、粒子の短径が０．５μｍ〜９μｍであり、粒子の外観における長径（Ａ）と短径（Ｂ）との比Ａ／Ｂが２〜１４である。 In the platinum powder of the present invention, the minor axis of the particles is 0.5 μm to 9 μm, and the ratio A / B of the major axis (A) to the minor axis (B) in the appearance of the particles is 2-14.
粒子形状は棒状である。粒子表面は凹凸を呈していてもよい。粒子は多孔質であってもよい。 The particle shape is rod-like. The particle surface may have irregularities. The particles may be porous.
粒子の短径は０．５μｍ〜６μｍであり、粒子の外観における長径（Ａ）と短径（Ｂ）との比Ａ／Ｂが３〜１０であることが好ましい。粒子の短径は１μｍ〜５μｍであり、粒子の外観における長径（Ａ）と短径（Ｂ）との比Ａ／Ｂが３〜８であることがさらに好ましい。 The minor axis of the particle is 0.5 μm to 6 μm, and the ratio A / B of the major axis (A) to the minor axis (B) in the appearance of the particle is preferably 3 to 10. The minor diameter of the particles is 1 μm to 5 μm, and the ratio A / B of the major diameter (A) to the minor diameter (B) in the appearance of the particles is more preferably 3 to 8.
次に白金粉末の製造方法を説明する。 Next, a method of producing platinum powder will be described.
本発明の白金粉末の製造方法は、テトラアンミン白金塩を５００℃未満の温度域で熱分解することを特徴とする白金粉末の製造方法である。熱分解温度は３００℃以上が好ましい。３３０℃以上がより好ましい。 The method for producing a platinum powder according to the present invention is a method for producing a platinum powder comprising: thermal decomposition of a tetraammine platinum salt in a temperature range of less than 500 ° C. The thermal decomposition temperature is preferably 300 ° C. or higher. 330 degreeC or more is more preferable.
テトラアンミン白金塩の具体例は、テトラアンミン白金（II）テトラクロロ白金（II）又はテトラアンミン白金炭酸水素塩である。 Specific examples of the tetraammine platinum salt are tetraammine platinum (II) tetrachloroplatinum (II) or tetraammine platinum hydrogen carbonate.
テトラアンミン白金（II）テトラクロロ白金（II）は、塩化白金酸にテトラアンミン白金ジクロライドを混合撹拌し、濾過することにより得られる。テトラアンミン白金炭酸水素塩は、テトラアンミン白金ジクロライドに重炭酸アンモニウムを混合し濾過することにより得られる。 Tetraammineplatinum (II) Tetrachloroplatinum (II) is obtained by mixing and stirring chloroplatinic acid and tetraammineplatinum dichloride, and filtering. The tetraammine platinum hydrogen carbonate can be obtained by mixing ammonium bicarbonate with tetraammine platinum dichloride and filtering.
テトラアンミン白金（II）テトラクロロ白金（II）は、マグヌス塩とも称呼され、化学式が [Pt(NH3)4][PtCl4] と表される白金の化合物であり、テトラアンミン白金の塩である。 Tetraammineplatinum (II) tetrachloro platinum (II) is also Magnus salt is referred is a compound of platinum formula is represented as [Pt (NH3) 4] [ PtCl 4], a salt of tetraammineplatinum.
テトラアンミン白金炭酸水素塩は、テトラアンミン白金の塩である。 Tetraammineplatinum hydrogen carbonate is a salt of tetraammineplatinum.
テトラアンミン白金（II）テトラクロロ白金（II）はテトラアンミン白金（II）とテトラクロロ白金（II）とが交互にポリマー状にならび棒状構造となる。テトラアンミン白金炭酸水素塩も棒状構造をとる。このような、棒状構造のテトラアンミン白金塩を５００℃未満の温度域で熱分解する。棒状構造をとる出発物質を熱分解することにより、得られる白金粉末において棒状構造の形状が保存され、棒状の白金粉末が得られる。 Tetraammineplatinum (II) Tetrachloroplatinum (II) has a rod-like structure in which tetraammineplatinum (II) and tetrachloroplatinum (II) alternately form a polymer. The tetraammine platinum hydrogen carbonate also has a rod-like structure. Such a rod-shaped tetraammine platinum salt is thermally decomposed in a temperature range of less than 500.degree. By pyrolyzing the starting material having a rod-like structure, the shape of the rod-like structure is preserved in the obtained platinum powder, and a rod-like platinum powder is obtained.
