WO2014136908A1 - 燃料電池電極材料用タンタル含有酸化スズ - Google Patents
燃料電池電極材料用タンタル含有酸化スズ Download PDFInfo
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- WO2014136908A1 WO2014136908A1 PCT/JP2014/055852 JP2014055852W WO2014136908A1 WO 2014136908 A1 WO2014136908 A1 WO 2014136908A1 JP 2014055852 W JP2014055852 W JP 2014055852W WO 2014136908 A1 WO2014136908 A1 WO 2014136908A1
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Definitions
- the present invention relates to tantalum-containing tin oxide for fuel cell electrode materials.
- the present invention also relates to a fuel cell electrode catalyst in which a catalyst is supported on tantalum-containing tin oxide, a membrane electrode assembly including the electrode catalyst, and a polymer electrolyte fuel cell.
- the polymer electrolyte fuel cell has a proton conductive polymer membrane such as a perfluoroalkylsulfonic acid type polymer as a solid electrolyte, and an oxygen electrode in which an electrode catalyst is applied to each surface of the solid polymer membrane.
- a membrane electrode assembly having a fuel electrode is provided.
- Electrocatalysts are generally formed by supporting various precious metal catalysts such as platinum on the surface of a conductive carbon material such as carbon black as a carrier.
- a conductive carbon material such as carbon black
- the electrode catalyst it is known that carbon is oxidized and corroded due to a potential change during operation of the fuel cell, and the supported metal catalyst is aggregated or dropped off. As a result, the performance of the fuel cell decreases as the operating time elapses. Therefore, in the manufacture of fuel cells, performance degradation is prevented by supporting a noble metal catalyst in a larger amount than is actually required on the carrier. However, this is not advantageous from an economic point of view.
- Patent Document 1 there are only Nb examples in which tin oxide is actually doped with other elements, and the effectiveness when doping other exemplified elements is not verified. Further, a carrier obtained by doping tin oxide with Nb cannot be said to have sufficiently high conductivity when compared with the surface area of particles. Therefore, it is impossible to achieve both high dispersibility of the supported catalyst and high conductivity as an electron flow path.
- An object of the present invention is to provide a tantalum-containing tin oxide for a fuel cell electrode catalyst that can eliminate the various disadvantages of the above-described prior art.
- Tin oxide contains tantalum, and the tantalum content is expressed by Ta (mol) / (Sn (mol) + Ta (mol)) ⁇ 100.
- a tantalum-containing tin oxide for a fuel cell electrode material that is 0.001 mol% or more and 30 mol% or less.
- the ratio of the integrated intensity I Ta2O5 of the (001) plane of Ta 2 O 5 to the integrated intensity I SnO2 of the (110) plane of SnO 2 is expressed as [I Ta2O5 / I SnO2 ] DOPE Ta 2 O 5 powder and SnO 2 powder in amounts corresponding to the molar ratio of Ta 2 O 5 and SnO 2 calculated from the molar ratio of tantalum and tin obtained by elemental analysis of the tantalum-containing tin oxide
- the present invention also provides a fuel cell electrode catalyst in which a catalyst is supported on the surface of the tantalum-containing tin oxide for a fuel cell electrode material.
- the present invention relates to a membrane electrode assembly in which a pair of electrodes composed of an oxygen electrode and a fuel electrode are disposed on each surface of a solid polymer electrolyte membrane.
- a membrane electrode assembly in which at least one of the oxygen electrode and the fuel electrode includes the fuel cell electrode catalyst is provided.
- the present invention provides a solid polymer electrolyte fuel cell comprising the membrane electrode assembly and a separator disposed on each surface of the membrane electrode assembly.
- FIG. 1 is a calibration curve showing the relationship between [I Ta2O5 / I SnO2 ] MIX and [X Ta2O5 / X SnO2 ].
- the tantalum-containing tin oxide for fuel cell electrode material of the present invention is one in which tantalum is contained in tin oxide particles.
- the tin oxide used in the present invention is composed of an oxide of tin. It is known that tin oxide is a highly conductive substance. Examples of the tin oxide include SnO 2 which is a tetravalent tin oxide and SnO which is a divalent tin oxide. In particular, the tin oxide is preferably composed mainly of SnO 2 from the viewpoint of enhancing acid resistance.
- the tantalum-containing tin oxide of the present invention is in the form of particles.
- the volume cumulative particle size D 50 at a cumulative volume of 50% by volume by the laser diffraction scattering type particle size distribution measurement method is 0.001 ⁇ m or more and 100 ⁇ m or less, preferably 0.005 ⁇ m or more and 20 ⁇ m or less. This is preferable because the specific surface area of tin oxide can be increased.
- grains What is necessary is just a shape which can enlarge a specific surface area. For example, various shapes such as a spherical shape, a polyhedral shape, a plate shape, a spindle shape, or a mixture thereof can be adopted.
