CN115894023A - Lamellar Cu @ La assembled from nanoparticles 1/2 Sr 1/2 CoO 3 Preparation method of conductive ceramic powder - Google Patents
Lamellar Cu @ La assembled from nanoparticles 1/2 Sr 1/2 CoO 3 Preparation method of conductive ceramic powder Download PDFInfo
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
技术领域technical field
本发明涉及导电陶瓷粉体的制备，具体涉及一种由纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体的制备方法，可应用于析氢电催化、光催化、电接触领域。The present invention relates to the preparation of conductive ceramic powder, in particular to a preparation method of flake-shaped Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder assembled by nanoparticles, which can be applied to hydrogen evolution electrocatalysis and photocatalysis , Electrical contact field.
背景技术Background technique
在电接触行业，AgCdO由于在航空航天，汽车电器，低压电器等领域普遍应用被称为万能触点材料，但是AgCdO在使用过程会释放Cd蒸汽会对人体造成危害，因而需要找到一种绿色环保的触点材料代替。In the electrical contact industry, AgCdO is known as a universal contact material because it is widely used in aerospace, automotive electrical appliances, low-voltage electrical appliances and other fields, but AgCdO will release Cd vapor during use, which will cause harm to the human body, so it is necessary to find a green of the contact material instead.
发明内容Contents of the invention
本发明要解决的技术问题是，克服现有技术中的不足，提供一种由纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体的制备方法。The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a preparation method of flake-like Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder assembled by nanoparticles.
为解决技术问题，本发明的解决方案的具体步骤如下：For solving technical problem, the concrete steps of solution of the present invention are as follows:
提供一种由纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体的制备方法，包括以下步骤：Provided is a method for preparing a flaky Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder assembled by nanoparticles, comprising the following steps:
(1)按摩尔比1︰0.5︰0.5取乙酸钴四水合物、乙酸镧和乙酸锶，加入去离子水中搅拌至完全溶解，得到淡红色溶液；(1) Take cobalt acetate tetrahydrate, lanthanum acetate and strontium acetate at a molar ratio of 1:0.5:0.5, add deionized water and stir until completely dissolved to obtain a light red solution;
(2)按照步骤(1)中各溶质的用量、分子式La1/2Sr1/2CoO3，并按Cu︰La1/2Sr1/2CoO3的质量比为2～6︰100，计算并称量硝酸铜，然后加入溶液中并混匀；(2) According to the amount of each solute in step (1), the molecular formula La 1/2 Sr 1/2 CoO 3 , and the mass ratio of Cu: La 1/2 Sr 1/2 CoO 3 is 2 to 6: 100, Calculate and weigh the copper nitrate, then add to the solution and mix well;
(3)按照螯合剂与溶液中总金属离子的摩尔比为3.5︰1，将螯合剂加入溶液中，并在室温下连续搅拌30min，得到带有浑浊颗粒的浅红色溶液；将溶液pH值调整为9.5，继续在室温下搅拌30分钟，形成***溶液；(3) According to the molar ratio of the chelating agent to the total metal ions in the solution being 3.5:1, the chelating agent was added to the solution, and stirred continuously at room temperature for 30 minutes to obtain a light red solution with turbid particles; adjust the pH value of the solution 9.5, continue stirring at room temperature for 30 minutes to form a purple solution;
(4)将溶液在加热条件下搅拌至形成具有粘度的溶胶；将溶胶加入至反应釜中，在180℃条件下保温30个小时；移除上清液后，洗涤、烘干得到La1/2Sr1/2CoO3前驱体；(4) Stir the solution under heating conditions until a viscous sol is formed; add the sol to the reaction kettle and keep it warm at 180°C for 30 hours; after removing the supernatant, wash and dry to obtain La 1/ 2 Sr 1/2 CoO 3 precursor;
(5)将La1/2Sr1/2CoO3前驱体进行煅烧处理，获得由纳米颗粒组装的薄片状Cu@La1/ 2Sr1/2CoO3导电陶瓷粉体。(5) The La 1/2 Sr 1/2 CoO 3 precursor was calcined to obtain flake-like Cu@La 1/ 2 Sr 1/2 CoO 3 conductive ceramic powder assembled by nanoparticles.
