CN108728872A - 铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料及制备方法 - Google Patents
铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料及制备方法 Download PDFInfo
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- 229910020935 Sn-Sb Inorganic materials 0.000 title claims abstract description 103
- 229910008757 Sn—Sb Inorganic materials 0.000 title claims abstract description 103
- 239000004411 aluminium Substances 0.000 title claims abstract description 92
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 92
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- 239000010949 copper Substances 0.000 title claims abstract description 42
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 92
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 20
- 229910006529 α-PbO Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000007747 plating Methods 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 13
- 229910006531 α-PbO2 Inorganic materials 0.000 claims description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 229940046892 lead acetate Drugs 0.000 claims description 10
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- 229920000159 gelatin Polymers 0.000 claims description 8
- 239000008273 gelatin Substances 0.000 claims description 8
- 235000019322 gelatine Nutrition 0.000 claims description 8
- 235000011852 gelatine desserts Nutrition 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- BJIQCYSMVVESCD-UHFFFAOYSA-N [Sb]([S-])([O-])[O-].[Na+].[Na+].[Na+] Chemical compound [Sb]([S-])([O-])[O-].[Na+].[Na+].[Na+] BJIQCYSMVVESCD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 6
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000010957 pewter Substances 0.000 claims description 5
- 229910000498 pewter Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910000906 Bronze Inorganic materials 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 230000004323 axial length Effects 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000010974 bronze Substances 0.000 claims 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- 239000003595 mist Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 241000196171 Hydrodictyon reticulatum Species 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 229910014474 Ca-Sn Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910017802 Sb—Ag Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/34—Electroplating: Baths therefor from solutions of lead