- tantalum can be present inside the tin oxide particles, or both inside and outside. Even if tantalum exists only outside the tin oxide particles, the effect of the present invention is not achieved.
- the tantalum is dissolved in the tin oxide or is present in the form of a tantalum compound (eg, tantalum oxide) in the tin oxide. That tantalum is in solid solution in tin oxide means that the site of tin in tin oxide is replaced with tantalum. It is preferable that tantalum is dissolved in tin oxide because the conductivity of the tantalum-containing tin oxide of the present invention is increased.
- the tantalum is mainly present on the surface of the tin oxide particles in the state of the compound.
- tantalum is present on the surface of tin oxide particles in its oxide state.
- the tantalum oxide include, but are not limited to, Ta 2 O 5 .
- the compound when the tantalum compound is present outside the tin oxide particles, the compound can be crystalline or amorphous.
- the tantalum compound when the tantalum compound is an oxide of tantalum, the oxide can be crystalline or amorphous.
- the tantalum oxide is preferably crystalline from the viewpoint of acid resistance.
- tantalum is present in the oxide state on the surface of the particles in addition to being contained in the tin oxide particles. Preferably it is. From the viewpoint of further improving the conductivity, tantalum is preferably dissolved in the tin oxide particles. If an oxide of tantalum is present on the surface of the particles, the activity of the metal catalyst can be expected to be supported by bringing the oxide into contact with a metal catalyst such as Pt.
- the tantalum-containing tin oxide of the present invention of the tantalum contained in the tantalum, the proportion of tantalum present in the state of crystalline oxide on the surface of the particles is less than 30 mol%, particularly less than 10 mol%. It is preferable from the point of increase. This ratio can be measured, for example, by the following method. XRD of the powder was measured for the tantalum-containing tin oxide of the present invention.
- Ta and Sn From the peak area of the X-ray reflection spectrum derived from crystalline Ta 2 O 5 and the peak area of the X-ray reflection spectrum derived from SnO 2 , Ta and Sn The ratio can be estimated, and the proportion of tantalum present in the state of crystalline oxide on the surface of the particle can be calculated from the equation Ta (mol) / (Sn (mol) + Ta (mol)) ⁇ 100.
- the content of tantalum contained in the tantalum-containing tin oxide of the present invention is expressed as Ta (mol) / (Sn (mol) + Ta (mol)) ⁇ 100, and is 0.001 mol% or more and 30 mol% or less.
- this value is referred to as “tantalum content”.
- the tantalum content is more preferably 0.1 mol% or more and 15 mol% or less.
- the tantalum content contained in the tantalum-containing tin oxide of the present invention can be measured, for example, by the following method.
- the tantalum-containing tin oxide is dissolved by an appropriate method to form a solution.
- This solution is analyzed by ICP emission analysis, and the concentration of tin and the concentration of tantalum are measured.
- ICP emission analysis fluorescent X-ray (XRF) analysis can also be used.
- the tantalum-containing tin oxide of the present invention is also characterized by the results of X-ray diffraction measurement. Specifically, the tantalum-containing tin oxide is subjected to X-ray diffraction measurement to determine the integrated intensity I Ta2O5 of the (001) plane of Ta 2 O 5 and the integrated intensity I SnO2 of the (110) plane of SnO 2. . Then, the ratio [I Ta2O5 / I SnO2 ] DOPE is obtained.
- the tantalum-containing tin oxide is subjected to elemental analysis to determine the molar ratio of tantalum and tin. For elemental analysis, for example, ICP emission analysis can be used.
- a plurality of types of mixed powders prepared by mixing Ta 2 O 5 powder and SnO 2 powder at various molar ratios are prepared.
- X-ray diffraction measurement is performed on the mixed powders of plural types, and the integrated intensity I Ta2O5 of the (001) plane of Ta 2 O 5 and the integrated intensity I SnO2 of the (110) plane of SnO 2 are obtained.
- [I Ta2O5 / I SnO2 ] MIX which is the ratio of both is obtained, and a calibration curve of [I Ta2O5 / I SnO2 ] MIX and the molar ratio of tantalum and tin is prepared.
- the ratio of the diffraction peak area of the (110) plane in SnO 2 by powder X-ray diffraction to the diffraction peak area of the (001) plane in Ta 2 O 5 is SnO 2 , so long as tantalum is not dissolved in tin oxide. It is known that it is proportional to the concentration ratio between 2 and Ta 2 O 5 (L. Alexander, and H. P. Klug, Anal. Chem., 20, pp. 886 (1948)).
- the calibration curve of [I Ta2O5 / I SnO2 ] MIX thus prepared is compared with the value of [I Ta2O5 / I SnO2 ] DOPE previously measured.
