CN108754545A - 一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法 - Google Patents
一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法 Download PDFInfo
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- CN108754545A CN108754545A CN201810459183.1A CN201810459183A CN108754545A CN 108754545 A CN108754545 A CN 108754545A CN 201810459183 A CN201810459183 A CN 201810459183A CN 108754545 A CN108754545 A CN 108754545A
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- graphene
- carbon nanotube
- heteropoly acid
- composite anode
- powder
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,属于新材料制备技术领域。将碳纳米管和/或石墨烯进行氨基化改性处理,将杂多酸溶于热水中得到浓度为0.0001~0.01mol/L杂多酸溶液,加入碳纳米管和/或石墨烯、分散剂,然后加入0.0005~0.2mol氯化钡,搅拌均匀,静置24小时,过滤得到杂多酸修饰碳纳米管和/或石墨烯复合粉体;高能球磨合金化;粉末冶金成型制得杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极。本方法工艺操作简单,得到的复合阳极成本低,催化性能优异,使用寿命与传统的铅阳极相仿。
Description
技术领域
本发明涉及一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,属于新材料制备技术领域。
背景技术
工业电积一般用铅合金作阳极,因其价格低廉、易加工成型、在硫酸溶液中的电化学性能较稳定,如锌电积一般用Pb–Ag(0.5wt.%~1.0wt.%)阳极,铜电积则采用Pb-Sb、Pb-Ca-Sn阳极。但铅合金阳极在生产中存在诸多缺陷,主要有:析氧电位高,密度大,强度低,易变形而造成短路等。冶金行业多年来致力于研发高强度、耐腐蚀、导电性好、析氧电位低、价格便宜、寿命长的新型节能阳极材料。
为解决铅及其合金阳极存在的问题,主要从铅阳极改良,即通过合金化、表面改性;非铅金属基阳极,如钛基、铝基、不锈钢基和镍基等阳极;用导电有机聚合物作阳极材料等三个方面进行,并取得了一定的效果。公开号201710228113.0的专利采用添加0.001~0.05%稀土来改进铅银合金阳极。公开号201610893044.0的专利添加稀土镧来降低Pb-Ag阳极合金腐蚀率。公开号CN200910237560.8的专利公开了属于电化学技术领域的一种复合阳极及其制备方法。该复合阳极由二氧化铅粉末、改性金属氧化物粉末和粘合剂粉末经压片制得,各组分的质量百分比为:二氧化铅粉末≥65%,5%≤改性金属氧化物粉末≤30%,粘合剂粉末≤5%。本发明的复合阳极在节约电耗和提高使用寿命上都比普通的基体PbO2阳极更具优势。本发明制备方法属于无基体制备法,从根本上避免了镀层脱落、析氧电位高等问题。公开号CN201310542693.2的专利公开了一种多孔二氧化铅材料的制备方法。包括对聚氨酯海绵基底依次进行除油、粗化、中和、预浸和化学氧化处理后作为阳极,以纯铅板作阴极进行电化学氧化处理,最后固化,干燥得到多孔二氧化铅材料。公开号201710083818.8的专利公开了一种多孔铅合金阳极的制备方法。采用泡沫金属作为造孔基体并配合特有装置的渗流法,包括泡沫金属表面预处理、熔融铅合金加压渗流及泡沫金属的溶出等步骤。公开号CN201210084089.5的专利提出一种铝基铅及铅合金复合阳极制备方法,工艺步骤:按铅或铅合金各组元比例配制浇铸成铅合金棒材;在铝基材料棒材表面加工若干条沿长度方向的线状燕尾槽;加工好燕尾槽的铝基材料棒材表面拉毛处理;铝基材料和铅或铅合金棒材送入包覆设备进行包覆铅或铅合金包覆材料层;包覆完后在包覆材料层表面立即进行增表处理得到圆弧凸凹状或锯齿状花纹;冷却即为复合材料;复合材料外表面经增表处理再经外形加工成阳极板面,由纯铅与铜排浇铸的导电梁,阳极板面和导电梁通过乙炔焰焊接成阳极。应用于有色金属电积过程可显著提高阳极板的导电性能,提高有色金属电积过程的电流效率,显著降低电积过程的能耗。公开号CN201310311974.7的专利提出了一种钛基纳米二氧化铅的制备方法。公开号CN201310114311.6的专利公开一种不锈钢基二氧化铅电极的制备方法。专利CN10413131B首次将碳纳米管和/或石墨烯等碳纳米材料引入铅合金阳极制备,得到了阳极电位与铅银合金接近的电极。
