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CN101884930A - Perovskite LaxCa1-xCoO3/Ag Composite Powder Oxygen Reduction Catalyst and Preparation Method - Google Patents

Perovskite LaxCa1-xCoO3/Ag Composite Powder Oxygen Reduction Catalyst and Preparation Method Download PDF

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CN101884930A
CN101884930A CN2010102197266A CN201010219726A CN101884930A CN 101884930 A CN101884930 A CN 101884930A CN 2010102197266 A CN2010102197266 A CN 2010102197266A CN 201010219726 A CN201010219726 A CN 201010219726A CN 101884930 A CN101884930 A CN 101884930A
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张正富
马全宝
杨伦权
陈庆华
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Kunming University of Science and Technology
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Abstract

本发明是一种钙钛矿型LaxCa1-xCoO3/Ag复合粉体氧还原催化剂的制备方法。以硝酸钙、硝酸钴和硝酸镧为原料经过溶胶-凝胶、干燥、陈化、烘干、高温焙烧等过程处理制得LaxCa1-xCoO3粉体。再以硝酸银为原料，蒸馏水为溶剂、氨水为络合剂进行化学反应制得银氨络合物溶液，然后再加入LaxCa1-xCoO3粉体，经液相化学还原在钙钛矿表面沉积单质Ag，得到LaxCa1-xCoO3/Ag复合粉体催化剂。本发明制得的复合粉体催化剂较以往的钙钛矿型氧化物催化剂电导率增加，催化活性增强；同时，成本比纯Ag单质催化剂大幅下降。该催化剂可用于低温碱性燃料电池、或者金属-空气电池中，作为阴极上将O2还原为OH-的催化剂。The invention relates to a method for preparing a perovskite type LaxCa1 -xCoO3 / Ag composite powder oxygen reduction catalyst. Using calcium nitrate, cobalt nitrate and lanthanum nitrate as raw materials, La x Ca 1-x CoO 3 powder was prepared through sol-gel, drying, aging, drying, high-temperature roasting and other processes. Silver nitrate is used as raw material, distilled water is used as solvent, and ammonia water is used as complexing agent to carry out chemical reaction to prepare silver ammonium complex solution, and then La x Ca 1-x CoO 3 powder is added, and the calcium titanium Elemental Ag is deposited on the surface of the ore to obtain a La x Ca 1-x CoO 3 /Ag composite powder catalyst. Compared with the previous perovskite type oxide catalyst, the composite powder catalyst prepared by the invention has higher electrical conductivity and enhanced catalytic activity; meanwhile, the cost is greatly lower than that of the pure Ag single substance catalyst. The catalyst can be used in low-temperature alkaline fuel cells or metal-air batteries as a catalyst for reducing O2 to OH- on the cathode.

Description

Ca-Ti ore type La xCa 1-xCoO 3/ Ag composite granule oxygen reduction catalyst and preparation method
Technical field
The present invention relates to a kind of Ca-Ti ore type La xCa 1-xCoO 3/ Ag composite granule oxygen reduction catalyst and preparation method thereof.This catalyst is as low-temperature alkali fuel battery negative pole oxygen reduction catalyst, or the metal-air battery cathod catalyst of alkalescence.It is the crucial electrode catalytic materials that influences power of battery density.
Background technology
For high energy low-temperature alkali fuel cell and high-energy metals-air green battery, oxygen electrode (or air electrode) catalyst is one of key factor that improves its performance, perovskite composite oxide is with its efficient, durable and cheap characteristics in adopted catalyst, and receives much concern.Because efficient, environmental protection characteristics that low-temperature fuel cell and metal-air battery are intrinsic are with a wide range of applications.At present, Japan, Europe, the U.S. and domestic how tame colleges and universities and scientific research institution have all carried out the research work of perovskite type composite oxide catalyst aspect.But the electronic conductivity of perofskite type oxide powder is not high, how to improve electrical conductivity and be always one of emphasis that the scientific worker studies.