- the value of [I Ta2O5 / I SnO2 ] DOPE is smaller than the value of [I Ta2O5 / I SnO2 ] MIX . That is, the value of [I Ta2O5 / I SnO2 ] DOPE is located below the calibration curve.
- the value of [I Ta2O5 / I SnO2 ] DOPE is smaller than the value of [I Ta2O5 / I SnO2 ] MIX in the tantalum-containing tin oxide of the present invention. This means that a part thereof exists in a state other than the crystalline Ta 2 O 5 state.
- tantalum is dissolved in tin oxide (SnO 2 ), is present on the surface of tin oxide particles in the form of amorphous Ta 2 O 5 , or is in the state of a compound other than an oxide. It exists on the surface of tin oxide particles.
- tin oxide SnO 2
- the tantalum-containing tin oxide of the present invention The specific surface area is increased, and the conductivity is increased.
- the value of [I Ta2O5 / I SnO2 ] DOPE described above is the value of [I Ta2O5 / I SnO2 ] MIX Is preferably 80% or less, and more preferably 60% or less.
- the tantalum-containing tin oxide of the present invention has a large specific surface area.
- the BET specific surface area is preferably 5 m 2 / g or more and 200 m 2 / g or less, more preferably 5 m 2 / g or more and 100 m 2 / g or less.
- the catalyst metal can be highly dispersed.
- the specific surface area is generally measured using physical adsorption such as nitrogen gas, and can be measured by, for example, the BET method.
- SA3100 manufactured by Bechman Coulter or flowsorb II manufactured by Micromeritics can be used for measurement of the specific surface area by the BET method.
- the tantalum-containing tin oxide of the present invention can be suitably produced by, for example, a wet synthesis method or a plasma synthesis method, but is not limited to these synthesis methods.
- a wet synthesis method and a plasma synthesis method will be described as examples.
- the wet synthesis method will be described.
- a coprecipitate containing tin and tantalum is generated from a solution containing a tin source and a tantalum source, and then the coprecipitate is baked to obtain a target tantalum-containing tin oxide. it can.
- the tin source compound examples include sodium stannate and tin chloride. These tin source compounds are dissolved in a solvent such as water to form a solution.
- the tantalum source compound for example, tantalum chloride, tantalum alkoxide, or the like can be used. These tantalum source compounds are dissolved in a solvent such as water or a water-soluble organic solvent such as ethanol to form a solution. Then, the solution is mixed, and using a mineral acid such as nitric acid or a basic compound such as ammonia, the pH is adjusted to produce a coprecipitate, and the coprecipitate containing tin and tantalum is contained in the liquid. Is generated. This operation can be performed at room temperature, for example.
- the coprecipitate When the coprecipitate is formed, it is aged. Aging is performed by allowing the liquid to stand at room temperature for a predetermined time, for example. The standing time can be set to 48 hours or less, for example. After aging, the liquid is filtered to recover the coprecipitate.
- the recovered coprecipitate is washed with repulp and dried to form a solid.
- This solid is fired in an oxygen-containing atmosphere.
- the target tantalum-containing tin oxide is obtained by this firing.
- the oxygen-containing atmosphere it is convenient to use air, for example.
- the firing temperature is preferably 400 ° C. or higher and 1200 ° C. or lower, and more preferably 600 ° C. or higher and 1000 ° C. or lower.
- the firing time is preferably 1 hour or more and 24 hours or less, and preferably 1 hour or more and 12 hours or less.
- the reaction temperature at the time of coprecipitate generation, the pH at the time of coprecipitate generation, the stirring speed of the raw material liquid, etc. may be controlled.
- the concentration ratio of Sn and Ta in the raw material liquid may be controlled.
- the firing temperature may be set to 600 ° C. or higher.
- the tantalum oxide In order for the tantalum oxide to be present on the surface of the tin oxide particles, for example, when synthesizing the tantalum-containing tin oxide of the present invention, tantalum exceeding the solid solubility limit is added, or the temperature gradient during firing is appropriately set. It may be adjusted to suppress tantalum solid solution in tin oxide. In order to make the tantalum oxide present on the surface of the tin oxide particles crystalline, for example, the firing temperature may be controlled to 1200 ° C.
- the firing temperature should be set high to promote solid solution of tantalum. .
- the plasma synthesis method is roughly divided into three steps: (i) synthesis of powder for spray drying, (ii) granulation by spray drying, and (iii) plasma synthesis.
- a coprecipitate containing tin and tantalum is produced from a solution containing a tin source and a tantalum source.
- the tin source compound and the tantalum source compound the same compounds as those used in the wet synthesis method can be used. These tin source compound and tantalum source compound are separately dissolved in a solvent to form a solution.
- the solvent for example, water or a water-soluble organic solvent such as ethanol can be used.
- a solution containing a tantalum source is added to a solution containing a tin source.