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
铜电积用铝棒Pb‑Sn‑Sb/α‑PbO2‑Co3O4复合电极材料及制备方法,所述电极材料包括铝棒基体(1)、复合在铝棒基体表面的Sn‑Sb合金镀层(2)、复合在Sn‑Sb合金镀层表面引入了纳米CeO2颗粒的Pb‑Sn‑Sb复合镀层(3)、覆盖于Pb‑Sn‑Sb复合镀层表面引入了纳米Co3O4颗粒的α‑PbO2复合镀层(4)。本发明制备的铜电积用铝棒Pb‑Sn‑Sb/α‑PbO2‑Co3O4复合电极材料与传统的铅基多元合金相比,在不改变电解槽结构、电解液组成和操作规范的基础上,导电性显著提高,产生气泡较小,带出的酸雾少,槽电压可降低120mV,材料成本降低20%,电流效率提高2%以上。
Description
技术领域
本发明涉及铜电积用阳极材料及其制备方法技术领域。
背景技术
在铜电积工业上最初用的不溶阳极是Pb-Sb或Pb-Sb-Ag阳极。研究发现Sb可以降低Pb-Sb阳极在铜电积过程中的析氧过电位。Pb-Sb阳极虽然容易制作,但其表面的氧化铅膜容易脱落,因此Pb-Sb阳极的使用寿命短,电积铜时阴极铜容易受铅的污染而使其标准降低。
目前国内外使用的铜电积阳极基本是Pb-0.06%Ca-1.2%Sn阳极材料,其使用寿命长,但析氧电位高,使用过程中容易变形,导致出现电流效率下降、铅含量高等现象。用稀土元素如Ce、Pr、Sm、Gd、Tb、Bi、Li等可以改善Pb-Ca-Sn合金阳极材料电化学性能,稀土元素Ce、Pr的添加可以抑制氢的析出,同时也可提高合金的耐腐蚀性,但稀土元素在铅合金中的成分分布均匀性难以控制。
铅基Pb-Co合金阳极和铅基Pb-Co3O4复合阳极是以铅或铅合金为基体,在其表面复合电沉积Pb-Co或Pb-Co3O4合金层。Co3O4被广泛用于电化学领域,具有优异的电催化活性。试验结果表明Co3+和Co3O4在铜电积过程中具有优异的电催化活性;工业试验表明以Pb合金为基体,在其表面复合沉积Pb-Co3O4复合合金层制得的阳极在电积铜过程中槽电压比传统Pb-Ca-Sn合金阳极可降低大约70mV,能耗可降低4%左右。Co3O4和Co的掺杂不仅可以降低析氧过电位还可以增加阳极的耐腐蚀性。但铅合金基体本身导电性差、易弯曲变形及易污染阴极产品等现象不可避免。
以轻质金属铝为内芯与外层铅合金通过熔铸或电镀的形式来互溶得到的阳极存在一些难以解决的问题,一是解决不了铅合金液的流动性以及大尺寸阳极板局部可能出现的孔洞;二是镀层会出现一些晶界缝隙,电解时产生的氧气透过镀层的晶界缝隙氧化铝基体,形成导电性差的三氧化二铝膜层,恶化阳极性能。
有色金属电积用栅栏型阳极板改善了电解液的流动性能,提高了电解有色金属收集的效果和质量,避免了阴极板进行起吊时,触碰阳极板的缺陷。采用廉价的铝棒作为基体,材料成本明显降低,但依然存在界面电阻和寿命短的问题。
α-PbO2作为阳极析氧过电位低、孔隙率高、耐蚀性较差,不能单独作为阳极,但通过加入颗粒复合电沉积能产生无内应力的镀层,且其致密性好,能在中等电流密度下长时间应用。
综上所述,进一步开发一种电流效率高、能耗低、价格便宜、工艺简单、阴极铜产品质量高(含铅少)的阳极十分必要。
发明内容
本发明的目的是为了克服上述现有技术存在的缺点,提供一种电催化活性好、槽电压低、使用寿命长、成本低、电效高的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料及其制备方法。
本发明的目的通过以下技术方案实现:
铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料,该电极材料包括铝棒基体、复合在铝棒基体表面的Sn-Sb合金镀层、复合在Sn-Sb合金镀层表面的引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层(3)、覆盖于Pb-Sn-Sb复合镀层(3)表面的引入了纳米Co3O4颗粒的α-PbO2复合镀层。
本发明所述的铝棒基体是外表面为不平整异构形状或锯齿状的圆棒或矩形棒;沉积形成Pb-Sn-Sb复合镀层后的外表面为波浪型或者锯齿型。所述的Pb-Sn-Sb复合镀层中的CeO2颗粒粒径为30~50nm,CeO2颗粒的质量含量为0.5~1.25wt.%;α-PbO2复合镀层中的Co3O4颗粒粒径为40~80nm,Co3O4颗粒的质量含量为1.0~2.4wt.%。所述铝棒基体为圆棒时,圆棒外径为3~10mm;所述铝棒基体为矩形棒时,矩形棒的长轴长为6~50mm、短轴长为2~10mm。所述Sn-Sb合金镀层厚度为0.5~10μm,Pb-Sn-Sb复合镀层厚度为0.2mm~5mm,α-PbO2复合镀层厚度为0.1~1.0mm。
