CN109338269A - 一种铜基导电陶瓷涂层电极材料的制备方法 - Google Patents
一种铜基导电陶瓷涂层电极材料的制备方法 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 93
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 92
- 239000000919 ceramic Substances 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 61
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 50
- 238000005507 spraying Methods 0.000 claims abstract description 39
- 239000007921 spray Substances 0.000 claims abstract description 30
- 229910009848 Ti4O7 Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000007788 roughening Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 238000007750 plasma spraying Methods 0.000 claims description 5
- 230000003746 surface roughness Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005524 ceramic coating Methods 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
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- 239000010936 titanium Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
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- 239000011241 protective layer Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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Abstract
本发明公开一种铜基导电陶瓷涂层电极材料的制备方法,先对铜基材料表面进行清洁粗糙化处理,再进行预热处理,在预热后的铜基材料表面采用等离子喷涂工艺喷涂Ti4O7陶瓷粉末,Ti4O7陶瓷粉末沉积在铜基体表面,得到铜基导电陶瓷涂层电极材料;本发明所制备的铜基导电陶瓷涂层电极材料具有析氧电位低、耐腐蚀性强、机械强度高、致密度高、使用寿命长和成本低等优点,同时Ti4O7陶瓷涂层与Cu基体的粘结力强,Ti4O7陶瓷粉末的沉积率较高,该电极材料可用于高性能铅酸蓄电池的正极板栅、氯碱工业、金属回收、金属箔生产以及印刷线路板蚀刻液的回用处理,具有广阔的发展前景。
Description
技术领域
本发明属于湿法冶金和电化学冶金技术领域,具体涉及一种铜基导电陶瓷涂层电极材料的制备方法。
背景技术
电极是湿法冶金行业和电化学工业中极其关键的部件,其选择和制备一直是学术界的难题和研究热点。在当前湿法冶金和电化学工业中常用的阳极材料有铅电极、钛基金属氧化物涂层电极以及石墨电极等,其中铅-银合金电极(简称铅电极)和钛基涂层电极(简称钛电极)的应用最为广泛。但是铅电极具有较高的析氧电位,且电阻率高,在电化学过程中易溶解,对电解液造成污染导致阴极电沉积产品中的杂质铅含量增加;而钛电极本身内阻较大,是其作为电极材料的主要缺陷,且钛电极主要以铱、钌、钽等稀贵金属氧化物作为活性催化涂层原料,不仅成本昂贵,且在硫酸体系中易钝化,其最致命缺点就是电极表面的稀贵金属氧化物活性层易脱落,导致电极寿命受到限制。