- the coprecipitate When the coprecipitate is formed, it is aged. Aging can be carried out in the same manner as in the wet synthesis method. After aging, the coprecipitate is washed, and the liquid is filtered to collect the coprecipitate. This coprecipitate is used as a powder for spray drying.
- the coprecipitate obtained in the step (i) is supplied to a spray dryer for granulation.
- the particle size of the granulated product is preferably 1 ⁇ m or more and 40 ⁇ m or less, and particularly preferably 1 ⁇ m or more and 10 ⁇ m or less from the viewpoint that the granulated product can be smoothly supplied to the plasma apparatus.
- the granulated product obtained in (ii) is supplied into a DC plasma flame.
- the rate at which the granulated material is supplied into the plasma flame can be, for example, 0.5 g / min or more and 2 g / min or less.
- the Ar gas flow rate from the main torch is preferably 4 SLM or more and 8 SLM or less.
- the Ar gas flow rate from the auxiliary torch is preferably 0.5 SLM or more and 2 SLM or less.
- the output is preferably 5 kW or more and 40 kW or less.
- the flow rate of argon as the carrier gas is preferably 1 SLM or more and 3 SLM or less. “SLM” is an abbreviation for Standard Litter per minute.
- the tantalum-containing tin oxide obtained by DC plasma may be dry collected or wet collected.
- fine particles sublimated at an ultra-high temperature can be further rapidly cooled, so that growth of tantalum-containing tin oxide particles can be suppressed.
- the powder resistivity of tantalum-containing tin oxide can be reduced.
- the output or the gas flow rate from the main torch may be changed. That is, the plasma temperature may be increased by increasing the output and decreasing the gas flow rate.
- the composition ratio of the raw materials may be changed.
- the tantalum is allowed to stay in the high-temperature plasma for a long time and is sufficiently sublimated.
- the composition ratio of the precursor may be changed to a concentration not lower than the solid solubility limit.
- the output may be reduced so that the tantalum oxide does not sublimate, or the amount of gas from the main torch is increased to reduce the plasma temperature and prevent it from staying in the plasma for a long time.
- the tantalum oxide thus precipitated is detected as Ta 2 O 5 with good crystallinity.
- solid solution of tantalum may be promoted as described above.
- the thus-obtained tantalum-containing tin oxide has various catalysts supported on its surface and becomes an electrode catalyst for a fuel cell.
- a noble metal such as Pt, Ir, Ag, or Pd
- metal oxides such as Ti and Zr, carbonitrides, and the like can be used, but are not limited thereto.
- These catalysts can be used alone or in combination of two or more.
- single elements of Pt, Ir, Ag, and Pd, which are noble metal catalysts exhibit high oxygen reduction activity. If only pure hydrogen is used as the fuel gas, the catalyst may be only the noble metal alone. However, when a reformed gas is used as the fuel gas, addition of Ru or the like is effective to prevent poisoning by CO.
- the catalyst can be an alloy based on Pt, Ir, Ag, Pd containing an additive metal such as Ru.
- the average particle diameter of the catalyst metal is preferably 1 nm or more and 10 nm or less, and particularly preferably 1 nm or more and 5 nm or less.
- the amount of the catalyst metal supported is preferably 1% by mass or more and 60% by mass or less, particularly preferably 1% by mass or more and 30% by mass or less based on the tantalum-containing tin oxide supporting the catalyst metal. By setting the amount of catalyst metal supported within this range, sufficient catalytic activity can be exhibited and the catalyst metal can be supported in a highly dispersed state.
- the amount of catalyst metal particles supported can be measured, for example, by ICP emission analysis.
- the tantalum-containing tin oxide may be heated in a reducing atmosphere. By this operation, the catalytic metal in the catalytic metal source is reduced and supported on the surface of the tantalum-containing tin oxide.
- An electrode catalyst of the present invention comprising a tantalum-containing tin oxide supporting a catalytic metal is a membrane electrode assembly having an oxygen electrode disposed on one surface of a solid polymer electrolyte membrane and a fuel electrode disposed on the other surface. It is contained in at least one of the oxygen electrode and the fuel electrode.
- the electrode catalyst of the present invention is preferably contained in both the oxygen electrode and the fuel electrode.
- the oxygen electrode and the fuel electrode preferably include a catalyst layer containing the electrode catalyst of the present invention and a gas diffusion layer.
- the electrode catalyst is preferably in contact with the solid polymer electrolyte membrane.
- the gas diffusion layer functions as a supporting current collector having a current collecting function. Furthermore, it has a function of sufficiently supplying gas to the electrode catalyst.
- the gas diffusion layer those similar to those conventionally used in this kind of technical field can be used.
- carbon paper and carbon cloth which are porous materials can be used. Specifically, it can be formed by, for example, a carbon cloth woven with yarns having a predetermined ratio of carbon fibers whose surfaces are coated with polytetrafluoroethylene and carbon fibers that are not coated.