作为本发明的优选方案，所述步骤(3)中的螯合剂是乙二胺四乙酸和柠檬酸，乙二胺四乙酸︰柠檬酸的摩尔比为2︰1.5。As a preferred version of the present invention, the chelating agent in the step (3) is ethylenediaminetetraacetic acid and citric acid, and the molar ratio of ethylenediaminetetraacetic acid:citric acid is 2:1.5.
作为本发明的优选方案，所述步骤(4)中的加热条件是指在水浴锅中保持80℃的温度，搅拌时间为2h。As a preferred solution of the present invention, the heating condition in the step (4) refers to maintaining a temperature of 80° C. in a water bath, and the stirring time is 2 hours.
作为本发明的优选方案，所述步骤(4)中将溶胶加入反应釜中时，是采用玻璃棒引流。As a preferred version of the present invention, when the sol is added to the reactor in the step (4), a glass rod is used for drainage.
作为本发明的优选方案，所述步骤(4)中的洗涤是指用去离子水和无水乙醇洗涤三遍。As a preferred solution of the present invention, the washing in step (4) refers to washing three times with deionized water and absolute ethanol.
作为本发明的优选方案，所述步骤(5)中的煅烧过程中，煅烧温度为750℃，保温时间8h，控制升温速率为12.5℃/min。As a preferred solution of the present invention, during the calcination process in the step (5), the calcination temperature is 750° C., the holding time is 8 hours, and the heating rate is controlled to be 12.5° C./min.
本发明进一步提供了前述薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体在制备电接触材料中的应用方法，是将该粉体产品与银通过高能球磨法得到Ag Cu@La1/2Sr1/2CoO3复合粉体；再将复合粉体进行初压初烧和复压复烧处理，最终制得电接触材料。The present invention further provides an application method of the aforementioned flaky Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder in the preparation of electrical contact materials. The powder product is mixed with silver to obtain Ag Cu@ La 1/2 Sr 1/2 CoO 3 composite powder; then the composite powder is subjected to initial pressure initial firing and re-pressure re-firing to finally obtain an electrical contact material.
作为本发明的优选方案，所述高能球磨工艺中，Ag粉与薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体的质量比为90:10，球料比为3:1，球磨机转动速度为180r/min,球磨时间为4h；在初压初烧和复压复烧处理时，初压的压力为600Mpa，复压的压力为800Mpa，保压时间均为30s，初烧和复烧的温度均为880℃，升温速率为10℃/Min，保温时间为6h。As a preferred solution of the present invention, in the high-energy ball milling process, the mass ratio of Ag powder to flake Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder is 90:10, and the ball-to-material ratio is 3:1 , the rotation speed of the ball mill is 180r/min, and the ball milling time is 4h; in the initial pressure initial firing and re-pressure re-firing treatment, the pressure of the initial pressure is 600Mpa, the pressure of the re-pressure is 800Mpa, and the holding time is 30s. The heating temperature and refiring temperature are both 880°C, the heating rate is 10°C/Min, and the holding time is 6h.
发明原理描述：Description of invention principle:
LaSrCoO3因具有高离子和电子传导性，已经被应用于燃料电池，气体传感器等电极领域及催化领域，但在电接触领域的应用还未见记载。Due to its high ion and electronic conductivity, LaSrCoO 3 has been used in fuel cells, gas sensors and other electrode fields and in the field of catalysis, but its application in the field of electrical contacts has not been documented.
LaCoO3具有典型的钙钛矿结构，当掺入锶后，晶体结构会发生扭曲，晶格常数和晶型会随温度和锶掺杂量改变，随着锶含量的增加，产生大量的氧空位，这些氧空位的存在使LaSrCoO3具有较高的电子运输能力和良好的光催化活性；并且LaSrCoO3在电弧作用下会分解产生氧气，与AgCdO在电弧作用下CdO的分解和蒸发产生大量Cd气体以吹散电弧有类似的作用。LaCoO 3 has a typical perovskite structure. When strontium is doped, the crystal structure will be distorted, and the lattice constant and crystal form will change with temperature and strontium doping amount. With the increase of strontium content, a large number of oxygen vacancies will be generated. , the existence of these oxygen vacancies makes LaSrCoO 3 have high electron transport ability and good photocatalytic activity; and LaSrCoO 3 will decompose to produce oxygen under the action of electric arc, and AgCdO will produce a large amount of Cd gas when it decomposes and evaporates CdO under the action of arc To blow off the arc has a similar effect.