发明内容
本发明的目的在于弥补现有技术的不足,采用密度小、成本低、电导率高、阳极电位低、机械加工性能好的铜电极作为基体材料,同时,为了保证铜板表面的稳定性,需要在其表面制备特殊的导电保护层,这一保护层需要具有高导电性和耐酸腐蚀性,根据材料的性能叠加效应和性能可设计性,采用等离子喷涂的方法,从外向内“环形间歇式”的喷涂路径在铜电极表面沉积具有催化活性高、耐腐蚀性强、析氧电位低、寿命长、不易溶解的Magneli 相亚氧化钛(Ti4O7)陶瓷粉末,制备出新型铜基导电陶瓷涂层电极材料。
本发明通过以下技术方案实现:
一种铜基导电陶瓷涂层电极材料的制备方法,具体包括以下步骤:
(1)对铜基材料表面进行清洁粗糙化处理,对经清洁粗糙化处理后的铜基材料进行预热处理;
(2)在步骤(1)预热后的铜基材料表面采用等离子喷涂工艺喷涂Ti4O7陶瓷粉末,Ti4O7陶瓷粉末经等离子电弧加热到熔融或半熔融状态,并高速喷向经过预处理的铜基表面,Ti4O7陶瓷粉末沉积在铜基体表面,得到铜基导电陶瓷涂层电极材料。
步骤(1)铜基材料清洁粗糙化处理的具体工艺是:铜基材料表面用丙酮清洗干净后,采用粒径为60~80目的刚玉砂进行喷砂粗糙化处理,直至表面粗糙度为1.5~3μm,再用压缩空气吹除表面上残留的砂粒。
步骤(1)采用喷枪对铜基材料进行预热处理,使铜基材料温度达到60~120℃。
步骤(2)Ti4O7陶瓷粉末在使用之前于90~130℃烘干以除去潮气,Ti4O7陶瓷粉末的粒度为微米级,粒径为325~400目。
步骤(2)等离子喷涂法的喷涂工艺的具体参数为:喷涂电压490~550V;以氢气和氮气作为等离子体工作气体,氢气流量为5~15L/h,氮气流量为1800~2500L/h;喷枪喷口距喷涂面的距离为10~16cm;送粉速率30~50g/min,喷涂厚度为80~120μm。
步骤(2)采用从外向内“环形间歇式”的喷涂方式,具体的是从铜基材料边缘开始喷涂,喷涂完一圈后停止送粉,按照相同的速度喷枪原路吹气冷却一圈,再送粉进行下一圈的喷涂,直至喷涂结束,如此可以保证涂层表面温度较低,以避免基体与涂层材料因热膨胀系数差异而造成的涂层开裂,同时喷涂结束后,需采用风扇进行冷却处理。
本发明的有益效果:
(1)本发明采用等离子喷涂法将Ti4O7的熔融或半熔融态粒子以较高的速度射向经过预处理的铜板表面,最终在铜板表面形成结合牢固的表面涂层,由于铜的内阻小,可以降低再生产过程中的电能损耗,从而实现节能的目的;铜的密度比铅合金的小,从而可以减轻电极材料的质量;铜的价格比钛合金、铅合金的低,从而可以大大降低原材料的成本。
(2)本发明采用等离子喷涂法的喷涂工艺从外向内“环形间歇式”的喷涂方式,环形路径有利于喷涂成形, 涂层温度场分布均匀,对应的残余应力低,波动范围小,Ti4O7陶瓷涂层结构致密,孔洞少,耐蚀性好。
(3)本发明根据材料的性能叠加效应和性能可设计性,在铜电极的上采用等离子喷涂法、“环形间歇式”的喷涂路径以制备铜基导电陶瓷电极材料,从而改善电极基体的导电性、耐腐蚀性和使用寿命。
(4)本发明所采用的工艺较为简单,直接在铜金属板载体表面进行喷涂,即可获得与铜板结合良好、导电性好、机械强度高和耐蚀性好的Ti4O7陶瓷涂层,该铜基导电陶瓷涂层电极材料可用作高性能铅酸蓄电池的正极板栅、氯碱工业、金属回收、金属箔生产以及印刷线路板蚀刻液的回用处理。
附图说明
图1是实施例1铜基导电陶瓷涂层电极材料的喷涂路径示意图;
图2是实施例 1、2、3制备的导电陶瓷涂层的XRD 图谱;
图3是实施例 1、2、3制备的铜基导电陶瓷涂层电极材料的SEM图(实施例1-a,实施例2-b,实施例3-c)。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1
