CN114892041A - 一种电解金属锌用阳极及其制备方法 - Google Patents
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 29
- 239000011701 zinc Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000155 melt Substances 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 238000005096 rolling process Methods 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003723 Smelting Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 229910000978 Pb alloy Inorganic materials 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- 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
- C22C11/08—Alloys based on lead with antimony or bismuth as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/22—Moulds for peculiarly-shaped castings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/02—Use of electric or magnetic effects
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- 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
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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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
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- 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
本发明提供一种电解金属锌用阳极的制备方法,包括:将金属Pb、Ag和Bi按预定比例加入到坩埚电阻炉中加热到600‑700℃进行熔炼得到熔体;在脉冲电流作用下,打开冷却装置,设置模具温度从600℃降温到100℃,降温时间为6小时,将S1中得到的熔体凝固成型得到坯板;将S2中制得的坯板用轧辊进行轧制;裁边后得电解金属锌用阳极。本发明解决了现有技术中能耗高、消耗大、成本高等问题。
Description
技术领域
本发明涉及锰电解槽阳极材料制备技术领域,具体涉及一种电解金属锌用阳极及其制备方法。
背景技术
电解锌是指采用铅合金材料作为阳极,纯铝板作为阴极,电解硫酸锌和硫酸的混合溶液,目前,铅阳极主要存在的问题如下:①电解过程中,金属铅的内阻大、析氧电位高、电能消耗大,电解锌过程一般电耗为3800-4300kWh·tZn,其中电解工序的能耗为3200kWh·tZn,阳极是整个电化学反应体系的核心主体,成为降低电解能耗的关键影响因素;②铅阳极易溶解等不可避免的缺陷,造成了电极自身消耗大,且污染电解液和阴极析出的锌产品;③阳极中需添加贵金属Ag,使得阳极制造成本较高;④铅合金阳极强度低且易弯曲蠕变,造成短路,降低电流效率,增加电能消耗。针对以上问题,研究具有导电性能好、机械强度高、耐腐蚀性能好、成本费用低、电催化性能好的铅合金阳极材料对于电解锌行业的发展具有重要的实用价值。
专利号为CN201810609359.7的锌电积用多孔铝棒铅合金表面镀膜复合阳极及其制备方法,所述复合阳极由基体铝棒(1)、包覆于基体铝棒上的强化层、包覆于强化层上的表面活性层(4)组成,所述强化层包括底层(2)和中间层(3),底层为Pb/Ag金属复合层,中间层为铅合金层;所述表面活性层为含纳米碳化钨的复合二氧化锰层,表面活性层中碳化钨的质量分数为0.6-2.4wt%。本发明制备的表面镀膜复合阳极应用于电积锌中,相比传统的铅银合金阳极,槽电压降120-240mV,使用寿命长,成本低,电流效率提高2-4%。
专利号CN201710083818.8提供了一种多孔铅阳极的制备方法及其应用,所述多孔铅合金阳极具有三维通孔结构,孔隙率大于50%。所述多孔铅合金阳极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,该发明制备的多孔铅合金阳极具有重量轻、抗蠕变、密度低、阳极过电位低、铅合金用量少以及操作方便、泡沫金属廉价易得等优点。
专利号为CN201910239624.1涉及阳极材料制备技术领域,尤其是一种低Ag铅合金复合阳极材料制备方法,采用的纳米复合氧化物以纳米二氧化钛颗粒、纳米二氧化铱(IrO2)颗粒、纳米二氧化铅颗粒为原料配制而成,使得加入之后,极大程度的降低了Pb-0.2%Ag合金中Ag的含量,而且提高Pb的相对含量,同时引入了纳米二氧化钛颗粒、纳米二氧化铱(IrO2)颗粒成分,使得材料的析氧电催化活性大幅度的提高,导电性好,电流效率高,节约了能源。
发明内容
本发明提供一种电解金属锌用阳极及其制备方法,通过在脉冲电流的作用下,在金属模中进行浇筑凝固成型得坯板后,再进行锻扎,该发明具有导电性能好、机械强度高、耐腐蚀性能好、费用低、电催化性能好等优点。解决现有技术中能耗高、消耗大、成本高等问题。
为了解决上述问题,本发明目的之一是提供一种电解金属锌用阳极,所述电解金属锰用阳极由按重量百分比计的下列原料制备:Ag 0.1%~0.2%,Bi 0.4%~1.2%,余量为Pb。
本发明同时还提供一种电解金属锌用阳极的制备方法,包括如下步骤:
S1:将金属Pb、Ag和Bi按预定比例加入到坩埚电阻炉中加热到600-700℃进行熔炼得到熔体;
S2:在脉冲电流作用下,打开冷却装置,设置模具温度从600℃降温到100℃,降温时间为6小时,将S1中得到的熔体凝固成型得到坯板;
S3:将S2中制得的坯板用轧辊进行轧制;
S4:裁边后得电解金属锌用阳极。
作为优选,所述S2中凝固成型过程中施加脉冲电流。