基于上述技术原理，本发明利用LaSrCoO3经溶胶水热法制备由纳米颗粒组装成的薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体，不仅能够增大La1/2Sr1/2CoO3导电陶瓷粉体的比表面积，使La1/2Sr1/2CoO3表面活性增加；同时还以原位掺杂方式掺入Cu使得改性后LSCO陶瓷粉体与银界面结合更紧密，提高触点材料的导电性和抗电弧冲击能力。此外，以纳米颗粒组装成的薄片状结构能够增大材料的热导率，在电弧冲击时能及时疏散热量，提高了触点材料的电寿命。因此，本发明提供的产品能够在电接触领域代替传统电接触材料AgCdO。Based on the above-mentioned technical principles, the present invention uses LaSrCoO 3 to prepare flake-like Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder assembled from nanoparticles through sol hydrothermal method, which can not only increase the size of La 1/2 Sr The specific surface area of 1/2 CoO 3 conductive ceramic powder increases the surface activity of La 1/2 Sr 1/2 CoO 3 ; at the same time, Cu is added by in-situ doping to make the interface between the modified LSCO ceramic powder and silver The combination is tighter, improving the electrical conductivity and arc shock resistance of the contact material. In addition, the flaky structure assembled with nanoparticles can increase the thermal conductivity of the material, and can dissipate heat in time when the arc strikes, improving the electrical life of the contact material. Therefore, the product provided by the invention can replace the traditional electrical contact material AgCdO in the electrical contact field.
溶胶凝胶法和水热法均为本领域常见的材料制备工艺，但前者存在难以调控显微形貌且无法达到引入掺杂Cu所需的温度和压力，后者存在产量低的缺陷。单独运用水热法制备LaSrCoO3产率极低，相同原料情况下溶胶凝胶法制得的LaSrCoO3粉体是水热法的6-7倍。但是是要原位掺杂Cu需要高温高压，单独的溶胶凝胶法在水浴加热的温度是80℃且在大气环境下，无法达到掺杂所需要的温度和压力。本发明创新地提出溶胶水热法，在克服各自原有技术缺陷的同时充分发挥两者的技术优势，利用水热法的高温高压条件采用原位掺杂Cu的方式达到改善LaSrCoO3导电性和润湿性的目的，同时还实现了溶胶凝胶法的高产率。由于溶胶凝胶法的高产率和水热法的高温高压条件采用原位Cu掺杂的原因，本发明不仅反应条件简单，原料成本低，提高产品产量，还改善了LaSrCoO3导电性和润湿性。Both the sol-gel method and the hydrothermal method are common material preparation processes in this field, but the former has difficulty in controlling the microscopic morphology and cannot reach the temperature and pressure required for introducing doped Cu, and the latter has the defect of low yield. The yield of LaSrCoO 3 prepared by the hydrothermal method alone is extremely low, and the LaSrCoO 3 powder prepared by the sol-gel method is 6-7 times that of the hydrothermal method under the same raw material conditions. However, in-situ doping of Cu requires high temperature and high pressure, and the temperature and pressure required for doping cannot be achieved in the sol-gel method alone in a water bath at a heating temperature of 80°C and in an atmospheric environment. The present invention innovatively proposes the sol hydrothermal method, which fully utilizes the technical advantages of the two while overcoming the respective original technical defects, and uses the high temperature and high pressure conditions of the hydrothermal method to improve the electrical conductivity of LaSrCoO 3 by in-situ doping Cu. The purpose of wettability, while also achieving the high yield of the sol-gel method. Due to the high yield of the sol-gel method and the high temperature and high pressure conditions of the hydrothermal method using in-situ Cu doping, the present invention not only has simple reaction conditions, low raw material costs, increases product yield, but also improves the electrical conductivity and wettability of LaSrCoO3 sex.