一种铜基导电陶瓷涂层电极材料的制备方法,具体包括以下步骤:
(1)将铜基材料表面用丙酮清洗干净后,采用粒径为60目的刚玉砂对表面进行喷砂粗糙化处理,直至表面粗糙度为1.5μm,再用压缩空气吹除表面上残留的砂粒,获得表面粗化的铜基材料,采用喷枪对铜基材料进行预热处理,使铜基材料温度达到60℃;
(2)在步骤(1)预热后的铜基材料表面采用等离子喷涂工艺喷涂Ti4O7陶瓷粉末,Ti4O7陶瓷粉末在使用之前于130℃干燥5小时,烘干以除去潮气,Ti4O7陶瓷粉末经等离子电弧加热到熔融或半熔融状态,并高速喷向经过预处理的铜基材料表面,Ti4O7陶瓷粉末沉积在铜基材料表面,形成铜基导电陶瓷涂层电极材料,具体的等离子喷涂工艺为:将铜基材料固定在工作架上,将粒径范围为325~400目的Ti4O7陶瓷粉末放入送粉器中,设定喷涂电压490V,氢气流量为5L/h,氮气流量为1800L/h;喷枪喷口距喷涂面的距离为10cm;送粉速率30g/min,检查设定参数无误和送粉器送粉均匀连续后,按照图1所示喷涂路径,采用从外向内“环形”间歇式的喷涂方式进行喷涂,具体的是从铜基材料边缘开始喷涂,喷涂完一圈后停止送粉,按照相同的速度喷枪原路吹气冷却一圈,再送粉进行下一圈的喷涂,直至喷涂结束,可以保证涂层温度较低,从而避免涂层的开裂,同时喷涂结束后,需采用风扇对材料进行冷却处理,喷涂厚度为110μm,亚氧化钛陶瓷涂层和铜板之间具有良好的结合力,获得高导电性、机械性能好的铜基导电陶瓷涂层电极材料。
实施例2
一种铜基导电陶瓷涂层电极材料的制备方法,具体包括以下步骤:
(1)将铜基材料表面用丙酮清洗干净后,采用粒径为70目的刚玉砂对涂层表面进行喷砂粗糙化处理,直至表面粗糙度为2μm,再用压缩空气吹除表面上残留的砂粒,获得表面粗化的铜基材料,采用喷枪对铜基材料进行预热处理,使铜基材料温度达到100℃;
(2)在步骤(1)预热后的铜基材料表面采用等离子喷涂工艺喷涂Ti4O7陶瓷粉末,Ti4O7陶瓷粉末在使用之前于90℃干燥10小时,烘干以除去潮气,Ti4O7陶瓷粉末经等离子电弧加热到熔融或半熔融状态,并高速喷向经过预处理的铜基材料表面,Ti4O7陶瓷粉末沉积在铜基材料表面,形成铜基导电陶瓷涂层电极材料,具体的等离子喷嚏工艺为:将铜基材料固定在工作架上,将粒径范围为325~400目的Ti4O7陶瓷粉末放入送粉器中,设定喷涂电压500V,氢气流量为10L/h,氮气流量为2000L/h;喷枪喷口距喷涂面的距离为15cm;送粉速率50g/min,检查设定参数无误和送粉器送粉均匀连续后,采用从外向内“环形”间歇式的喷涂方式进行喷涂,具体的是从铜基材料边缘开始喷涂,喷涂完一圈后停止送粉,按照相同的速度喷枪原路吹气冷却一圈,再送粉进行下一圈的喷涂,直至喷涂结束,可以保证涂层温度较低,从而避免涂层的开裂,同时喷涂结束后,需采用风扇对材料进行冷却处理,喷涂厚度为80μm,利用亚氧化钛陶瓷涂层和铜板之间具有良好的结合力从而获得高导电性、机械性能好的铜基导电陶瓷涂层电极材料。
实施例3
一种铜基导电陶瓷涂层电极材料的制备方法,具体包括以下步骤:
(1)将铜基材料表面用丙酮清洗干净后,采用粒径为80目的刚玉砂对涂层表面进行喷砂粗糙化处理,直至表面粗糙度为3μm,再用压缩空气吹除表面上残留的砂粒,获得表面粗化的铜基材料,采用喷枪对铜基材料进行预热处理,使铜基材料温度达到120℃;