上述阳极较传统的铅及其合金阳极性能有所改进,但依然存在成本高、使用寿命有限、机械性能不足的问题,从而限制了其广泛的推广使用。
发明内容
针对上述现有技术存在的问题及不足,本发明提供一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法。该方法首先在碳纳米管和/或石墨烯表面引入氨基,通过表面氨基与杂多酸分子的静电作用实现碳纳米管和/或石墨烯的表面功能化修饰,过量的杂多酸与钡形成难溶性盐,以修饰后碳纳米管和/或石墨烯为晶核,实现包覆型共沉积。利用碳纳米管和/或石墨烯的高导电性,制备出高导电性的杂多酸碳纳米管和/或石墨烯复合粉体,然后采用高能球磨方法将上述粉体与金属铅粉进行合金化,实现粉体在金属中的深度嵌入式结合,最后通过粉末冶金的方法制备出杂多酸/碳纳米管或石墨烯增强的铅基复合阳极。阳极结合了杂多酸的高催化性、碳纳米管和/或石墨烯具有优异的力学和电学性能,制得的复合阳极机械性能提升,导电能力增强,催化性能提高,本发明通过以下技术方案实现。
一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其具体步骤如下:
步骤1、氨基化改性处理:将碳纳米管和/或石墨烯进行氨基化改性处理;
步骤2、表面修饰:将杂多酸溶于热水中得到浓度为0.0001~0.01mol/L杂多酸溶液,加入经步骤1氨基化改性处理的碳纳米管和/或石墨烯、分散剂,超声使得碳纳米管和/或石墨烯在杂多酸溶液中分散均匀得到含碳纳米管和/或石墨烯颗粒的溶液,碳纳米管和/或石墨烯加入量为0.01~2g每升含碳纳米管和/或石墨烯颗粒的溶液,分散剂加入量为0.5~10g/每升含碳纳米管和/或石墨烯颗粒的溶液,然后按照每升含碳纳米管和/或石墨烯颗粒的溶液加入0.0005~0.2mol氯化钡,搅拌均匀,静置24小时,过滤得到杂多酸修饰碳纳米管和/或石墨烯复合粉体;
步骤3、高能球磨合金化:将金属铅粉和步骤2得到的杂多酸修饰碳纳米管和/或石墨烯复合粉体在真空或惰性气氛环境下高能球磨机中合金化得到复合阳极粉体;杂多酸修饰碳纳米管和/或石墨烯复合粉体占复合阳极粉体质量的0.1~1%;
步骤4、粉末冶金成型:将步骤3得到的复合阳极粉体在20~50MPa下冷压成型,在250℃还原性气氛下烧结4h即制得杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极。
所述步骤1中碳纳米管为多壁碳纳米管、单壁碳纳米管中的一种或两种任意比例混合物。
所述步骤2中杂多酸为K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O、K10[Co(H2O)2(SiW10O35)2]•8.25H2O中的一种或两种任意比例混合物。
所述步骤2中分散剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、明胶、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、烷基脂肪醇聚氧乙烯醚、脂肪胺聚氧乙烯醚、烷基醇酰胺聚氧乙烷醚、嵌段聚氧乙烯-聚氧丙烯醚、烷基醇酰胺、聚乙烯吡咯烷酮中的一种或几种任意比例混合物。
所述步骤2中金属铅粉粒度小于200目,纯度大于99.5%。
所述步骤2中高能球磨机为行星式,磨料为氧化锆球,球料比大于10,转速100~300转/分,球磨时间10~30分钟。
上述步骤2的杂多酸K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O合成方法为:33g钨酸钠和3.3g磷酸氢二钠溶入100ml水中,用乙酸调pH=7,在搅拌条件下滴加300g/乙酸钴溶液30ml,125℃下加热回流2小时,热过滤,滤液加入5g乙酸钾,降温结晶后得到K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O。图4为杂多酸的红外光谱图。