与现有技术相比，本发明的技术效果是：Compared with prior art, technical effect of the present invention is:
(1)本发明综合利用溶胶凝胶法和水热法的技术优势，创新提出溶胶水热法制备出由纳米颗粒组装成的薄片状Cu@La1/2Sr1/2CoO3导电陶瓷粉体。该方法具有反应条件简单、原料成本低、产量高的优点。(1) The present invention comprehensively utilizes the technical advantages of the sol-gel method and the hydrothermal method, and innovatively proposes the sol-hydrothermal method to prepare thin-sheet Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder assembled from nanoparticles body. The method has the advantages of simple reaction conditions, low raw material cost and high yield.
(2)相较于传统的颗粒状La1/2Sr1/2CoO3，本发明获得的产品具有更高的比面积，与银润湿性极好、导电性能好等综合电接触性能，因而电接触等相关领域得到良好的应用前景。(2) Compared with the traditional granular La 1/2 Sr 1/2 CoO 3 , the product obtained by the present invention has a higher specific area, excellent wettability with silver, good electrical conductivity and other comprehensive electrical contact properties, Therefore, electrical contacts and other related fields have good application prospects.
附图说明Description of drawings
图1为实施例2中薄片状Cu@La1/2Sr1/2CoO3陶瓷粉体SEM照片。Fig. 1 is the SEM photo of the flaky Cu@La 1/2 Sr 1/2 CoO 3 ceramic powder in Example 2.
图2为实施例2中薄片状Cu@La1/2Sr1/2CoO3陶瓷粉体SEM照片。Fig. 2 is the SEM photo of the flaky Cu@La 1/2 Sr 1/2 CoO 3 ceramic powder in Example 2.
图3为对比例1中La1/2Sr1/2CoO3制成陶瓷基底后与银的润湿角示意。Fig. 3 is a schematic diagram of the wetting angle between La 1/2 Sr 1/2 CoO 3 and silver after it is made into a ceramic substrate in Comparative Example 1.
图4为实施例2中Cu@La1/2Sr1/2CoO3制成陶瓷基底后与银的润湿角示意。Fig. 4 is a schematic diagram of the wetting angle with silver after Cu@La 1/2 Sr 1/2 CoO 3 is made into a ceramic substrate in Example 2.
具体实施方式Detailed ways
下面通过具体实施方式对本发明的实现进行示例性的描述。The implementation of the present invention will be exemplarily described below through specific embodiments.
实施例1Example 1
将0.01mol乙酸钴四水合物(C4H6CoO4·4H2O)、0.005mol乙酸镧(La(CH3COO)3))、0.005mol乙酸锶(C4H6O4Sr)加入50mL的去离子水中，室温下搅拌10分钟至完全溶解形成淡红色的溶液。按照Cu：La1/2Sr1/2CoO3质量比为2:100，将0.17g(Cu(NO3)2)加入溶液搅拌10min。再按照乙二胺四乙酸、柠檬酸与与溶液总金属离子的摩尔比为2︰1.5︰1，将作为螯合剂的乙二胺四乙酸和柠檬酸分别加入溶液中并在室温下连续搅拌30min形成带有浑浊颗粒的浅红色溶液。然后再以缓慢滴定的速度滴加氨水将溶液PH调至9.5，继续在室温下搅拌30分钟，形成***溶液。将配好的溶液移至温度为80℃水浴锅中加热搅拌2h形成有一定粘度的溶胶。用玻璃棒将溶胶引流至反应釜，在180℃的烘箱中保温30个小时。保温结束后，将溶胶从反应釜中取出，移除上清液，用去离子水和无水乙醇洗涤三遍，烘干得到La1/2Sr1/ 2CoO3前驱体。再放到低温马弗炉中煅烧，具体的煅烧工艺：升温速率为12.5℃/min，保温温度750℃，保温时间8h，最终获得纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3粉体。Add 0.01mol cobalt acetate tetrahydrate (C 4 H 6 CoO 4 4H 2 O), 0.005mol lanthanum acetate (La(CH 3 COO) 3 )), and 0.005mol strontium acetate (C 4 H 6 O 4 Sr) 50mL of deionized water, stirred at room temperature for 10 minutes until completely dissolved to form a light red solution. According to the Cu:La 1/2 Sr 1/2 CoO 3 mass ratio of 2:100, 0.17 g (Cu(NO 3 ) 2 ) was added to the solution and stirred for 10 min. According to the molar ratio of ethylenediaminetetraacetic acid, citric acid and the total metal ions in the solution of 2:1.5:1, add ethylenediaminetetraacetic acid and citric acid as chelating agents into the solution respectively and continuously stir at room temperature for 30min A reddish solution with cloudy particles formed. Then