(2)在步骤(1)预热后的铜基材料表面采用等离子喷涂工艺喷涂Ti4O7陶瓷粉末,Ti4O7陶瓷粉末在使用之前于120℃干燥6小时,烘干以除去潮气,Ti4O7陶瓷粉末经等离子电弧加热到熔融或半熔融状态,并高速喷向经过预处理的铜基材料表面,Ti4O7陶瓷粉末沉积在铜基材料表面,形成铜基导电陶瓷涂层电极材料,具体的等离子喷嚏工艺为:将铜基材料固定在工作架上,将粒径范围为325~400目的Ti4O7陶瓷粉末放入送粉器中,设定喷涂电压550V,氢气流量为15L/h,氮气流量为2500L/h;喷枪喷口距喷涂面的距离为16cm;送粉速率40g/min,检查设定参数无误和送粉器送粉均匀连续后,采用从外向内“环形”间歇式的喷涂方式进行喷涂,具体的是从铜基材料边缘开始喷涂,喷涂完一圈后停止送粉,按照相同的速度喷枪原路吹气冷却一圈,再送粉进行下一圈的喷涂,直至喷涂结束,可以保证涂层温度较低,从而避免涂层的开裂,同时喷涂结束后,需采用风扇对材料进行冷却处理,喷涂厚度为120μm,利用亚氧化钛陶瓷涂层和铜板之间具有良好的结合力从而获得高导电性、机械性能好的铜基导电陶瓷涂层电极材料。
将实施例1、2、3得到电极材料在1mol/L的H2SO4溶液、电流密度为4A/cm2下进行强化寿命试验测试,同时采用四探针法测试电极电阻率,结果如表1所示,从表中可知,实施例1、2、3得到的电极材料的加速强化寿命均长于传统铅基电极,分别是传统铅基电极的该1.34倍、1.43倍、1.54倍;电阻率均远小于传统铅基电极的电阻率,因此实施例1、2、3制备出来的铜基导电陶瓷涂层电极材料具有高导电、强耐腐蚀性的特点。
表1
图2是实施例 1、2、3制备的导电陶瓷涂层的XRD 图谱,从图中可知,实施例1、2、3的涂层以Ti4O7的衍射峰为主,并含有少量的TiO2,可能由于喷涂温度过高少量Ti4O7发生了氧化而生成的;对涂层的成分进行定量分析,实施例1、2、3中Ti4O7的含量分别约为约为89.8%、89.3%、87.4%。
图3是实施例 1、2、3制备的铜基导电陶瓷涂层电极材料的SEM图(实施例1-a,实施例2-b,实施例3-c),实施例1的涂层致密且厚度为110μm,实施例2的涂层致密且厚度为80μm,实施例3的涂层致密且厚度为120μm,三个实施例的铜基均和导电陶瓷涂层结合良好。
Claims (6)
1.一种铜基导电陶瓷涂层电极材料的制备方法,其特征在于,具体包括以下步骤:
(1)对铜基材料表面进行清洁粗糙化处理,再进行预热处理;
(2)在步骤(1)预热后的铜基材料表面采用等离子喷涂工艺喷涂Ti4O7陶瓷粉末,得到铜基导电陶瓷涂层电极材料。
2.根据权利要求1所述铜基导电陶瓷涂层电极材料的制备方法,其特征在于,步骤(1)铜基材料清洁粗糙化处理的具体工艺是:铜基材料表面用丙酮清洗干净后,采用粒径为60~80目的刚玉砂进行喷砂粗糙化处理,直至表面粗糙度为1.5~3μm,再用压缩空气吹除表面残留的砂粒。
3.根据权利要求1所述铜基导电陶瓷涂层电极材料的制备方法,其特征在于,步骤(1)铜基材料预热处理后的温度为60~120℃。
4.根据权利要求1所述铜基导电陶瓷涂层电极材料的制备方法,其特征在于,步骤(2)Ti4O7陶瓷粉末使用之前于90~130℃烘干,Ti4O7陶瓷粉末的粒径为325~400目。
5.根据权利要求1所述铜基导电陶瓷涂层电极材料的制备方法,其特征在于,步骤(2)等离子喷涂法的喷涂工艺的具体参数为:喷涂电压为490~550V;以氢气和氮气作为等离子体工作气体,氢气流量为5~15L/h,氮气流量为1800~2500L/h;喷枪喷口距喷涂面的距离为10~16cm;送粉速率30~50g/min,喷涂厚度为80~120μm。
6.根据权利要求1所述铜基导电陶瓷涂层电极材料的制备方法,其特征在于,步骤(2)采用从外向内“环形间歇式”的喷涂方式进行喷涂,具体的是从铜基材料边缘开始喷涂,喷涂完一圈后停止送粉,按照相同的速度喷枪原路吹气冷却一圈,再送粉进行下一圈的喷涂,直至喷涂结束后,采用风扇进行冷却处理。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110690459A (zh) * | 2019-09-25 | 2020-01-14 | 中国华能集团清洁能源技术研究院有限公司 | 一种提高熔融碳酸盐燃料电池电极催化性能的方法 |
CN111419387A (zh) * | 2020-03-27 | 2020-07-17 | 上海健康医学院 | 一种压电喷涂方式制备球囊表面消融电极的方法 |