上述步骤2中杂多酸 K10[Co(H2O)2(SiW10O35)2]•8.25H2O合成方法:0.55mol钨酸钠溶于300ml水中,在剧烈搅拌下缓慢加入4mol/L的盐酸溶液165ml,加入0.5mol/L硅酸钠溶液100ml,调节pH于5和6之间,反应100分钟,加入90g氯化钾,15分钟后过滤得到K8[SiW11O39]•14H2O。将得到的K8[SiW11O39] •14H2O约15g溶于150ml水中,用碳酸钾调pH=9.1,搅拌30分钟,加入40g氯化钾,沉淀得到K8[SiW10O36] •12H2O。在1mol/L氯化钾溶液20ml中加入0.4mmol氯化钴,1g HK8[SiW10O36] •12H2O,调pH=4.5,50℃条件下搅拌反应30分钟,降温结晶得到K10[Co(H2O)2(SiW10O35)2]•8.25H2O。
上述其他试剂均能市购得到。
本发明的有益效果是:
(1)本方法工艺操作简单,得到的复合阳极成本低,催化性能优异,使用寿命与传统的铅阳极相仿;(2)杂多酸与碳纳米管/石墨烯的复合解决了催化性能和导电性能方面的问题,同时碳纳米管/石墨烯表面引入杂多酸有效防止了其易于团聚的难题;(3)高能球磨工艺实现了复合粉体在金属铅中的分散问题;(3)本方法环境友好,本发明所使用的原料对环境影响小。
附图说明
图1是本发明工艺流程图;
图2是本发明实施例1制备得到的杂多酸修饰碳纳米管增强铅基复合阳极照片;
图3是本发明实施例1制备得到的杂多酸修饰碳纳米管增强铅基复合阳极(▽-)与铅阳极(-□-)和工业用铅银钙合金阳极(Pb0.75%Ag1%Ca)(○-)在锌电积液中的析氧电势比较图(j=500A/cm2)。
图4为杂多酸K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O的红外光谱图。
具体实施方式
下面结合附图和具体实施方式,对本发明作进一步说明。
实施例1
如图1所示,该杂多酸修饰的碳纳米管增强铅基复合阳极制备方法,其具体步骤如下:
步骤1、氨基化改性处理:将碳纳米管进行氨基化改性处理;
步骤1.1、羧基化:将多壁碳纳米管在体积比为3:1的硫酸(98wt%)和硝酸(68wt%)的混合溶液中,在温度为60℃氧化4小时,然后过滤,去离子水清洗至中性,50℃下真空干燥得到羧基化多壁碳纳米管;
步骤1.2、酰氯化:将1g步骤1.1得到的羧基化多壁碳纳米管,加入20mL二氯亚砜,70℃下搅拌回流24小时,过滤后用四氢呋喃清洗,50℃下真空干燥得到酰氯化多壁碳纳米管;
步骤1.3、酰胺化:将1g步骤1.2得到的酰氯化多壁碳纳米管,加入5g碳酸铵,滴加50mL氨水,搅拌下反应6小时,过滤,用去离子水清洗,50℃下真空干燥得到酰胺化多壁碳纳米管;
步骤1.4霍夫曼消去反应:将1g步骤1.3得到的酰胺化多壁碳纳米管0~5℃条件下滴加30mL次氯酸钠,滴加时间30min,然后搅拌反应4小时,升温至70℃,反应2小时,冷却后过滤,50℃下真空干燥得到氨基化改性处理的碳纳米管;
步骤2、表面修饰:将杂多酸(K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O)溶于95℃100mL热水中得到浓度为0.0001mol/L杂多酸溶液,加入经步骤1氨基化改性处理的碳纳米管、分散剂(聚乙烯吡咯烷酮),超声(超声频率为40kHz)使得碳纳米管在杂多酸溶液中分散均匀得到含碳纳米管颗粒的溶液,碳纳米管加入量为0.05g每升含碳纳米管颗粒的溶液,分散剂加入量为0.5g/每升含碳纳米管颗粒的溶液,然后按照每升含碳纳米管颗粒的溶液加入0.05mol氯化钡,搅拌均匀,静置24小时,过滤得到杂多酸修饰碳纳米管复合粉体;
步骤3、高能球磨合金化:将金属铅粉(金属铅粉粒度小于200目,纯度大于99.5%)和步骤2得到的杂多酸修饰碳纳米管复合粉体在真空气氛环境下(真空度<0.1kPa)高能球磨机中合金化得到复合阳极粉体;杂多酸修饰碳纳米管复合粉体占复合阳极粉体质量的0.1%;高能球磨机为行星式,磨料为氧化锆球,球料比20,转速200转/分,球磨时间30分钟;
步骤4、粉末冶金成型:将步骤3得到的复合阳极粉体在30MPa下冷压成型,在250℃还原性气氛(H2流量为250L/h)下烧结4h即制得杂多酸修饰的碳纳米管增强铅基复合阳极。
本实施例制备得到的杂多酸修饰碳纳米管增强铅基复合阳极照片如图2所示。
为进一步比较该杂多酸修饰碳纳米管增强铅基复合阳极的电催化性能,在工业锌电积液(160g/LH2SO4+60g/LZn2+)中,电流密度为500A/m2条件下,杂多酸修饰碳纳米管增强铅基复合阳极(▽-)与铅阳极(-□-)和工业用铅银钙合金阳极(Pb0.75%Ag1%Ca)(-○-)在锌电积液中的析氧电势比较,具体析氧电位随时间变化的关系示于图3。从图3中可以看出杂多酸修饰碳纳米管增强铅基复合阳极的超电位最低,在1.48V左右,而纯铅和铅银合金分别为1.62V和1.56V。这表明在锌电积条件下,杂多酸修饰碳纳米管增强铅基复合阳极与工业用铅银钙合金阳极相比,超电压降低了80mV,与纯铅比降低了170mV。