本发明所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法如下:
a.将铝棒基体进行除油和活化,在质量分数10~20%的NaOH溶液中,控制温度在40~60℃,进行除油1~20min,之后水洗干净,然后浸入质量分数5~30%的HC1中活化2~30min,控制温度20℃~50℃,去离子水洗净;
b.将步骤a处理后的铝棒基体置于镀锡锑溶液中浸泡0.5~30min,控制温度40~90℃,形成Sn-Sb合金镀层;所述的镀锡锑溶液配方为:锡酸钾60~120g/L、硫代亚锑酸钠15~60g/L、硫化钠20~120g/L、氢氧化钠30~60g/L、硫酸钠50~110g/L、表面活性剂0.2~1.0g/L;
c.将步骤b制得的形成了Sn-Sb合金镀层的铝棒置于超声分散后的酸性复合电镀液中,以纯铅作为阳极,温度为30~60℃,电流密度为5~20A/dm2,在机械搅拌下电镀2~24小时,在铝棒锡锑合金表面沉积得到引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层;所述的酸性复合电镀液中含有醋酸铅120~180g/L、氟硼酸亚锡20~60g/L、酒石酸锑钾10~20g/L、硼酸30~60g/L、明胶0.2~2g/L、纳米CeO2颗粒5~20g/L;
d.将步骤c制得的沉积了Pb-Sn-Sb复合镀层的铝棒立即置入拉拔挤压机中以4~8m/min的速度拉拔,控制拉拔模具温度在100~200℃下,控制挤压出来的Pb-Sn-Sb复合镀层的厚度在0.2mm~5mm,经过醋酸溶液清洗后,置于超声分散后的碱性复合电镀液中,以不锈钢作为阴极,阳阴极面积比为1:2,控制温度为30~60℃,电流密度为1~6A/dm2,在机械搅拌下电镀3~8小时,在铝棒Pb-Sn-Sb复合镀层表面沉积得到引入了纳米Co3O4颗粒的α-PbO2复合镀层,得到铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料;所述电镀溶液组成为:醋酸铅50~80g/L、醋酸40~60g/L、氢氧化钠20~80g/L、乙二胺四乙酸钠20~60g/L、纳米四氧化三钴颗粒5~20g/L。
本发明相比现有技术具有如下优点:
1、将铝棒基体在盐酸溶液中进行活化处理,延长了铝在空气中的氧化时间,并与后续沉积的Sn-Sb合金结合牢固。
2、Sn-Sb合金中引入Sb元素极大地提高了合金的硬度,避免了后续挤压拉拔过程中合金层与基体A1因强度不同产生脱落现象。
3、纳米CeO2颗粒引入电沉积的Pb-Sn-Sb合金中,提高了复合镀层的致密性,强化了复合镀层的硬度,延长了阳极的使用寿命。
4、采用挤压拉拔技术对铝棒Pb-Sn-Sb进行晶粒强化处理,能显著减少合金的孔隙率,有利于提高Pb-Sn-Sb复合镀层与后续电沉积α-PbO2复合镀层结合致密性。
5、采用复合电沉积得到α-PbO2-Co3O4镀层内应力小,在电积铜使用过程中易转化为耐蚀性高的β-PbO2,并且电解铜液不需添加钴离子;电极的析氧过电位低,使用寿命长。
本发明制备的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料应用于电积铜中,与传统的铅基多元合金阳极(如Pb-0.06wt.%Ca-1.2wt.%Sn阳极)相比,在不改变电解槽结构、电解液组成和操作规范的基础上,导电性显著提高,产生气泡较小,带出的酸雾少,槽电压可降低120mV,使用寿命长,材料成本降低20%,电流效率提高2%以上。
附图说明
图1为铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的横截面结构示意图;
图2是α-PbO2-Co3O4的表面形貌图。
具体实施方式
下面通过实施例对本发明做进一步详细说明,但本发明保护范围不局限于所述内容。
如图1所示,本发明的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料包括铝棒基体1、复合在铝棒基体表面的Sn-Sb合金镀层2、复合在Sn-Sb合金镀层表面引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层3、覆盖于Pb-Sn-Sb复合镀层表面引入了纳米Co3O4颗粒的α-PbO2复合镀层4。所述铝棒基体1是外表面为不平整异构形状或锯齿状的圆棒或矩形棒,沉积形成Pb-Sn-Sb复合镀层3后的外表面为波浪型或者锯齿型。所述铝棒基体为圆棒时,圆棒外径为3~10mm;铝棒基体为矩形棒时,矩形棒的长轴长为6~50mm、短轴长为2~10mm。图1所示的铝棒基体1是外表面为锯齿状的圆棒,Pb-Sn-Sb复合镀层3的外表面为波浪型。
本发明所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法如下。
实施例1
铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法,步骤如下:
a.将铝棒基体1进行除油和活化,在质量分数20%的NaOH溶液中,控制温度在45℃,进行除油10min,之后水洗干净,然后浸入质量分数30%的HC1中活化2min,控制温度50℃,用去离子水洗净;
b.将步骤a处理后的铝棒基体置于镀锡锑溶液中浸泡0.5min,控制温度90℃,形成厚度为0.5μm的Sn-Sb合金镀层2;所述的镀锡锑溶液配方为:锡酸钾60g/L、硫代亚锑酸钠15g/L、硫化钠20g/L、氢氧化钠30g/L、硫酸钠50g/L、表面活性剂聚乙烯吡咯烷酮(PVP)0.2g/L;
c.将步骤b制得的形成了Sn-Sb合金镀层的铝棒置于超声分散后的酸性复合电镀液中,以纯铅作为阳极,温度为60℃,电流密度为5A/dm2,在机械搅拌下电镀24小时,在铝棒锡锑合金表面沉积得到厚度为5mm的引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层3;Pb-Sn-Sb复合镀层中的CeO2颗粒粒径为50nm,CeO2颗粒在复合镀层中的质量含量为1.15wt.%;所述的酸性复合电镀液中含有醋酸铅180g/L、氟硼酸亚锡(Sn(BF4)2)60g/L、酒石酸锑钾20g/L、硼酸60g/L、明胶2g/L、纳米CeO2颗粒5g/L;
d.将步骤c制得的沉积了Pb-Sn-Sb复合镀层的铝棒立即置入拉拔挤压机中以4m/min的速度拉拔,控制拉拔模具温度在150℃下,控制挤压出来的Pb-Sn-Sb复合镀层的厚度在5mm,经过醋酸溶液清洗后,置于超声分散后的碱性复合电镀液中,以不锈钢作为阴极,阳阴极面积比为1:2,控制温度为60℃,电流密度为6A/dm2,在机械搅拌下电镀3小时,在铝棒Pb-Sn-Sb复合镀层表面沉积得到厚度为0.7mm的引入了纳米Co3O4颗粒的α-PbO2复合镀层4,得到铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料;α-PbO2复合镀层4中的Co3O4颗粒粒径为70nm,Co3O4颗粒在α-PbO2复合镀层4的质量含量为1.8wt.%;所述电镀溶液组成为:醋酸铅(Pb(AC)2)60g/L、醋酸60g/L、氢氧化钠80g/L、乙二胺四乙酸钠60g/L、纳米四氧化三钴颗粒20g/L。
本实施例制备的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料在铜电解液中,电解条件是电解液铜离子浓度为45g/L,硫酸浓度为200g/L,电解温度为45℃,20mg/LC1-离子,该铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的电效比传统Pb-0.06wt.%Ca-1.2wt.%Sn合金阳极板提高3%,槽电压低120mV,寿命延长1.5倍。
实施例2
铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法,步骤如下:
a.将铝棒基体1进行除油和活化,在质量分数10%的NaOH溶液中,控制温度在50℃,进行除油4min,之后立即水洗干净,然后浸入质量分数20%的HC1中活化8min,控制温度40℃,用去离子水洗净;
b.将步骤a处理后的铝棒基体置于镀锡锑溶液中浸泡10min,控制温度60℃,形成厚度为5μm的Sn-Sb合金镀层2;所述的镀锡锑溶液配方为:锡酸钾100g/L、硫代亚锑酸钠40g/L、硫化钠80g/L、氢氧化钠40g/L、硫酸钠80g/L、聚乙烯吡咯烷酮0.5g/L;
c.将步骤b制得的形成了Sn-Sb合金镀层的铝棒置于超声分散后的酸性复合电镀液中,以纯铅作为阳极,温度为50℃,电流密度为10A/dm2,在机械搅拌下电镀12小时,在铝棒锡锑合金表面沉积得到厚度为3.1mm的引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层3;Pb-Sn-Sb复合镀层中的CeO2颗粒粒径为40nm,CeO2颗粒在复合镀层中的质量含量为0.8wt.%;所述的酸性复合电镀液中含有醋酸铅160g/L、氟硼酸亚锡40g/L、酒石酸锑钾15g/L、硼酸40g/L、明胶1g/L、纳米CeO2颗粒10g/L;
d.将步骤c制得的沉积了Pb-Sn-Sb复合镀层的铝棒立即置入拉拔挤压机中以5m/min的速度拉拔,控制拉拔模具温度在100℃,控制挤压出来的Pb-Sn-Sb复合镀层的厚度在4mm,经过醋酸溶液清洗后,置于超声分散后的碱性复合电镀液中,以不锈钢作为阴极,阳阴极面积比为1:2,控制温度为40℃,电流密度为2A/dm2,在机械搅拌下电镀4小时,在铝棒Pb-Sn-Sb复合镀层表面沉积得到厚度为0.28mm的引入了纳米Co3O4颗粒的α-PbO2复合镀层4,得到铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料;α-PbO2复合镀层4中的Co3O4颗粒粒径为60nm,Co3O4颗粒在α-PbO2复合镀层4的质量含量为1.6wt.%(见图2);所述电镀溶液组成为:醋酸铅80g/L、醋酸40g/L、氢氧化钠40g/L、乙二胺四乙酸钠40g/L、纳米四氧化三钴颗粒10g/L。