add ammonia water dropwise at a slow titration rate to adjust the pH of the solution to 9.5, and continue to stir at room temperature for 30 minutes to form a purple-red solution. Move the prepared solution to a water bath at 80°C and heat and stir for 2 hours to form a sol with a certain viscosity. The sol was drained into the reactor with a glass rod, and kept in an oven at 180°C for 30 hours. After the incubation, the sol was taken out from the reactor, the supernatant was removed, washed three times with deionized water and absolute ethanol, and dried to obtain the La 1/2 Sr 1/ 2 CoO 3 precursor. Then put it into a low-temperature muffle furnace for calcination. The specific calcination process: the heating rate is 12.5°C/min, the holding temperature is 750°C, and the holding time is 8h. Finally, the thin-sheet Cu@La 1/2 Sr 1/2 assembled by nanoparticles is obtained. CoO 3 powder.
实施例2Example 2
将0.01mol乙酸钴四水合物(C4H6CoO4·4H2O)、0.005mol乙酸镧(La(CH3COO)3))、0.005mol乙酸锶(C4H6O4Sr)加入50mL的去离子水中，室温下搅拌10分钟至完全溶解形成淡红色的溶液。按照Cu：La1/2Sr1/2CoO3质量比为4:100，将0.35g(Cu(NO3)2)加入溶液搅拌10min。再按照乙二胺四乙酸、柠檬酸与与溶液总金属离子的摩尔比为2︰1.5︰1，将作为螯合剂的乙二胺四乙酸和柠檬酸分别加入溶液中，并在室温下连续搅拌30min，形成带有浑浊颗粒的浅红色溶液。然后再以滴定的速度滴加氨水将溶液PH调至9.5，继续在室温下搅拌30分钟，形成***溶液。将配好的溶液移至温度为80℃水浴锅中加热搅拌2h形成有一定粘度的溶胶。用玻璃棒将溶胶引流至反应釜，在180℃的烘箱中保温30个小时。保温结束后，将溶胶从反应釜中取出，移除上清液，用去离子水和无水乙醇洗涤三遍，烘干得到La1/2Sr1/2CoO3前驱体。再放到低温马弗炉中煅烧，具体的煅烧工艺：升温速率为12.5℃/min，保温温度750℃，保温时间8h，最终获得纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3粉体。Add 0.01mol cobalt acetate tetrahydrate (C 4 H 6 CoO 4 4H 2 O), 0.005mol lanthanum acetate (La(CH 3 COO) 3 )), and 0.005mol strontium acetate (C 4 H 6 O 4 Sr) 50mL of deionized water, stirred at room temperature for 10 minutes until completely dissolved to form a light red solution. According to Cu: La 1/2 Sr 1/2 CoO 3 mass ratio of 4:100, 0.35 g (Cu(NO 3 ) 2 ) was added to the solution and stirred for 10 min. According to the molar ratio of ethylenediaminetetraacetic acid, citric acid and the total metal ions in the solution to be 2:1.5:1, add ethylenediaminetetraacetic acid and citric acid as chelating agents into the solution respectively, and continuously stir at room temperature After 30 min, a light red solution with turbid particles was formed. Then ammonia water was added dropwise at a titration rate to adjust the pH of the solution to 9.5, and the stirring was continued at room temperature for 30 minutes to form a purple-red solution. Move the prepared solution to a water bath at 80°C and heat and stir for 2 hours to form a sol with a certain viscosity. The sol was drained into the reactor with a glass rod, and kept in an oven at 180°C for 30 hours. After the incubation, the sol was taken out from the reactor, the supernatant was removed, washed three times with deionized water and absolute ethanol, and dried to obtain the La 1/2 Sr 1/2 CoO 3 precursor. Then put it into a low-temperature muffle furnace for calcination. The specific calcination process: the heating rate is 12.5°C/min, the holding temperature is 750°C, and the holding time is 8h. Finally, the thin-sheet Cu@La 1/2 Sr 1/2 assembled by nanoparticles is obtained. CoO 3 powder.