Summary of the invention
The objective of the invention is at the not high defective of perovskite type composite oxide catalyst electrical conductivity, the La that a kind of catalysis characteristics is better, electrical conductivity is higher is provided xCa 1-xCoO 3/ Ag composite powder body catalyst and preparation method.
Technical scheme of the present invention is:
La xCa 1-xCoO 3/ Ag composite powder body catalyst prepares by the following method:
The first step: in molar ratio 0.2～0.8: 1: 1～0.2, take by weighing calcium nitrate Ca (NO 3) 24H 2O, cobalt nitrate Co (NO 3) 26H 2O, lanthanum nitrate
Figure BSA00000175488000011
Be dissolved in the distilled water stand-byly, the solution that takes a morsel is adjusted to 0.9～3.0 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 1～5%wt, and solution makes colloidal sol 40～95 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 10～72 hours under the room temperature;
The 3rd step: the gel after the ageing is put in the Muffle furnace, begins to be warming up to 500 ℃ from room temperature, be incubated 2～8 hours, the remaining nitrate anion in the gel is decomposed, cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, place corundum crucible, 700～900 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 6～24 hours, make La xCa 1-xCoO 3Powder;
The 5th step: the AgNO of preparation 1M～5M 3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex.Then, be toward silver ammonia complex solution in to add the La that made at 0.90～0.999: 0.10～0.001 by the mass ratio of perovskite oxide and Ag xCa 1-xCoO 3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.2～2 times of reduction silver ion aequum; And temperature constant is between 20～60 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface xCa 1-xCoO 3/ Ag composite granule.
The present invention uses the auxiliary sol-gel process of organic acid to prepare La xCa 1-xCoO 3Perofskite type oxide, then, by the liquid phase chemical reduction method at La xCa 1-xCoO 3Particle surface deposition simple substance Ag makes La xCa 1-xCoO 3/ Ag composite powder body catalyst has silver-colored addition minimizing, the more high outstanding advantage of electrical conductivity.Because the concerted catalysis effect of Ag and perovskite oxide, the hydrogen reduction catalytic activity of the catalyst that the present invention obtains is also higher, even more taller than the catalyst activity that just adds silver ion before the roasting.This catalyst can be used in low-temperature alkali fuel cell or the metal-air battery, as on the negative electrode with O 2Be reduced to OH -Catalyst.This composite powder body catalyst can promote the exploitation of high efficiency oxygen electrode or air electrode, and then promotes the industrialization of above-mentioned novel green battery.
The present invention has prepared the La that catalytic activity is better, electrical conductivity is higher xCa 1-xCoO 3/ Ag composite granule, and the preparation method is simple, and process is easy to control.
The specific embodiment
Embodiment one:
The first step: 0.6: 1: 0.4 in molar ratio, take by weighing calcium nitrate Ca (NO 3) 24H 2O, cobalt nitrate Co (NO 3) 26H 2O, lanthanum nitrate
Figure BSA00000175488000021
Be dissolved in the distilled water stand-byly, the solution that takes a morsel adjusts to 1.8 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 2%wt, and solution makes colloidal sol 80 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 48 hours under the room temperature;
The 3rd step: the gel of ageing after 48 hours is put in the Muffle furnace under the above-mentioned room temperature, begins to be warming up to 500 ℃ from room temperature, is incubated 4 hours, and the remaining nitrate anion in the gel is decomposed, and cooling naturally obtains black powder afterwards;
The 4th goes on foot: above-mentioned black powder is transferred to ground fine ground in the alms bowl, place corundum crucible again, 700 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 24 hours, obtain La 0.4Ca 0.6CoO 3Powder;
The 5th step: the AgNO of preparation 2M 3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex, then, is the La that adding had made in the silver ammonia complex solution in 0.98: 0.02 by the mass ratio of perovskite oxide and Ag 0.4Ca 0.6CoO 3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.5 times of reduction silver ion aequum; And temperature constant is between 30 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface 0.4Ca 0.6CoO 3/ Ag composite granule, the deposition of simple substance Ag is controlled at 2%wt.