本発明の白金粉末の製造方法は、具体的には、塩化白金（II）酸水溶液にテトラアンミン白金ジクロライド水溶液を添加撹拌し、濾過してテトラアンミン白金（II）テトラクロロ白金（II）からなる化合物の沈殿物とし、それを乾燥させ、乾燥させた固体を、大気中で５００℃以下の温度で熱処理、粉砕して白金粉末を得る。 Specifically, the method for producing a platinum powder of the present invention comprises adding a tetraammineplatinum dichloride aqueous solution to a platinum (II) chloride acid aqueous solution with stirring, filtering and adding a compound comprising tetraammineplatinum (II) tetrachloroplatinum (II) The precipitate is dried, and the dried solid is heat-treated at a temperature of 500 ° C. or less in the atmosphere to be crushed to obtain platinum powder.
本発明の白金粉末の製造方法は、または、テトラアンミン白金ジクロライド水溶液に重炭酸アンモニウムを添加し、濾過してテトラアンミン白金炭酸水素塩からなる化合物の沈殿物とし、それを乾燥させ、乾燥させた固体を、大気中で５００℃以下の温度で熱処理、粉砕して、白金粉末を得る。 In the method for producing platinum powder of the present invention, alternatively, ammonium bicarbonate is added to an aqueous solution of tetraammineplatinum dichloride, followed by filtration to obtain a precipitate of a compound consisting of tetraammineplatinum hydrogencarbonate, which is dried and dried. Heat treatment and pulverization in the atmosphere at a temperature of 500 ° C. or less to obtain platinum powder.
次にペーストを説明する。 Next, the paste will be described.
本願の棒状白金粉末と、 酸素イオン伝導性を有する固体電解質と、樹脂と、溶剤とを混合してペーストを製造する。 A paste is produced by mixing the rod-like platinum powder of the present invention, a solid electrolyte having oxygen ion conductivity, a resin and a solvent.
具体的には、固体電解質はイットリア安定化ジルコニア、酸化スカンジウム安定化ジルコニア、イットリア安定化セリアを使用することができる。 Specifically, as the solid electrolyte, yttria-stabilized zirconia, scandium oxide-stabilized zirconia, or yttria-stabilized ceria can be used.
イットリア安定化ジルコニア粒子は、平均粒径０．１〜１．５μｍのものが使用できる。 Yttria-stabilized zirconia particles having an average particle diameter of 0.1 to 1.5 μm can be used.
樹脂は、例えば、エチルセルロース、アルキッド、ポリビニルブチラール、アクリル樹脂などを用いることができる。 As the resin, for example, ethyl cellulose, alkyd, polyvinyl butyral, acrylic resin and the like can be used.
溶剤は、タービネオール、エチレングリコール、プロピレングリコール、エチレングリコールモノフェニルエーテル、ベンジルアルコール、ケロシン、パラフィン、γ―ブチロラクトン、Ｎ−メチルピロリドン、ブチルカルビトール、テレピン油、α―テルピネオール、テルソルブを用いることができる。 As the solvent, terbineol, ethylene glycol, propylene glycol, ethylene glycol monophenyl ether, benzyl alcohol, kerosene, paraffin, γ-butyrolactone, N-methylpyrrolidone, butyl carbitol, turpentine oil, α-terpineol, tersorb can be used. .
以下、本発明を実施例によりさらに具体的に説明する。 Hereinafter, the present invention will be more specifically described by way of examples.