- solid polymer electrolyte those similar to those conventionally used in this kind of technical field can be used.
- a perfluorosulfonic acid polymer-based proton conductor film a hydrocarbon polymer compound doped with an inorganic acid such as phosphoric acid, or an organic / inorganic hybrid polymer partially substituted with a proton conductor functional group
- proton conductors in which a polymer matrix is impregnated with a phosphoric acid solution or a sulfuric acid solution.
- the membrane electrode assembly is made into a polymer electrolyte fuel cell by providing a separator on each surface.
- a separator for example, a separator in which a plurality of protrusions (ribs) extending in one direction are formed at a predetermined interval on the surface facing the gas diffusion layer can be used. Between adjacent convex parts, it is a groove part with a rectangular cross section. The groove is used as a supply / discharge flow path for an oxidant gas such as fuel gas and air. The fuel gas and the oxidant gas are supplied from the fuel gas supply unit and the oxidant gas supply unit, respectively.
- Each separator disposed on each surface of the membrane electrode assembly is preferably disposed so that the grooves formed therein are orthogonal to each other.
- the above configuration constitutes the minimum unit of the fuel cell, and a fuel cell can be configured from a cell stack formed by arranging several tens to several hundreds of this configuration in parallel.
- the tantalum-containing tin oxide of the present invention is used as a support for an electrode catalyst of a solid polymer electrolyte fuel cell has been mainly described. It can be used as a catalyst carrier in various fuel cells such as fuel cells other than molecular electrolyte fuel cells, such as alkaline fuel cells and phosphoric acid fuel cells.
- the SnO 2 powder and the Ta 2 O 5 powder are 4.855 g and 0.145 g, 4.642 g and 0.358 g, 4.503 g and 0.497 g, and 4.300 g and 0.700 g, respectively. Weighed and mixed with mortar to make standard samples 2-5.
- the contained metal Sn mass concentration and the metal Ta mass concentration were determined by ICP emission analysis. Assuming that the metal Sn and the metal Ta are all SnO 2 and Ta 2 O 5 , respectively, the ratio of the SnO 2 molar concentration (X SnO2 ) and the Ta 2 O 5 molar concentration (X Ta2O5 ) [X Ta2O5 / X SnO2 ] value was determined.
- tantalum-containing tin oxide particles were synthesized by a wet synthesis method.
- An amount of TaCl 5 shown in Table 1 was added to 50 mL of ethanol to obtain a tantalum-containing solution having five different concentrations.
- Na 2 SnO 3 .3H 2 O was dissolved in pure water to obtain a 0.33 mol / L tin-containing aqueous solution.
- 800 mL of a 0.5 mol / L nitric acid aqueous solution was added to this solution.
- the content rate of tantalum was measured by the above-mentioned method.
- the value of [I Ta2O5 / I SnO2 ] DOPE was determined by the method described above.
- the particle size D 50 was measured by the method described above.
- the BET specific surface area was measured using SA3100 (Example 1) manufactured by Bechman Coulter and flowsorb II (Example 2 and later and comparative examples) manufactured by Micromeritics. The results are shown in Table 1.
- the electrode catalyst made of tantalum-containing tin oxide particles carrying platinum was obtained by drying at 80 ° C. for 15 hours.
- the amount of platinum supported measured by ICP emission analysis was 10% with respect to the platinum-supported tantalum-containing tin oxide particles.
- niobium-containing tin oxide particles were synthesized by a wet synthesis method.
- the amount of NbCl 5 shown in Table 2 was added to 50 mL of ethanol to dissolve it, thereby obtaining niobium-containing solutions having four concentrations.
- the amount of Na 2 SnO 3 .3H 2 O shown in Table 2 was dissolved in pure water to obtain a 0.33 mol / L tin-containing aqueous solution.
- tin oxide in the obtained particles was composed of SnO 2, and it was confirmed that niobium was dissolved.
- the niobium-containing tin oxide particles were measured for niobium content in the same manner as in Example 1.
- the niobium content (%) is defined as Nb (mol) / (Sn (mol) + Nb (mol)) ⁇ 100.
- the BET specific surface area was measured by the method described above. The results are shown in Table 2.
- tantalum-containing tin oxide particles were synthesized by a plasma synthesis method.
- SnCl 4 was dissolved in pure water to obtain 6000 g of a 60% aqueous SnCl 4 solution.
- TaCl 5 ethanol solution and 60% SnCl 4 aqueous solution were weighed in the amounts shown in Table 3, and pure water was mixed to make a mixed solution of about 1.6 L. Further, pure water was added to 25% NH 3 water as a neutralizing solution to obtain 12.5% NH 3 water.