实施例2
如图1所示,该杂多酸修饰的石墨烯增强铅基复合阳极制备方法,其具体步骤如下:
步骤1、氨基化改性处理:将石墨烯进行氨基化改性处理;
步骤1.1、羧基化:将石墨烯在体积比为3:1的硫酸(98wt%)和硝酸(68wt%)的混合溶液中,在温度为60℃氧化4小时,然后过滤,去离子水清洗至中性,50℃下真空干燥得到羧基化石墨烯;
步骤1.2、酰氯化:将1g步骤1.1得到的羧基化石墨烯,加入20mL二氯亚砜,70℃下搅拌回流24小时,过滤后用四氢呋喃清洗,50℃下真空干燥得到酰氯化石墨烯;
步骤1.3、酰胺化:将1g步骤1.2得到的酰氯化石墨烯,加入5g碳酸铵,滴加50mL氨水,搅拌下反应6小时,过滤,用去离子水清洗,50℃下真空干燥得到酰胺化石墨烯;
步骤1.4霍夫曼消去反应:将1g步骤1.3得到的酰胺化石墨烯0~5℃条件下滴加30mL次氯酸钠,滴加时间30min,然后搅拌反应4小时,升温至70℃,反应2小时,冷却后过滤,50℃下真空干燥得到氨基化改性处理的石墨烯;
步骤2、表面修饰:将杂多酸(K10[Co(H2O)2(SiW10O35)2]•8.25H2O)溶于95℃100mL热水中得到浓度为0.01mol/L杂多酸溶液,加入经步骤1氨基化改性处理的石墨烯、分散剂(质量比为1:1:1的十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵混合物),超声(超声频率为40kHz)使得石墨烯在杂多酸溶液中分散均匀得到含石墨烯颗粒的溶液,石墨烯加入量为0.01g每升含石墨烯颗粒的溶液,分散剂加入量为10g/每升含石墨烯颗粒的溶液,然后按照每升含石墨烯颗粒的溶液加入0.2mol氯化钡,搅拌均匀,静置24小时,过滤得到杂多酸修饰石墨烯复合粉体;
步骤3、高能球磨合金化:将金属铅粉(金属铅粉粒度小于200目,纯度大于99.5%)和步骤2得到的杂多酸修饰石墨烯复合粉体在惰性气氛环境下高能球磨机中合金化得到复合阳极粉体;杂多酸修饰石墨烯复合粉体占复合阳极粉体质量的1%;高能球磨机为行星式,磨料为氧化锆球,球料比15,转速300转/分,球磨时间20分钟;
步骤4、粉末冶金成型:将步骤3得到的复合阳极粉体在20MPa下冷压成型,在250℃还原性气氛(H2流量为300L/h)下烧结4h即制得杂多酸修饰的碳纳米管增强铅基复合阳极。
实施例3
如图1所示,该杂多酸修饰的碳纳米管和石墨烯增强铅基复合阳极制备方法,其具体步骤如下:
步骤1、氨基化改性处理:将碳纳米管和石墨烯进行氨基化改性处理;
步骤1.1、羧基化:将质量比为1:1的碳纳米管和石墨烯混合颗粒在体积比为3:1的硫酸(98wt%)和硝酸(68wt%)的混合溶液中,在温度为60℃氧化4小时,然后过滤,去离子水清洗至中性,50℃下真空干燥得到羧基化碳纳米管和石墨烯;
步骤1.2、酰氯化:将1g步骤1.1得到的羧基化碳纳米管和石墨烯,加入20mL二氯亚砜,70℃下搅拌回流24小时,过滤后用四氢呋喃清洗,50℃下真空干燥得到酰氯化碳纳米管和石墨烯;
步骤1.3、酰胺化:将1g步骤1.2得到的酰氯化碳纳米管和石墨烯,加入5g碳酸铵,滴加50mL氨水,搅拌下反应6小时,过滤,用去离子水清洗,50℃下真空干燥得到酰胺化碳纳米管和石墨烯;
步骤1.4霍夫曼消去反应:将1g步骤1.3得到的酰胺化碳纳米管和石墨烯0~5℃条件下滴加30mL次氯酸钠,滴加时间30min,然后搅拌反应4小时,升温至70℃,反应2小时,冷却后过滤,50℃下真空干燥得到氨基化改性处理的碳纳米管和石墨烯;
步骤2、表面修饰:将杂多酸(体积比为1:1的K10[Co(H2O)2(SiW10O35)2]•8.25H2O和K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O混合酸)溶于95℃100mL热水中得到浓度为0.001mol/L杂多酸溶液,加入经步骤1氨基化改性处理的碳纳米管和石墨烯、分散剂(质量比为1:1:1的明胶、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚混合物),超声(超声频率为40kHz)使得碳纳米管和石墨烯在杂多酸溶液中分散均匀得到含碳纳米管和石墨烯颗粒的溶液,碳纳米管和石墨烯加入量为2g每升含碳纳米管和石墨烯颗粒的溶液,分散剂加入量为8g/每升含碳纳米管和石墨烯颗粒的溶液,然后按照每升含纳米管和石墨烯颗粒的溶液加入0.0005mol氯化钡,搅拌均匀,静置24小时,过滤得到杂多酸修饰碳纳米管和石墨烯复合粉体;