本实施例制备的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料在铜电解液中,电解条件是电解液铜离子浓度为45g/L,硫酸浓度为200g/L,电解温度为45℃,20mg/LC1-离子,该铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的电效比传统Pb-0.06wt.%Ca-1.2wt.%Sn合金阳极板提高4%,槽电压低160mV,寿命延长2倍。
实施例3
铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法,步骤如下:
a.将铝棒基体1进行除油和活化,在质量分数10%的NaOH溶液中,控制温度在40℃,进行除油1min,之后立即水洗干净,然后浸入质量分数5%的HC1中活化2min,控制温度20℃,用去离子水洗净;
b.将步骤a处理后的铝棒基体置于镀锡锑溶液中浸30min,控制温度60℃,形成厚度为2.2μm的Sn-Sb合金镀层2;所述的镀锡锑溶液配方为:锡酸钾100g/L、硫代亚锑酸钠50g/L、硫化钠100g/L、氢氧化钠50g/L、硫酸钠90g/L、表面活性剂明胶0.5g/L;
c.将步骤b制得的形成了Sn-Sb合金镀层的铝棒置于超声分散后的酸性复合电镀液中,以纯铅作为阳极,温度为30℃,电流密度为20A/dm2,在机械搅拌下电镀4小时,在铝棒锡锑合金表面沉积得到厚度为4.2mm的引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层3;Pb-Sn-Sb复合镀层中的CeO2颗粒粒径为45nm,CeO2颗粒在复合镀层中的质量含量为0.5wt.%;所述的酸性复合电镀液中含有醋酸铅120g/L、氟硼酸亚锡20g/L、酒石酸锑钾10g/L、硼酸30g/L、明胶0.2g/L、纳米CeO2颗粒20g/L;
d.将步骤c制得的沉积了Pb-Sn-Sb复合镀层的铝棒立即置入拉拔挤压机中以6m/min的速度拉拔,控制拉拔模具温度在180℃,控制挤压出来的Pb-Sn-Sb复合镀层的厚度在4mm,经过醋酸溶液清洗后,置于超声分散后的碱性复合电镀液中,以不锈钢作为阴极,阳阴极面积比为1:2,控制温度为30℃,电流密度为3A/dm2,在机械搅拌下电镀3小时,在铝棒Pb-Sn-Sb复合镀层表面沉积得到厚度为1mm的引入了纳米Co3O4颗粒的α-PbO2复合镀层4,得到铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料;α-PbO2复合镀层4中的Co3O4颗粒粒径为80nm,Co3O4颗粒在α-PbO2复合镀层4的质量含量为2wt.%;所述电镀溶液组成为:醋酸铅50g/L、醋酸40g/L、氢氧化钠20g/L、乙二胺四乙酸钠20g/L、纳米四氧化三钴颗粒5g/L。
本实施例制备的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料在铜电解液中,电解条件是电解液铜离子浓度为45g/L,硫酸浓度为200g/L,电解温度为45℃,30mg/LC1-离子,该铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的电效比传统Pb-0.06wt.%Ca-1.2wt.%Sn合金阳极板提高1%,槽电压低60mV,寿命延长1倍。
实施例4
铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法,步骤如下:
a.将铝棒基体1进行除油和活化,在质量分数10%的NaOH溶液中,控制温度在60℃,进行除油20min,之后立即水洗干净,然后浸入质量分数5%的HC1中活化30min,控制温度20℃,用去离子水洗净;
b.将步骤a处理后的铝棒基体置于镀锡锑溶液中浸泡30min,控制温度40℃,形成厚度为10μm的Sn-Sb合金镀层2;所述的镀锡锑溶液配方为:锡酸钾120g/L、硫代亚锑酸钠60g/L、硫化钠120g/L、氢氧化钠60g/L、硫酸钠110g/L、表面活性剂明胶1g/L;
c.将步骤b制得的形成了Sn-Sb合金镀层的铝棒置于超声分散后的酸性复合电镀液中,以纯铅作为阳极,温度30℃,电流密度为5A/dm2,在机械搅拌下电镀2小时,在铝棒锡锑合金表面沉积得到厚度为0.2mm的引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层3;Pb-Sn-Sb复合镀层中的CeO2颗粒粒径为30nm,CeO2颗粒在复合镀层中的质量含量为1.25wt.%;所述的酸性复合电镀液中含有醋酸铅120g/L、氟硼酸亚锡20g/L、酒石酸锑钾10g/L、硼酸30g/L、明胶0.2g/L、纳米CeO2颗粒20g/L;