- the value of [I Ta2O5 / I SnO2 ] DOPE was determined by the method described above. Further, the BET specific surface area and the particle diameter D 50 were measured by the above-described method. The results are shown in Table 3. As a result of X-ray diffraction measurement, it was confirmed that the tin oxide in this particle was composed of SnO 2 and tantalum was dissolved. Of Examples 6 to 9, in Examples 6 and 7, as a result of X-ray diffraction measurement, only a peak derived from the crystal structure of tin oxide was confirmed. Further, in Examples 8 and 9, it was confirmed from the results of X-ray diffraction measurement that crystalline Ta 2 O 5 was present on the surface of the tin oxide particles.
- volume resistivity was measured about the particle
- the volume resistivity was measured in a uniaxial pressure state of 18 kN. At this time, the relative density of the sample with respect to SnO 2 was 47 to 51%.
- a tantalum-containing tin oxide for a fuel cell electrode material having high conductivity when compared with the surface area of particles is provided.
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Abstract
Description
前記タンタル含有酸化スズのX線回折測定におけるTa2O5の(001)面のピークの積分強度ITa2O5と、SnO2の(110)面のピークの積分強度ISnO2との比を〔ITa2O5/ISnO2〕DOPEとし、
前記タンタル含有酸化スズを元素分析して得られたタンタルとスズとのモル比から算出された、Ta2O5とSnO2とのモル比に対応する量のTa2O5粉とSnO2粉との混合粉について行ったX線回折測定におけるTa2O5の(001)面のピークの積分強度ITa2O5と、SnO2の(110)面のピークの積分強度ISnO2との比を〔ITa2O5/ISnO2〕MIXとしたとき、
〔ITa2O5/ISnO2〕DOPEの値が、〔ITa2O5/ISnO2〕MIXの値よりも小さい、燃料電池電極材料用タンタル含有酸化スズを提供するものである。
前記酸素極又は前記燃料極の少なくとも一方が、前記の燃料電池用電極触媒を含んでいる膜電極接合体を提供するものである。
(1)タンタル含有酸化スズ粒子の合成
本実施例では湿式合成法によってタンタル含有酸化スズ粒子を合成した。50mLのエタノール中に表1に示す量のTaCl5を添加してこれを溶解させた5種類の濃度のタンタル含有溶液を得た。これとは別に、Na2SnO3・3H2Oを純水に溶解させて、0.33mol/Lのスズ含有水溶液を得た。各濃度のタンタル含有溶液それぞれに0.5mol/Lの硝酸水溶液を800mL添加した後、この溶液にスズ含有水溶液を600mL添加した。この添加によって液中に沈殿物が生成した。液を25℃で1時間静置して沈殿物の熟成を行った後、濾過によって沈殿物を回収し、更にリパルプ洗浄した。次いで120℃で15時間乾燥させて固形物を得た。この固形物を大気雰囲気下、5時間焼成して目的とするタンタル含有酸化スズ粒子を得た。焼成温度は800℃及び1000℃での2種類とした。X線回折測定の結果、得られた粒子における酸化スズはSnO2から構成されており、タンタルが固溶していることが確認された。このタンタル含有酸化スズ粒子について、上述の方法でタンタルの含有率を測定した。また上述の方法で〔ITa2O5/ISnO2〕DOPEの値を求めた。更に、上述の方法で粒径D50を測定した。BET比表面積については、Bechman Coulter社製のSA3100(実施例1)、及びMicromeritics社製のflowsorb II(実施例2以降及び比較例)を用いて測定した。結果を表1に示す。