实施例3Example 3
将0.01mol乙酸钴四水合物(C4H6CoO4·4H2O)、0.005mol乙酸镧(La(CH3COO)3))、0.005mol乙酸锶(C4H6O4Sr)加入50mL的去离子水中，室温下搅拌10分钟至完全溶解形成淡红色的溶液。按照Cu：La1/2Sr1/2CoO3质量比为6:100，将0.53g(Cu(NO3)2)加入溶液搅拌10min。再按照乙二胺四乙酸、柠檬酸与与溶液总金属离子的摩尔比为2︰1.5︰1，将作为螯合剂的乙二胺四乙酸和柠檬酸分别加入溶液中，并在室温下连续搅拌30min，形成带有浑浊颗粒的浅红色溶液。然后再以缓慢滴定的速度滴加氨水将溶液PH调至9.5，继续在室温下搅拌30分钟，形成***溶液。将配好的溶液移至温度为80℃水浴锅中加热搅拌2h形成有一定粘度的溶胶。用玻璃棒将溶胶引流至反应釜，在180℃的烘箱中保温30个小时。保温结束后，将溶胶从反应釜中取出，移除上清液，用去离子水和无水乙醇洗涤三遍，烘干得到La1/2Sr1/ 2CoO3前驱体。再放到低温马弗炉中煅烧，具体的煅烧工艺：升温速率为12.5℃/min，保温温度750℃，保温时间8h，最终获得纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3粉体。Add 0.01mol cobalt acetate tetrahydrate (C 4 H 6 CoO 4 4H 2 O), 0.005mol lanthanum acetate (La(CH 3 COO) 3 )), and 0.005mol strontium acetate (C 4 H 6 O 4 Sr) 50mL of deionized water, stirred at room temperature for 10 minutes until completely dissolved to form a light red solution. According to the Cu:La 1/2 Sr 1/2 CoO 3 mass ratio of 6:100, 0.53 g (Cu(NO 3 ) 2 ) was added to the solution and stirred for 10 min. According to the molar ratio of ethylenediaminetetraacetic acid, citric acid and the total metal ions in the solution to be 2:1.5:1, add ethylenediaminetetraacetic acid and citric acid as chelating agents into the solution respectively, and continuously stir at room temperature After 30 min, a light red solution with turbid particles was formed. Then add ammonia water dropwise at a slow titration rate to adjust the pH of the solution to 9.5, and continue to stir at room temperature for 30 minutes to form a purple-red solution. Move the prepared solution to a water bath at 80°C and heat and stir for 2 hours to form a sol with a certain viscosity. The sol was drained into the reactor with a glass rod, and kept in an oven at 180°C for 30 hours. After the incubation, the sol was taken out from the reactor, the supernatant was removed, washed three times with deionized water and absolute ethanol, and dried to obtain the La 1/2 Sr 1/ 2 CoO 3 precursor. Then put it into a low-temperature muffle furnace for calcination. The specific calcination process: the heating rate is 12.5°C/min, the holding temperature is 750°C, and the holding time is 8h. Finally, the thin-sheet Cu@La 1/2 Sr 1/2 assembled by nanoparticles is obtained. CoO 3 powder.