d.将步骤c制得的沉积了Pb-Sn-Sb复合镀层的铝棒立即置入拉拔挤压机中以8m/min的速度拉拔,控制拉拔模具温度在200℃,控制挤压出来的Pb-Sn-Sb复合镀层的厚度在0.2mm,经过醋酸溶液清洗后,置于超声分散后的碱性复合电镀液中,以不锈钢作为阴极,阳阴极面积比为1:2,控制温度为30℃,电流密度为1A/dm2,在机械搅拌下电镀8小时,在铝棒Pb-Sn-Sb复合镀层表面沉积得到厚度为1.0mm的引入了纳米Co3O4颗粒的α-PbO2复合镀层4,得到铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料;α-PbO2复合镀层4中的Co3O4颗粒粒径为40nm,Co3O4颗粒在α-PbO2复合镀层4的质量含量为1wt.%;所述电镀溶液组成为:醋酸铅50g/L、醋酸50g/L、氢氧化钠20g/L、乙二胺四乙酸钠20g/L、纳米四氧化三钴颗粒5g/L。
Claims (6)
1.铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料,其特征在于,该电极材料包括铝棒基体(1)、复合在铝棒基体表面的Sn-Sb合金镀层(2)、复合在Sn-Sb合金镀层(2)表面的引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层(3)、覆盖于Pb-Sn-Sb复合镀层(3)表面的引入了纳米Co3O4颗粒的α-PbO2复合镀层(4)。
2.根据权利要求1所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料,其特征在于,所述的铝棒基体(1)是外表面为不平整异构形状或锯齿状的圆棒或矩形棒;沉积形成Pb-Sn-Sb复合镀层(3)后的外表面为波浪型或者锯齿型。
3.根据权利要求1所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料,其特征在于,所述的Pb-Sn-Sb复合镀层(3)中的CeO2颗粒粒径为30~50nm,CeO2颗粒的质量含量为0.5~1.25wt.%;α-PbO2复合镀层(4)中的Co3O4颗粒粒径为40~80nm,Co3O4颗粒的质量含量为1.0~2.4wt.%。
4.根据权利要求1所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料,其特征在于,所述铝棒基体为圆棒时,圆棒外径为3~10mm;所述铝棒基体为矩形棒时,矩形棒的长轴长为6~50mm、短轴长为2~10mm。
5.根据权利要求1所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料,其特征在于,所述Sn-Sb合金镀层(2)厚度为0.5~10μm,Pb-Sn-Sb复合镀层(3)厚度为0.2mm~5mm,α-PbO2复合镀层(4)厚度为0.1~1.0mm。
6.如权利要求1~5任一项所述的铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料的制备方法,其特征在于,方法步骤如下:
a.将铝棒基体(1)进行除油和活化,在质量分数10~20%的NaOH溶液中,控制温度在40~60℃,进行除油1~20min,之后水洗干净,然后浸入质量分数5~30%的HC1中活化2~30min,控制温度20℃~50℃,去离子水洗净;
b.将步骤a处理后的铝棒基体置于镀锡锑溶液中浸泡0.5~30min,控制温度40~90℃,形成Sn-Sb合金镀层(2);所述的镀锡锑溶液配方为:锡酸钾60~120g/L、硫代亚锑酸钠15~60g/L、硫化钠20~120g/L、氢氧化钠30~60g/L、硫酸钠50~110g/L、表面活性剂0.2~1.0g/L;
c.将步骤b制得的形成了Sn-Sb合金镀层的铝棒置于超声分散后的酸性复合电镀液中,以纯铅作为阳极,温度为30~60℃,电流密度为5~20A/dm2,在机械搅拌下电镀2~24小时,在铝棒锡锑合金表面沉积得到引入了纳米CeO2颗粒的Pb-Sn-Sb复合镀层(3);所述的酸性复合电镀液中含有醋酸铅120~180g/L、氟硼酸亚锡20~60g/L、酒石酸锑钾10~20g/L、硼酸30~60g/L、明胶0.2~2g/L、纳米CeO2颗粒5~20g/L;
d.将步骤c制得的沉积了Pb-Sn-Sb复合镀层的铝棒立即置入拉拔挤压机中以4~8m/min的速度拉拔,控制拉拔模具温度在100~200℃下,控制挤压出来的Pb-Sn-Sb复合镀层的厚度在0.2mm~5mm,经过醋酸溶液清洗后,置于超声分散后的碱性复合电镀液中,以不锈钢作为阴极,阳阴极面积比为1:2,控制温度为30~60℃,电流密度为1~6A/dm2,在机械搅拌下电镀3~8小时,在铝棒Pb-Sn-Sb复合镀层表面沉积得到引入了纳米Co3O4颗粒的α-PbO2复合镀层(4),得到铜电积用铝棒Pb-Sn-Sb/α-PbO2-Co3O4复合电极材料;所述电镀溶液组成为:醋酸铅50~80g/L、醋酸40~60g/L、氢氧化钠20~80g/L、乙二胺四乙酸钠20~60g/L、纳米四氧化三钴颗粒5~20g/L。
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