Behind above-mentioned catalyst fines sample compressing tablet, measure electrical conductivity by bridge method; Simultaneously, utilization powder electrode technology is measured the apparent exchange current density of catalyst powder, adopts three-electrode system in the measurement, and the KOH solution of 6M is electrolyte, feeds pure oxygen in the electrolytic cell continuously.Measurement shows, through the La of above-mentioned liquid phase chemical reduction deposition 2%wt Ag simple substance 0.4Ca 0.6CoO 3The electrical conductivity of/Ag composite powder is 0.85 Ω -1Cm -1, apparent exchange current density reaches 0.4171A/m 2
Comparison example: the process at preparation La-Ca-Co-O sol-gel is just added 2%wtAg +The La of ion 0.4Ca 0.6CoO 3The electrical conductivity of powder is 1.89 * 10 -1Ω -1Cm -1, apparent exchange current density is 0.2988A/m 2
So, use method of the present invention, deposit simple substance Ag at La by liquid phase chemical reduction 0.4Ca 0.6CoO 3The composite powder body catalyst of particle surface has better catalysis characteristics.
Embodiment two:
The first step: 0.8: 1: 0.2 in molar ratio, take by weighing calcium nitrate Ca (NO 3) 24H 2O, cobalt nitrate Co (NO 3) 26H 2O, lanthanum nitrate
Figure BSA00000175488000031
Be dissolved in the distilled water stand-byly, the solution that takes a morsel adjusts to 2.5 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 4%wt, and solution makes colloidal sol 50 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 72 hours under the room temperature;
The 3rd step: the gel of ageing after 72 hours is put in the Muffle furnace under the above-mentioned room temperature, begins to be warming up to 500 ℃ from room temperature, is incubated 8 hours, and the remaining nitrate anion in the gel is decomposed, and cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, sample is placed corundum crucible, 800 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 14 hours, obtain La 0.2Ca 0.8CoO 3Powder;
The 5th step: the AgNO of preparation 1M 3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex, then, is the La that adding had made in the silver ammonia complex solution in 0.99: 0.01 by the mass ratio of perovskite oxide and Ag 0.2Ca 0.8CoO 3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.2 times of reduction silver ion aequum; And temperature constant is between 60 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface 0.2Ca 0.8CoO 3/ Ag composite granule, the deposition of simple substance Ag is controlled at 1%wt.
The performance characterization of composite powder such as embodiment one.By the La of present embodiment through liquid phase chemical reduction deposition 1%wt Ag simple substance 0.4Ca 0.6CoO 3The electrical conductivity of/Ag composite powder is 0.26 Ω -1Cm -1, apparent exchange current density reaches 0.3012A/m 2La 0.4Ca 0.6CoO 3/Ag
Comparison example: just add 1%wt Ag at sol-gel process +The La of ion 0.2Ca 0.8CoO 3The electrical conductivity of powder is 4.73 * 10 -2Ω -1Cm -1, apparent exchange current density is 0.0600A/m 2
Embodiment three:
The first step: 0.2: 1: 0.8 in molar ratio, take by weighing calcium nitrate Ca (NO 3) 24H 2O, cobalt nitrate Co (NO 3) 26H 2O, lanthanum nitrate
Figure BSA00000175488000032
Be dissolved in the distilled water stand-byly, the solution that takes a morsel adjusts to 0.9 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 1%wt, and solution makes colloidal sol 95 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 24 hours under the room temperature;
The 3rd step: the gel of ageing after 48 hours is put in the Muffle furnace under the above-mentioned room temperature, begins to be warming up to 500 ℃ from room temperature, is incubated 2 hours, and the remaining nitrate anion in the gel is decomposed, and cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, sample is placed corundum crucible, 900 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 6 hours, obtain La 0.8Ca 0.2CoO 3Powder;
The 5th step: the AgNO of preparation 4M 3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex.Then, be toward silver ammonia complex solution in to add the La that made at 0.96: 0.04 by the mass ratio of perovskite oxide and Ag 0.8Ca 0.2CoO 3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.9 times of reduction silver ion aequum; And temperature constant is between 45 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface 0.8Ca 0.2CoO 3/ Ag composite granule, the deposition of simple substance Ag is controlled at 4%wt.