步骤3、高能球磨合金化:将金属铅粉(金属铅粉粒度小于200目,纯度大于99.5%)和步骤2得到的杂多酸修饰碳纳米管和石墨烯复合粉体在惰性气氛环境下高能球磨机中合金化得到复合阳极粉体;杂多酸修饰碳纳米管和石墨烯复合粉体占复合阳极粉体质量的0.5%;高能球磨机为行星式,磨料为氧化锆球,球料比15,转速100转/分,球磨时间10分钟;
步骤4、粉末冶金成型:将步骤3得到的复合阳极粉体在50MPa下冷压成型,在250℃还原性气氛(H2流量为200L/h)下烧结4h即制得杂多酸修饰的碳纳米管增强铅基复合阳极。
以上结合附图对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (6)
1.一种杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其特征在于具体步骤如下:
步骤1、氨基化改性处理:将碳纳米管和/或石墨烯进行氨基化改性处理;
步骤2、表面修饰:将杂多酸溶于热水中得到浓度为0.0001~0.01mol/L杂多酸溶液,加入经步骤1氨基化改性处理的碳纳米管和/或石墨烯、分散剂,超声使得碳纳米管和/或石墨烯在杂多酸溶液中分散均匀得到含碳纳米管和/或石墨烯颗粒的溶液,碳纳米管和/或石墨烯加入量为0.01~2g每升含碳纳米管和/或石墨烯颗粒的溶液,分散剂加入量为0.5~10g/每升含碳纳米管和/或石墨烯颗粒的溶液,然后按照每升含碳纳米管和/或石墨烯颗粒的溶液加入0.0005~0.2mol氯化钡,搅拌均匀,静置24小时,过滤得到杂多酸修饰碳纳米管和/或石墨烯复合粉体;
步骤3、高能球磨合金化:将金属铅粉和步骤2得到的杂多酸修饰碳纳米管和/或石墨烯复合粉体在真空或惰性气氛环境下高能球磨机中合金化得到复合阳极粉体;杂多酸修饰碳纳米管和/或石墨烯复合粉体占复合阳极粉体质量的0.1~1%;
步骤4、粉末冶金成型:将步骤3得到的复合阳极粉体在20~50MPa下冷压成型,在250℃还原性气氛下烧结4h即制得杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极。
2.根据权利要求1所述的杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其特征在于:所述步骤1中碳纳米管为多壁碳纳米管、单壁碳纳米管中的一种或两种任意比例混合物。
3.根据权利要求1所述的杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其特征在于:所述步骤2中杂多酸为K16[Co(H2O)6(OH)3(HPO4)2(PW9O34)3]•30H2O、K10[Co(H2O)2(SiW10O35)2]•8.25H2O中的一种或两种任意比例混合物。
4.根据权利要求1所述的杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其特征在于:所述步骤2中分散剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、明胶、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、烷基脂肪醇聚氧乙烯醚、脂肪胺聚氧乙烯醚、烷基醇酰胺聚氧乙烷醚、嵌段聚氧乙烯-聚氧丙烯醚、烷基醇酰胺、聚乙烯吡咯烷酮中的一种或几种任意比例混合物。
5.根据权利要求1所述的杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其特征在于:所述步骤2中金属铅粉粒度小于200目,纯度大于99.5%。
6.根据权利要求1所述的杂多酸修饰的碳纳米管和/或石墨烯增强铅基复合阳极制备方法,其特征在于:所述步骤2中高能球磨机为行星式,磨料为氧化锆球,球料比大于10,转速180~300转/分,球磨时间10~60分钟。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110644020A (zh) * | 2019-10-29 | 2020-01-03 | 昆明冶金研究院 | 一种掺杂石墨烯的锌电积用铅银合金阳极制备工艺 |
CN112436114A (zh) * | 2020-11-16 | 2021-03-02 | 扬州大学 | 一种三维石墨烯/碳纳米管/磷钨酸/硫复合材料、制备方法及其应用 |
CN112467418A (zh) * | 2020-10-19 | 2021-03-09 | 南京盟瑞自动化有限公司 | 一种具有防雷功能的射频连接器 |