作为优选,所述脉冲电流为10-30Hz峰值300A的脉冲电流。
本发明上述一个或多个技术方案具有如下技术效果:
本发明所提供的电解金属锌用阳极及其制备方法,通过在脉冲电流的作用下,在金属模中进行浇筑凝固成型得坯板后,再进行锻扎,该发明具有导电性能好、机械强度高、耐腐蚀性能好、费用低、电催化性能好等优点。解决现有技术中能耗高、消耗大、成本高等问题。电解金属锌用的阳极Ag0.1%~0.2%,Ag含量较低,使用成本较低;铋元素的加入可以细化晶粒、避免偏析现象、元素银在铅中分布均匀、增加材料的硬度;脉冲电流使共晶合金在晶界和树枝晶网的偏聚大大减少,变成了近似球状的共晶质点弥散在晶内和晶界附近,有效地改善阳极中Pb和Ag的成分偏析问题,且脉冲电流同样能使晶粒细化,均匀的结构和细小的晶粒有助于加速阳极内部的电子传输,从而降低电极电阻,降低析氧电位和槽电压,减少能源消耗,致密组织更容易发生均匀腐蚀,从而有效阻止电解液的深入而侵蚀导致电极失效,耐腐蚀性能较好。
附图说明
图1、一种电解金属锌用阳极的制备工艺流程图。
具体实施方式
本发明实施例提供一种电解金属锌用阳极及其制备方法,通过在脉冲电流的作用下,在金属模中进行浇筑凝固成型得坯板后,再进行锻扎,该发明具有导电性能好、机械强度高、耐腐蚀性能好、费用低、电催化性能好等优点。解决现有技术中能耗高、消耗大、成本高等问题。
为了使本发明的目的及优点更加清楚,以下结合实施例和附图1对本发明进行进一步详细说明。应当理解,下面实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
一种电解金属锌用阳极的制备方法,包括如下步骤:
S1:将Ag0.2%,Bi1.0%,余量为Pb称量配料后在坩埚电阻炉中加热到600~700℃进行熔炼得熔体;
S2:在15Hz峰值300A脉冲电流的作用下,打开冷却装置,设置模具温度从600℃降温到100℃,降温时间为6小时,凝固成型得到坯板;
S3:将坯板用轧辊进行轧制;
S4:裁边后得电解金属锌用阳极。
阳极材料的电导率为4.3MS/m,测定纤维硬度为15.99HV0.01,Pb-Ag-Bi阳极在500A/m2的恒电流密度条件下,在ZnSO4-H2SO4溶液中电解120h,Pb-Ag-Bi的析氧电位为1.74V左右,槽电压为3.35V,电流效率为92.4%,腐蚀速率为2.54g/m2·h。
实施例2
一种电解金属锌用阳极的制备方法,包括如下步骤:
S1:将Ag0.2%,Bi0.5%,余量为Pb称量配料后在坩埚电阻炉中加热到600-700℃进行熔炼得A品;
S2:在脉冲电流20Hz峰值300A的脉冲电流作用下,打开冷却装置,设置模具温度从600℃降温到100℃,凝固成型得到坯板;
S3:将坯板用轧辊进行轧制;
S4:裁边后得电解金属锌用阳极。
阳极材料的电导率为4.2MS/m,测定纤维硬度为15.36HV0.01,Pb-Ag-Bi阳极在500A/m2的恒电流密度条件下,在ZnSO4-H2SO4溶液中电解120h,Pb-Ag-Bi的析氧电位为1.72V左右,槽电压为3.34V,电流效率为92.1%,腐蚀速率为2.38g/m2·h。
对比例1
一种电解金属锌用阳极的制备方法,包括如下步骤:
S1:将金属Ag0.2%,余量为Pb称量配料后在坩埚电阻炉中加热到600-700℃进行熔炼;
S2:熔体凝固成型得到坯板;
S3:将坯板用轧辊进行轧制;
S4:裁边后得电解金属锌用阳极。
测定阳极材料的电导率为4.1MS/m,纤维硬度为13.52HV0.01,Pb-Ag阳极在500A/m2的恒电流密度条件下,在ZnSO4-H2SO4溶液中极化120h,Pb-Ag极的析氧电位为1.84V左右,槽电压3.45V,电流效率为90.2%,腐蚀速率为3.24g/m2·h。
表1.实施例与对比例对比表
由表1可知,本发明实施例可以说明,在铋元素的加入与脉冲电流的作用,可以明显提高电导率和显微硬度,降低析氧电位和槽电压、提高电流效率、降低阳极的腐蚀速率。
Claims (4)
1.一种电解金属锌用阳极,其特征在于,所述电解金属锰用阳极由按重量百分比计的下列原料制备:Ag 0.1%~0.2%,Bi 0.4%~1.2%,余量为Pb。
2.一种电解金属锌用阳极的制备方法,其特征在于,包括如下步骤:
S1:将金属Pb、Ag和Bi按预定比例加入到坩埚电阻炉中加热到600-700℃进行熔炼得到熔体;
S2:在脉冲电流作用下,打开冷却装置,设置模具温度从600℃降温到100℃,降温时间为6小时,将S1中得到的熔体凝固成型得到坯板;
S3:将S2中制得的坯板用轧辊进行轧制;
S4:裁边后得电解金属锌用阳极。
3.根据权利要求2所述的电解金属锌用阳极的制备方法,其特征在于:所述S2中凝固成型过程中施加脉冲电流。
4.根据权利要求3所述的电解金属锌用阳极的制备方法,其特征在于:所述脉冲电流为10-30Hz峰值300A的脉冲电流。
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US20050158629A1 (en) * | 2003-05-26 | 2005-07-21 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery, grid for lead-acid battery and lead-acid battery |
CN102206838A (zh) * | 2011-04-22 | 2011-10-05 | 昆明理工恒达科技有限公司 | 一种有色金属电积用新型阳极材料的制备方法 |
CN105925862A (zh) * | 2016-06-22 | 2016-09-07 | 中南大学 | 一种镁合金阳极材料及其制备方法 |
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US20050158629A1 (en) * | 2003-05-26 | 2005-07-21 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery, grid for lead-acid battery and lead-acid battery |
CN102206838A (zh) * | 2011-04-22 | 2011-10-05 | 昆明理工恒达科技有限公司 | 一种有色金属电积用新型阳极材料的制备方法 |
CN105925862A (zh) * | 2016-06-22 | 2016-09-07 | 中南大学 | 一种镁合金阳极材料及其制备方法 |
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