（白金粉末の実施例１）
白金１０ｇを含む塩化白金（II）酸水溶液５０ｍｌに白金１０ｇを含むテトラアンミン白金ジクロライド水溶液２００ｍｌを室温で添加撹拌し、濾過してテトラアンミン白金（II）テトラクロロ白金（II）からなる化合物の沈殿物を得た。それを乾燥させた。その固体を、大気中で３５０℃で熱処理、粉砕して白金粉末を得た。得られた粒子の走査型電子顕微鏡（ＳＥＭ）写真を撮影した。図１にその写真を示す。
(Example 1 of platinum powder)
Add 200 ml of tetraammine platinum dichloride aqueous solution containing 10 g of platinum to 50 ml of platinum chloride (II) acid aqueous solution containing 10 g of platinum, stir at room temperature, filter and precipitate the compound consisting of tetraammine platinum (II) tetrachloroplatinum (II) Obtained. I dried it. The solid was heat-treated at 350 ° C. in the atmosphere and pulverized to obtain platinum powder. A scanning electron microscope (SEM) picture of the resulting particles was taken. The photograph is shown in FIG.
（白金粉末の実施例２）
白金１０ｇを含むテトラアンミン白金ジクロライド水溶液２００ｍｌに重炭酸アンモニウムを室温で添加し、濾過してテトラアンミン白金炭酸水素塩からなる化合物の沈殿物を得た。それを乾燥させた。その固体を、大気中で３５０℃で熱処理、粉砕して、白金粉末を得た。得られた粒子の走査型電子顕微鏡（ＳＥＭ）写真を撮影した。図２にその写真を示す。
(Example 2 of platinum powder)
Ammonium bicarbonate was added to 200 ml of an aqueous solution of tetraammine platinum dichloride containing 10 g of platinum at room temperature, followed by filtration to obtain a precipitate of a compound consisting of tetraammine platinum hydrogen carbonate. I dried it. The solid was heat-treated at 350 ° C. in the atmosphere to be crushed to obtain platinum powder. A scanning electron microscope (SEM) picture of the resulting particles was taken. The photograph is shown in FIG.
（白金粉末の比較例）
比較例の白金粉末は、塩化白金酸水溶液にヒドラジン水和物を加えて還元し、得られた沈澱を洗浄、ろ過、乾燥を行って作成した。白金粉末は平均粒径が１μｍの球形粉末であった。得られた粒子の走査型電子顕微鏡（ＳＥＭ）写真を撮影した。図３にその写真を示す。
(Comparative example of platinum powder)
The platinum powder of the comparative example was prepared by adding hydrazine hydrate to a chloroplatinic acid aqueous solution for reduction, and washing, filtering and drying the resulting precipitate. The platinum powder was a spherical powder with an average particle size of 1 μm. A scanning electron microscope (SEM) picture of the resulting particles was taken. The photograph is shown in FIG.
得られた粒子の形状寸法は走査型電子顕微鏡写真より測定した。アスペクト比（Ａ／Ｂ）は、走査型電子顕微鏡写真の該粒子撮影像における長径（Ａ）と短径（Ｂ）との比として求めた。円形度（Ｄ／Ｃ）は、該粒子撮影像の周長（Ｃ）と該粒子撮影像と同面積を有する円の円周（Ｄ）との比として求めた。粒子３０点の形状寸法の測定結果（平均値）を表１に示す。測定結果の最小最大値は、粉末実施例１では、短径：０．５μｍ〜３．０μｍ、アスペクト比：２〜１４であった。粉末実施例２では、短径：１．４μｍ〜８．７μｍ、アスペクト比：３〜１２であった。 The shape and size of the obtained particles were measured from a scanning electron micrograph. The aspect ratio (A / B) was determined as the ratio of the major axis (A) to the minor axis (B) in the particle image of the scanning electron micrograph. The degree of circularity (D / C) was determined as the ratio of the circumferential length (C) of the particle photographed image to the circumference (D) of a circle having the same area as the particle photographed image. The measurement results (average value) of the shape and size of 30 particles are shown in Table 1. In Powder Example 1, the minimum maximum value of the measurement result was 0.5 μm to 3.0 μm, and the aspect ratio was 2 to 14. In Powder Example 2, the minor axis: 1.4 μm to 8.7 μm, and the aspect ratio: 3 to 12.