对比例1(对照组)Comparative example 1 ( control group )
将0.01mol乙酸钴四水合物(C4H6CoO4·4H2O)、0.005mol乙酸镧(La(CH3COO)3))、0.005mol乙酸锶(C4H6O4Sr)加入50mL的去离子水中，室温下搅拌10分钟至完全溶解形成淡红色的溶液。再按照乙二胺四乙酸、柠檬酸与与溶液总金属离子的摩尔比为2︰1.5︰1，将作为螯合剂的乙二胺四乙酸和柠檬酸分别加入溶液中并在室温下连续搅拌30min形成带有浑浊颗粒的浅红色溶液,形成带有浑浊颗粒的浅红色溶液。后再以缓慢滴定的速度滴加氨水将溶液PH调至9.5，继续在室温下搅拌30分钟，形成***溶液。将配好的溶液移至温度为80℃水浴锅中加热搅拌2h形成有一定粘度的溶胶。用玻璃棒将溶胶引流至反应釜，在180℃的烘箱中保温30个小时。保温结束后，将溶胶从反应釜中取出，移除上清液，用去离子水和无水乙醇洗涤三遍，烘干得到La1/2Sr1/2CoO3前驱体。再放到低温马弗炉中煅烧，具体的煅烧工艺：升温速率为12.5℃/min，保温温度750℃，保温时间8h，最终获得颗粒状La1/2Sr1/2CoO3粉体。Add 0.01mol cobalt acetate tetrahydrate (C 4 H 6 CoO 4 4H 2 O), 0.005mol lanthanum acetate (La(CH 3 COO) 3 )), and 0.005mol strontium acetate (C 4 H 6 O 4 Sr) 50mL of deionized water, stirred at room temperature for 10 minutes until completely dissolved to form a light red solution. According to the molar ratio of ethylenediaminetetraacetic acid, citric acid and the total metal ions in the solution of 2:1.5:1, add ethylenediaminetetraacetic acid and citric acid as chelating agents into the solution respectively and continuously stir at room temperature for 30min A light red solution with turbid particles is formed, and a light red solution with turbid particles is formed. Then add ammonia water dropwise at a slow titration rate to adjust the pH of the solution to 9.5, and continue to stir at room temperature for 30 minutes to form a purple-red solution. Move the prepared solution to a water bath at 80°C and heat and stir for 2 hours to form a sol with a certain viscosity. The sol was drained into the reactor with a glass rod, and kept in an oven at 180°C for 30 hours. After the incubation, the sol was taken out from the reactor, the supernatant was removed, washed three times with deionized water and absolute ethanol, and dried to obtain the La 1/2 Sr 1/2 CoO 3 precursor. Then put it into a low-temperature muffle furnace for calcination. The specific calcination process: the heating rate is 12.5°C/min, the holding temperature is 750°C, and the holding time is 8h. Finally, granular La 1/2 Sr 1/2 CoO 3 powder is obtained.
对比例2：Comparative example 2:
市购获得温州宏丰电工合金股份有限公司商用AgCdO电接触产品，作为对比例2。Commercially available AgCdO electrical contact products from Wenzhou Hongfeng Electrical Alloy Co., Ltd. were purchased as Comparative Example 2.
按以下方式将本发明各实施例和对比例1的产品制备成电接触材料。The products of the examples of the present invention and Comparative Example 1 were prepared as electrical contact materials in the following manner.
首先将各实施例中制备得到的不同Cu掺杂比例的增强相La1/2Sr1/2CoO3粉体放入到氧化锆球磨罐中，加入少量的酒精在磁力搅拌机上搅拌，再将Ag粉缓慢的加入到球磨罐中，然后采用高能球磨工艺制备AgLa1/2Sr1/2CoO3复合粉体。其中Ag粉与增强相粉体的质量比为90:10，球料比为3:1，球磨机转动速度为180r/min,球磨时间为4h。将得到的复合粉体分别记为AgLSCO-2％Cu、AgLSCO-4％Cu、AgLSCO-6％Cu及AgLSCO。利用电动压片机和马弗炉进行初压初烧复压复烧将上述复合粉体制备成电接触材料(片材)。其中初压为600Mpa,复压为800Mpa,保压时间为30s，初烧复烧温度为880℃，升温速率为10℃/Min，保温6h。First, put the reinforcement phase La 1/2 Sr 1/2 CoO 3 powders prepared in various examples with different Cu doping ratios into a zirconia ball mill jar, add a small amount of alcohol and stir on a magnetic stirrer, and then The Ag powder was slowly added into the ball mill jar, and then the AgLa 1/2 Sr 1/2 CoO 3 composite powder was prepared by high-energy ball milling process. Among them, the mass ratio of Ag powder to reinforcing phase powder is 90:10, the ball-to-material ratio is 3:1, the rotation speed of the ball mill is 180r/min, and the ball milling time is 4h. The obtained composite powders were respectively referred to as AgLSCO-2% Cu, AgLSCO-4% Cu, AgLSCO-6% Cu, and AgLSCO. The above-mentioned composite powder is prepared into an electrical contact material (sheet) by using an electric tablet press and a muffle furnace for initial pressing, initial firing, repressing and refiring. Among them, the initial pressure is 600Mpa, the re-pressure is 800Mpa, the holding time is 30s, the initial firing and re-firing temperature is 880°C, the heating rate is 10°C/Min, and the heat preservation time is 6h.