The performance characterization of composite powder such as embodiment one.By the La of present embodiment through liquid phase chemical reduction deposition 4%wt Ag simple substance 0.8Ca 0.2CoO 3The electrical conductivity of/Ag composite powder is 1.06 Ω -1Cm -1, apparent exchange current density reaches 0.6032A/m 2
Comparison example: just add 4%wt Ag at sol-gel process +The La of ion 0.8Ca 0.2CoO 3The electrical conductivity of powder is 4.12 * 10 -1Ω -1Cm -1, apparent exchange current density is 0.0509A/m 2
Can find out by embodiment one, two, three, in the colloidal sol preparation process, just add Ag +Catalyst powder, catalytic activity increases synchronously with the increase of silver amount.And employing La xCa 1-xCoO 3Powder preparation well after, at the composite granule of liquid phase chemical deposition Ag simple substance, increase with silver content, the exchange current density of electrical conductivity and catalytic reaction all increases synchronously.Therefore, Ag is deposited on La through liquid phase chemical reduction among employing the present invention xCa 1-xCoO 3Technology on the particle can be brought into play La better xCa 1-xCoO 3Catalyzing cooperation effect with Ag gets a greater increase catalytic performance.

Claims (2)

1.一种钙钛矿型LaxCa1-xCoO3/Ag复合粉体氧还原催化剂的制备方法，其特征在于按以下步骤进行：1. A preparation method of perovskite type La x Ca 1-x CoO 3 /Ag composite powder oxygen reduction catalyst, characterized in that it is carried out in the following steps: 第一步：按摩尔比0.2～0.8∶1∶1～0.2，称取硝酸钙Ca(NO3)2·4H2O、硝酸钴Co(NO3)2·6H2O、硝酸镧La(NO3)26H2O溶于蒸馏水中待用，取少量溶液，用硝酸和氨水将pH值调整到0.9～3.0间，添加1～5％wt的柠檬酸，然后溶液在40～95℃恒温水解，制得溶胶；Step 1: Weigh calcium nitrate Ca(NO 3 ) 2 ·4H 2 O, cobalt nitrate Co(NO 3 ) 2 ·6H 2 O, lanthanum nitrate La(NO 3 ) Dissolve 2 6H 2 O in distilled water for later use, take a small amount of solution, adjust the pH value to 0.9-3.0 with nitric acid and ammonia water, add 1-5%wt citric acid, and then hydrolyze the solution at a constant temperature of 40-95°C , to obtain a sol; 第二步：将溶胶的水分蒸干，获得粉红色凝胶，室温下陈化10～72小时；Step 2: Evaporate the water in the sol to obtain a pink gel, and age it at room temperature for 10 to 72 hours; 第三步：将陈化后的凝胶放到马弗炉中，从室温开始升温至500℃，保温2～8小时，使凝胶中的残余硝酸根分解，之后自然冷却，得到黑色粉末；Step 3: Put the aged gel in a muffle furnace, heat up from room temperature to 500°C, and keep it warm for 2 to 8 hours to decompose the residual nitrate in the gel, and then cool naturally to obtain a black powder; 第四步：将黑色粉末转移到碾钵中碾细，置于刚玉坩埚中，用电炉在700～900℃下焙烧，使其在高温下转变为钙钛矿结构相，保温6～24小时，制得LaxCa1-xCoO3粉体；Step 4: Transfer the black powder to a mortar and grind it finely, place it in a corundum crucible, and roast it in an electric furnace at 700-900°C to transform it into a perovskite structure phase at a high temperature, and keep it warm for 6-24 hours. Prepare La x Ca 1-x CoO 3 powder; 第五步：配制1M～5M的AgNO3溶液，在溶液中加入氨水，生成沉淀，继续加入氨水使沉淀消失，使其形成银氨络合物，然后，按钙钛矿氧化物与Ag的质量比为0.90～0.999∶0.10～0.001往银氨络合物溶液中加入已制得的LaxCa1-xCoO3粉体；再滴加还原剂水合肼或甲醛、或酒石酸钾钠的溶液，边搅拌边滴加，加入量为还原银离子所需量的1.2～2倍；且温度恒定在20～60℃间，经过滤、清洗、加热蒸干制得单质银沉积在钙钛矿型氧化物表面的LaxCa1-xCoO3/Ag复合粉体。