CN112340817A (zh) * | 2020-11-09 | 2021-02-09 | 南通科技职业学院 | 一种纳米氧化亚钛催化电极材料及其制备方法 |
CN112809318A (zh) * | 2020-12-26 | 2021-05-18 | 陕西航空电气有限责任公司 | 一种电化学处理辅助象形电极的快速成型方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104775087A (zh) * | 2014-12-05 | 2015-07-15 | 襄阳航泰动力机器厂 | 一种金属复合陶瓷热障涂层的制备方法 |
CN105297073A (zh) * | 2015-10-30 | 2016-02-03 | 昆明理工大学 | 一种铜基亚氧化钛电极板的制备方法 |
EP3375904A1 (en) * | 2017-03-14 | 2018-09-19 | Materion Advanced Materials Germany GmbH | Cylindrical titanium oxide sputtering target and process for manufacturing the same |
-
2018
- 2018-10-30 CN CN201811275748.7A patent/CN109338269A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104775087A (zh) * | 2014-12-05 | 2015-07-15 | 襄阳航泰动力机器厂 | 一种金属复合陶瓷热障涂层的制备方法 |
CN105297073A (zh) * | 2015-10-30 | 2016-02-03 | 昆明理工大学 | 一种铜基亚氧化钛电极板的制备方法 |
EP3375904A1 (en) * | 2017-03-14 | 2018-09-19 | Materion Advanced Materials Germany GmbH | Cylindrical titanium oxide sputtering target and process for manufacturing the same |
Non-Patent Citations (1)
Title |
---|
编委会: "《徐滨士文集》", 31 May 2014, 北京冶金工业出版社 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110690459A (zh) * | 2019-09-25 | 2020-01-14 | 中国华能集团清洁能源技术研究院有限公司 | 一种提高熔融碳酸盐燃料电池电极催化性能的方法 |
CN111419387A (zh) * | 2020-03-27 | 2020-07-17 | 上海健康医学院 | 一种压电喷涂方式制备球囊表面消融电极的方法 |
CN112340817A (zh) * | 2020-11-09 | 2021-02-09 | 南通科技职业学院 | 一种纳米氧化亚钛催化电极材料及其制备方法 |
CN112340817B (zh) * | 2020-11-09 | 2022-11-29 | 南通科技职业学院 | 一种纳米氧化亚钛催化电极材料及其制备方法 |
CN112809318A (zh) * | 2020-12-26 | 2021-05-18 | 陕西航空电气有限责任公司 | 一种电化学处理辅助象形电极的快速成型方法 |
CN112809318B (zh) * | 2020-12-26 | 2023-09-19 | 陕西航空电气有限责任公司 | 一种电化学处理辅助象形电极的快速成型方法 |
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