特開平9-47659号公報の記載に準拠し白金を担持したが、この方法に限定されるものではない。以下に具体的担持法について述べる。濃度が200g/Lであるジニトロジアミン硝酸白金水溶液1mLを用意し、これに水を加えて全体を60mLとした。この水溶液に、(1)で得られたタンタル含有酸化スズ粒子を1.800g添加し、超音波分散させた。次いで、この水溶液にエタノールを4mL添加した後、90-95℃で6時間にわたって加熱還元を行った。この操作によって、タンタル含有酸化スズ粒子の表面に白金を担持させた。次いで濾過・洗浄を行い、80℃で15時間乾燥させることで、白金を担持したタンタル含有酸化スズ粒子からなる電極触媒を得た。ICP発光分析法で測定した白金の担持量は、白金担持タンタル含有酸化スズ粒子に対して10%であった。
本比較例では、タンタルを含有しない単体の酸化スズ粒子を合成した。以下の表1に示す条件を用いる以外は、実施例1と同様にして単体の酸化スズ粒子を合成した。得られた酸化スズ粒子について、上述の方法でBET比表面積及び粒径D50を測定した。結果を表1に示す。更に、得られた酸化スズ粒子について、実施例1と同様にして白金を担持させて、白金を担持した酸化スズ粒子からなる電極触媒を得た。
本比較例では湿式合成法によってニオブ含有酸化スズ粒子を合成した。50mLのエタノール中に表2に示す量のNbCl5を添加してこれを溶解させた4種類の濃度のニオブ含有溶液を得た。これとは別に、表2に示す量のNa2SnO3・3H2Oを純水に溶解させて、0.33mol/Lのスズ含有水溶液を得た。各濃度のニオブ含有溶液それぞれに0.5mol/Lの硝酸水溶液を800mL添加した後、この溶液にスズ含有水溶液を600mL添加した。この添加によって液中に沈殿物が生成した。液を25℃で1時間静置して沈殿物の熟成を行った後、濾過によって沈殿物を回収し、更にリパルプ洗浄した。次いで120℃で15時間乾燥させて固形物を得た。この固形物を大気雰囲気下、5時間焼成して目的とするニオブ含有酸化スズ粒子を得た。焼成温度は800℃及び1000℃での2種類とした。X線回折測定の結果、得られた粒子における酸化スズはSnO2から構成されており、ニオブが固溶していることが確認された。このニオブ含有酸化スズ粒子について、実施例1と同様の方法でニオブの含有率を測定した。ニオブの含有率(%)は、Nb(mol)/(Sn(mol)+Nb(mol))×100で定義される。また上述の方法でBET比表面積を測定した。結果を表2に示す。
実施例1と同様にした。ICP発光分析法で測定した白金の担持量は、白金担持ニオブ含有酸化スズ粒子に対して10%であった。
本実施例ではプラズマ合成法によってタンタル含有酸化スズ粒子を合成した。
(i)スプレードライ用の粉の合成
TaCl5100gをエタノール500mLに溶かし、TaCl5エタノール溶液を得た。一方、SnCl4を純水に溶かし、60%のSnCl4水溶液6000gを得た。TaCl5エタノール溶液、及び60%SnCl4水溶液を表3に示す量を量り取り、純水を混ぜて約1.6Lの混合溶液とした。また、中和溶液として25%NH3水に純水を加え、12.5%NH3水とした。混合溶液に、中和溶液を加えていき、pH=7とした。なお、中和反応中は、60℃程度の液温が維持されるようにした。常温にて一晩熟成させた後、純水にて4回リパルプ洗浄を行った。濾過残渣に純水を加え撹拌し、全量を5.5Lのスラリーとした。これを、スプレードライ用の原料スラリーとした。
2流体ノズルを用いたスプレードライヤによって原料スラリーを乾燥、造粒して、二次粒径が3~5μm程度の造粒物を得た。この造粒物を、DCプラズマ用の原料粉とした。用いたスプレードライヤは、大川原加工機(株)製のL-8iであった。
スプレードライヤによって得られた造粒物を、DCプラズマ炎中に導入して、目的とするタンタル含有酸化スズ粒子を得た。この粒子をスプレー水によって湿式回収した。用いたDCプラズマ装置は、エアロプラズマ(株)製のAPS7000であった。プラズマ合成の条件は,メイントーチからのArガス流量8SLM、補助トーチからのArガス流量1SLM、出力9.6kWであった。プラズマ炎内に試料を投入する速度は1~2g/minとし、そのキャリアガスはArで2SLMとした。得られたタンタル含有酸化スズ粒子について、上述の方法でタンタルの含有率を測定した。また上述の方法で〔ITa2O5/ISnO2〕DOPEの値を求めた。更に、上述の方法でBET比表面積及び粒径D50を測定した。結果を表3に示す。X線回折測定の結果、この粒子における酸化スズはSnO2から構成されており、タンタルが固溶していることが確認された。また、実施例6ないし9のうち、実施例6及び7では、X線回折測定の結果、酸化スズの結晶構造由来のピークのみが確認された。更に実施例8及び9では、酸化スズ粒子の表面に結晶質のTa2O5が存在していることが、X線回折測定の結果から確認された。
実施例1と同様にした。ICP発光分析法で測定した白金の担持量は、白金担持タンタル含有酸化スズ粒子に対して10%であった。
各実施例及び各比較例で得られた粒子について体積抵抗率を測定した。その結果を表1ないし表3に示す。これらの表に示す結果から明らかなとおり、酸化スズにタンタルが少量でも固溶していると体積抵抗率が低下するが、体積抵抗率の値にはタンタルの固溶量に関して極小値が存在することが判る。また、タンタルとニオブとを比較すると、粒子の表面積が同じである場合には、タンタルの方が、体積抵抗率が低いことが判る。なお、体積抵抗率は、実施例1ないし5及び比較例1では次の2種類の方法で測定した。比較例2ないし5では、4探針法で測定した。実施例6ないし9では、PAUW法で測定した。