Step 5: Prepare a 1M ~ 5M AgNO 3 solution, add ammonia water to the solution to form a precipitate, continue to add ammonia water to make the precipitate disappear, and make it form a silver-ammonia complex, and then, according to the mass of perovskite oxide and Ag The ratio is 0.90～0.999:0.10～0.001. Add the prepared La x Ca 1-x CoO 3 powder to the silver ammonia complex solution; then add the solution of reducing agent hydrazine hydrate or formaldehyde, or potassium sodium tartrate dropwise, Add dropwise while stirring, the amount added is 1.2 to 2 times the amount required to reduce silver ions; and the temperature is kept between 20 and 60°C. After filtering, washing, heating and evaporating to dryness, the elemental silver is deposited on the perovskite type oxidation La x Ca 1-x CoO 3 /Ag composite powder on the surface of the object. 2.一种按权利要求1所述的钙钛矿型LaxCa1-xCoO3/Ag复合粉体氧还原催化剂的制备方法制备的LaxCa1-xCoO3/Ag复合粉体氧还原催化剂。2. a kind of La x Ca 1-x CoO 3 /Ag composite powder oxygen prepared by the preparation method of perovskite type La x Ca 1-x CoO 3 /Ag composite powder oxygen reduction catalyst according to claim 1 reduction catalyst.
CN2010102197266A 2010-07-07 2010-07-07 Perovskite LaxCa1-xCoO3/Ag Composite Powder Oxygen Reduction Catalyst and Preparation Method Pending CN101884930A (en)

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CN102166517A (en) * 2011-03-21 2011-08-31 北京中航长力能源科技有限公司 Preparation method and application of perovskite type composite oxide catalyst
CN102166517B (en) * 2011-03-21 2012-06-27 北京中航长力能源科技有限公司 Preparation method and application of perovskite type composite oxide catalyst
CN102179242A (en) * 2011-03-23 2011-09-14 天津大学 Preparation and application of non-noble metal nitrogen oxide storage and reduction catalyst LaMnO3/K/ZrTiO4
CN102862954A (en) * 2011-07-07 2013-01-09 中国石油化工股份有限公司 Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production
CN102862954B (en) * 2011-07-07 2014-10-15 中国石油化工股份有限公司 Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production
CN102658152A (en) * 2012-04-19 2012-09-12 常州优特科新能源科技有限公司 Method for preparing oxygen electrode perovskite-type catalyst
CN102658152B (en) * 2012-04-19 2014-05-14 常州优特科新能源科技有限公司 Method for preparing oxygen electrode perovskite-type catalyst
CN103413924B (en) * 2013-06-17 2016-03-30 昆明理工大学 A kind of La 1-xca xcoO 3coated lithium ion battery LiNi 1/3co 1/3mn 1/3o 2positive electrode and preparation method thereof
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