以业内通用检测方法对本发明各实施例和对比例的产品进行测试。其中，比表面积是针对Cu@La1/2Sr1/2CoO3粉体，润湿角是针对Cu@La1/2Sr1/2CoO3陶瓷基片，电接触性能是针对经过初压初烧复压复烧后所得到的AgCu@La1/2Sr1/2CoO3电接触材料。The products of the various embodiments of the present invention and the comparative examples are tested with the common detection method in the industry. Among them, the specific surface area is for the Cu@La 1/2 Sr 1/2 CoO 3 powder, the wetting angle is for the Cu@La 1/2 Sr 1/2 CoO 3 ceramic substrate, and the electrical contact performance is for the initial pressure The AgCu@La 1/2 Sr 1/2 CoO 3 electrical contact material obtained after initial firing, repressing and refiring.
表1 Cu@La1/2Sr1/2CoO3导电陶瓷粉体性能表征Table 1 Characterization of Cu@La 1/2 Sr 1/2 CoO 3 conductive ceramic powder
表2 AgCu@La1/2Sr1/2CoO3电接触材料性能表征Table 2 Characterization of AgCu@La 1/2 Sr 1/2 CoO 3 electrical contact materials
从表1中可以看出，相较于对比例1未掺杂的颗粒状La1/2Sr1/2CoO3，以及对比例2商用的AgCdO，本发明获得的La1/2Sr1/2CoO3具有比表面积高和与银润湿性极好的优势。例如，对比例1中未掺杂Cu，将其颗粒状La1/2Sr1/2CoO3制成陶瓷基底后，与银的润湿角为148°(如图3所示)。在本发明的实施例2中，将其纳米颗粒组装的薄片状Cu@La1/2Sr1/2CoO3粉体制成陶瓷基底后，与银的润湿角为45°，明显得到改善(如图4所示)。It can be seen from Table 1 that compared with the undoped granular La 1/2 Sr 1/2 CoO 3 in Comparative Example 1 and the commercial AgCdO in Comparative Example 2, the La 1/2 Sr 1/2 CoO 3 obtained in the present invention 2 CoO 3 has the advantages of high specific surface area and excellent wettability with silver. For example, in Comparative Example 1, Cu was not doped, and its granular La 1/2 Sr 1/2 CoO 3 was made into a ceramic substrate, and the wetting angle with silver was 148° (as shown in Figure 3). In Example 2 of the present invention, after making the flaky Cu@La 1/2 Sr 1/2 CoO 3 powder assembled with nanoparticles into a ceramic substrate, the wetting angle with silver was 45°, which was significantly improved (As shown in Figure 4).
从表2可以看出，本发明实施例1-3掺杂Cu的AgCu@La1/2Sr1/2CoO3电阻率都要比对比例1未掺杂Cu的Ag La1/2Sr1/2CoO3和对比例2商用的AgCdO要低，导电性能更好，且电寿命性能优异。It can be seen from Table 2 that the resistivity of AgCu@La 1/2 Sr 1/2 CoO 3 doped with Cu in Example 1-3 of the present invention is higher than that of Ag La 1/2 Sr 1 without Cu in Comparative Example 1 . /2 CoO 3 and the AgCdO commercially available in Comparative Example 2 are lower, have better electrical conductivity, and have excellent electrical life performance.
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| CN117003292A (en) * | 2023-04-07 | 2023-11-07 | 浙江大学 | Preparation method and application of fibrous LSCO conductive ceramic material |
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