PAUW法:タンタル含有酸化スズ粒子を約1g秤量し、一軸加圧成形によりφ18×約1tのペレットからなる試料を作製し、これをN2中で500℃、3時間加熱した。この試料の表面の円周上の位置に、等分で4点(φ1mm)に金を蒸着させ、測定電極を形成した。このサンプルをvan der pauw法にて抵抗率を測定した。このときのペレットのSnO2(d=6.95g/cm3)に対する相対密度は47~50%であった。4探針法:装置は三菱アナリテック社製MCP-M610を用いた。試料2.000gを秤量してφ20mmの測定部に入れた後、18kNの一軸加圧状態で体積抵抗率の測定を行った。このときの試料のSnO2に対する相対密度は47~51%であった。
各実施例で得られたタンタル含有酸化スズ粒子及び比較例1で得られた酸化スズ粒子の電極触媒について酸素還元開始電位を測定した。その結果を表1及び表3に示す。これらの表に示す結果から明らかなとおり、各実施例のタンタル含有酸化スズ粒子を用いた電極触媒は、酸素還元に関して活性が高いことが判る。酸素還元開始電位は、次の方法で測定した。
(1)電極の作製
各実施例で得られた電極触媒を90.4mg秤量した。この操作とは別に、6mLのイソプロピルアルコールに純水を加えて全量を25mLとした。この含水イソプロピルアルコールに、秤量した電極触媒を添加混合した。この液を5分間にわたって超音波の照射による前処理をした。次いで5%ナフィオン(登録商標)溶液を100μL添加し、引き続き30分間にわたり超音波分散処理をした。このようにして得られた液を、グラッシーカーボン製の回転ディスク電極に塗布した。塗布量は10μLとした。次いで60℃で30分間乾燥させて、電気化学測定用電極を得た。
触媒の酸素還元反応(ORR)の活性は北斗電工(株)製の電気化学測定システムHZ-3000を用いて実施した。25℃の0.1Nの過塩素酸水溶液に酸素ガスを30分間以上バブリングして酸素ガスを飽和させ、この過塩素酸水溶液を電解液に用いた。ORRは電位走査速度を10mV/sとし、電位走査範囲-0.20から1.0V(対Ag/AgCl)で測定した。電極の回転数が1600rpmで測定したときに、-2μAの酸素還元電流が得られた電位を酸化還元開始電位とした。
Claims (6)
- 酸化スズにタンタルが含有されてなり、タンタルの含有率が、Ta(mol)/(Sn(mol)+Ta(mol))×100で表して0.001mol%以上30mol%以下である燃料電池電極材料用タンタル含有酸化スズであって、
前記タンタル含有酸化スズのX線回折測定におけるTa2O5の(001)面のピークの積分強度ITa2O5と、SnO2の(110)面のピークの積分強度ISnO2との比を〔ITa2O5/ISnO2〕DOPEとし、
前記タンタル含有酸化スズを元素分析して得られたタンタルとスズとのモル比から算出された、Ta2O5とSnO2とのモル比に対応する量のTa2O5粉とSnO2粉との混合粉について行ったX線回折測定におけるTa2O5の(001)面のピークの積分強度ITa2O5と、SnO2の(110)面のピークの積分強度ISnO2との比を〔ITa2O5/ISnO2〕MIXとしたとき、
〔ITa2O5/ISnO2〕DOPEの値が、〔ITa2O5/ISnO2〕MIXの値よりも小さい、燃料電池電極材料用タンタル含有酸化スズ。 - 酸化スズの粒子中にタンタルが含有されていることに加えて、該粒子の表面に、タンタルの酸化物が存在している請求項1に記載の燃料電池電極材料用タンタル含有酸化スズ。
- タンタルの酸化物が結晶質のものである請求項2に記載の燃料電池電極材料用タンタル含有酸化スズ。
- 請求項1ないし3のいずれか一項に記載の燃料電池電極触媒用タンタル含有酸化スズの表面に、触媒が担持されてなる燃料電池用電極触媒。
- 固体高分子電解質膜の各面に酸素極及び燃料極からなる一対の電極が配置されてなる膜電極接合体において、
前記酸素極又は前記燃料極の少なくとも一方が、請求項4に記載の燃料電池用電極触媒を含んでいる膜電極接合体。 - 請求項5に記載の膜電極接合体と、該膜電極接合体の各面に配されたセパレータとを備えることを特徴とする固体高分子形燃料電池。
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Also Published As
Publication number | Publication date |
---|---|
CN104662720A (zh) | 2015-05-27 |
JP5623680B1 (ja) | 2014-11-12 |
EP2966715A1 (en) | 2016-01-13 |
KR101516273B1 (ko) | 2015-05-04 |
EP2966715A4 (en) | 2016-10-26 |
JPWO2014136908A1 (ja) | 2017-02-16 |
US20150243999A1 (en) | 2015-08-27 |
KR20150032751A (ko) | 2015-03-27 |
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