CN113634282A (zh) * | 2021-06-11 | 2021-11-12 | 盐城工学院 | 一种Co/Ni-Keggin型杂多酸-碳纳米纤维电极及其制备方法和应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040045816A1 (en) * | 2002-09-11 | 2004-03-11 | The Board Of Trustees Of The University Of Illinois | Solids supporting mass transfer for fuel cells and other applications and solutions and methods for forming |
CN103614672A (zh) * | 2013-12-09 | 2014-03-05 | 国家电网公司 | 碳纳米管增强铝基复合材料的制备方法 |
CN104131318A (zh) * | 2014-08-01 | 2014-11-05 | 昆明理工大学 | 一种碳纳米管和/或石墨烯增强铅基复合阳极制备方法 |
CN105154724A (zh) * | 2015-09-01 | 2015-12-16 | 苏州莱特复合材料有限公司 | 一种碳纳米管增强铝基复合材料及其制备方法 |
CN106399766A (zh) * | 2016-10-11 | 2017-02-15 | 西南交通大学 | 一种碳纳米管和石墨烯协同增强铝基复合材料及制备方法 |
-
2018
- 2018-05-15 CN CN201810459183.1A patent/CN108754545B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040045816A1 (en) * | 2002-09-11 | 2004-03-11 | The Board Of Trustees Of The University Of Illinois | Solids supporting mass transfer for fuel cells and other applications and solutions and methods for forming |
CN103614672A (zh) * | 2013-12-09 | 2014-03-05 | 国家电网公司 | 碳纳米管增强铝基复合材料的制备方法 |
CN104131318A (zh) * | 2014-08-01 | 2014-11-05 | 昆明理工大学 | 一种碳纳米管和/或石墨烯增强铅基复合阳极制备方法 |
CN105154724A (zh) * | 2015-09-01 | 2015-12-16 | 苏州莱特复合材料有限公司 | 一种碳纳米管增强铝基复合材料及其制备方法 |
CN106399766A (zh) * | 2016-10-11 | 2017-02-15 | 西南交通大学 | 一种碳纳米管和石墨烯协同增强铝基复合材料及制备方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110644020A (zh) * | 2019-10-29 | 2020-01-03 | 昆明冶金研究院 | 一种掺杂石墨烯的锌电积用铅银合金阳极制备工艺 |
CN112467418A (zh) * | 2020-10-19 | 2021-03-09 | 南京盟瑞自动化有限公司 | 一种具有防雷功能的射频连接器 |
CN112467418B (zh) * | 2020-10-19 | 2021-06-22 | 南京盟瑞自动化有限公司 | 一种具有防雷功能的射频连接器 |
CN112436114A (zh) * | 2020-11-16 | 2021-03-02 | 扬州大学 | 一种三维石墨烯/碳纳米管/磷钨酸/硫复合材料、制备方法及其应用 |
CN113634282A (zh) * | 2021-06-11 | 2021-11-12 | 盐城工学院 | 一种Co/Ni-Keggin型杂多酸-碳纳米纤维电极及其制备方法和应用 |
CN113634282B (zh) * | 2021-06-11 | 2023-07-25 | 盐城工学院 | 一种Co/Ni-Keggin型杂多酸-碳纳米纤维电极及其制备方法和应用 |
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