（ペーストの実施例）
実施例１にて合成した白金粉末を濃度７０ｍａｓｓ％と、イットリア安定化ジルコニア濃度を１０ｍａｓｓ％と、ビヒクル（エチルセルロースおよびターピネオール）濃度を約２０ｍａｓｓ％とし、３本ロールミルにて混練して、ペーストを得た。
(Example of paste)
The platinum powder synthesized in Example 1 is mixed with a concentration of 70 mass%, an yttria stabilized zirconia concentration of 10 mass%, and a vehicle (ethyl cellulose and terpineol) concentration of about 20 mass% by a triple roll mill to obtain a paste The
（ペーストの比較例１）
球形状の白金粉末を濃度７０ｍａｓｓ％と、イットリア安定化ジルコニア濃度を１０ｍａｓｓ％と、ビヒクル（エチルセルロースおよびターピネオール）濃度を約２０ｍａｓｓ％として３本ロールミルにて混練し、ペーストを得た。
(Comparative example 1 of paste)
A spherical platinum powder was kneaded at a concentration of 70 mass%, a yttria-stabilized zirconia concentration of 10 mass%, and a vehicle (ethyl cellulose and terpineol) concentration of about 20 mass% with a three roll mill to obtain a paste.
（ペーストの比較例２）
球形状の白金粉末を濃度７０ｍａｓｓ％と、イットリア安定化ジルコニア濃度を１０ｍａｓｓ％と、ビヒクル（エチルセルロースおよびターピネオール）濃度を約１２ｍａｓｓ％と、造孔材を８ｍａｓｓ％として３本ロールミルにて混練し、ペーストを得た。
(Comparative example 2 of paste)
A mixture of spherical platinum powder with a concentration of 70 mass%, a yttria-stabilized zirconia concentration of 10 mass%, a vehicle (ethyl cellulose and terpineol) concentration of approximately 12 mass%, and a pore former of 8 mass% is kneaded with a three roll mill. I got
ジルコニアグリーンシート両面に実施例、比較例１および２のペーストを印刷し、１５００℃２時間焼成して電極触媒層を作成した。ジルコニアグリーンシート両面の電極触媒層間のインピーダンスを、周波数特性分析器を用いて測定した。インピーダンス測定は大気中６００℃、電圧値５０ｍＶ、周波数１００ｋＨｚ〜１００ｍＨｚで行った。得られたインピーダンスの値から、両面の電極触媒層の抵抗（電極界面抵抗という）を算出した。 The pastes of Examples and Comparative Examples 1 and 2 were printed on both sides of the zirconia green sheet, and fired at 1500 ° C. for 2 hours to form an electrode catalyst layer. The impedance between the electrode catalyst layers on both sides of the zirconia green sheet was measured using a frequency characteristic analyzer. The impedance measurement was performed at 600 ° C. in the air at a voltage value of 50 mV and a frequency of 100 kHz to 100 mHz. From the value of the obtained impedance, the resistance (referred to as electrode interface resistance) of the electrode catalyst layer on both sides was calculated.
得られた結果を表２に示す。表２の通り、ペーストの実施例では、比較例１、比較例２と比べて電極界面抵抗が低くなるという優れた特性を示す。比抵抗については比較例１と同等の特性を示している。 The obtained results are shown in Table 2. As shown in Table 2, the paste examples show excellent characteristics that the electrode interface resistance is lower than that of Comparative Examples 1 and 2. The resistivity shows the same characteristics as in Comparative Example 1.
Claims (7)
該粒子の外観における長径（Ａ）と短径（Ｂ）との比Ａ／Ｂが２〜１４であることを特徴とする白金粉末。 The minor diameter of the particles is 0.5 μm to 9 μm,
A platinum powder characterized in that the ratio A / B of the major axis (A) to the minor axis (B) in the appearance of the particles is 2 to 14.
酸素イオン伝導性を有する固体電解質と、
樹脂と、
溶剤と、
を含むことを特徴とするペースト。 The powder according to claim 1 or 2,
A solid electrolyte having oxygen ion conductivity;
With resin,
Solvent,
A paste characterized in that it contains
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