CN1104687A - Active low-hydrogen over-potential cathode and its manufacture - Google Patents
Active low-hydrogen over-potential cathode and its manufacture Download PDFInfo
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- CN1104687A CN1104687A CN 93114575 CN93114575A CN1104687A CN 1104687 A CN1104687 A CN 1104687A CN 93114575 CN93114575 CN 93114575 CN 93114575 A CN93114575 A CN 93114575A CN 1104687 A CN1104687 A CN 1104687A
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Abstract
The active cathode is made up by use of plasma technique through spraying composite Ni-Al-Co-Mo powder onto substrate of low-carbon steel or nickel and removing Al by immersing in 20 Wt.% NaOH solution at 90 deg.C to form Raney Ni-Co-Mo porous structure. Under 15 Wt.% NaOH, 60 deg.C and 220 mA/sq.cm, its hydrogen-educing over-potential is 340 mv lower than that of low-C steel cathode, the voltage of single tank is lowered by more than 0.15 V, electric energy is saved by 6-8% and service life is over 3 years. It may be used in chlorine-alkali industry and electrolysis of industrial water.
Description
The present invention relates to activated cathode and manufacture method thereof that chlorine industry and electrolysis of industrial water are used, especially low-hydrogen over-potential activated cathode and manufacture method thereof.
Activated cathode is the energy-conservation novel material that early eighties rises, and it is to reach the purpose that reduces the electrolytic bath pressure by reducing overpotential of hydrogen evolution.The negative electrode great majority of chlorine industry and electrolysis of industrial water application at present are soft steel or nickel, and its overpotential of hydrogen evolution can reach 350～400 millivolts, account for 10% of whole electrolytic bath pressure, are big major reasons of electrolyzer power consumption.Therefore, the exploitation of low-hydrogen over-potential activated cathode becomes energy-conservation main contents of chlorine industry.Activated cathode generally is the combined electrode that is made of activated coating and matrix, and the matrix great majority are soft steel or nickel.The activated cathode coating has tens of kinds at present, is broadly divided into five classes: and oxide compound of (1) nickel or sulfide (Electrochimica Acta.Vol.29,1984, p297); (2) precious metal and oxide compound thereof (J.Appl.Electrochem, Vol.17,1987, p1190); (3) porous Raney Ni(USP4354915); (4) Ni-Mo class alloy (USP4116804); (5) Ni-Mo adds transiting group metal elements (USP4240895).Precious metal and oxide compound thereof are owing to cost an arm and a leg, and Practical significance is little.Ni-Mo class alloy or Ni-Mo-magnesium-yttrium-transition metal coating have only the more of porous Raney Ni application because bonding strength is low, and the life-span is shorter.Raney Ni activated cathode majority is to adopt plasma spraying Ni-Al alloy (USP4240895) or electroplated Ni-Zn alloy (USP4104133) at present, prepares after alkali soaks Al or Zn.Because its chemical ingredients is single, and is vesicular structure, its physical strength and over-all properties are inevitable relatively poor.Chemical Industry ﹠ Metallrygy Research Office of CAS utilizes the RaneyNi activated cathode of spraying technology development to find when reality is used on the chlor-alkali groove, 0.24 volt of initial stage electrolytic bath drops, but later on annually then rise with 28% speed, loss of activity is very fast, and after finding each demoulding, groove presses and rises greatlyyer, illustrate that coating machine intensity is hanged down and causes coating shedding.In addition, the electrolyzer outage also makes groove press liter, shows that the ability of its anti-reversible circulation is relatively poor.Thereby the physical strength and the over-all properties that improve Raney Ni become the important content that activated cathode is studied.
E.Endoh etc. once adopted composite electric plating method to add Ni in Raney Ni and inhaled hydrogen compound (LaNi5) and improved the physical strength of Raney Ni and the ability (Int.J.Hydrogen of anti-reversible circulation significantly, Vol.12, No.7, PP473-479,1987), want but this processing method is multiple, price is more expensive.K.Lohrberg etc. then adopt in Raney Ni and add new element, as 10%Mo, or (1～15) %Fe, or add Mo and Ti(European Pat.009830Al(1979 simultaneously)) improve the polarization performance of Raney Ni, but do not improve the ability of its anti-reversible circulation.
The purpose of this invention is to provide a kind of physical strength, over-all properties, anti-reversible circulation ability all significantly improves and processing method is simple, cost is low low-hydrogen over-potential activated cathode and manufacture method thereof.
Concrete solution of the present invention is:
A kind of low-hydrogen over-potential activated cathode is made up of matrix and top coat, and it is characterized in that: coating ingredients is: Ni-Al-Co-Mo; The structure of coating is: porous Raney Ni, and contain the Co3Mo intermediate phase.The chemical constitution at coated composite powder end is: 30～60%Ni, and 35～50%Al, 3～15%Co, 1～10%Mo, powder size is: 200～300 orders, coat-thickness is: 150～250um.A kind of manufacture method of low-hydrogen over-potential activated cathode comprises: derust → oil removing → activation or sandblast → prime coat → spraying → alkali soaks, it is characterized in that: be coated with above-mentioned Ni-Al-Mo-Co composite powder on matrix with plasma technology; In spraying coating process, the main system parameter of spraying is: (1) spray gun power: 15～30kw; (2) powder sending quantity: 10～30g/min; (3) spray distance: 100～200mm; In the alkali soaking technology, the condition flag that its alkali soaks Al is: concentration of lye: 20%(wt) NaOH, the etch temperature: 90 ℃, the time: 4～6 hours, boiling water boiled 4 hours.
Advantage of the present invention and positively effect are as follows:
(1) the present invention has improved the physical strength and the over-all properties of Raney Ni activated cathode by changing the chemical ingredients and the structure of coating.
(2) the present invention adds Mo and Co makes it to form Raney Ni-Mo-Co compound coating in Raney Ni, and this compound coating contains Raney Ni and Co
3It is long-pending that Mo intermediate phase, porous Raney Ni have very big real surface, reduced cathode current density and overpotential of hydrogen evolution effectively, but electrocatalysis anti-phase Co
3Mo has improved the ability of anti-reversible circulation, has also improved the physical strength of Raney Ni simultaneously.
(3) present, the situation of Raney Ni activated cathode industrial application on the chlor-alkali diaphram tank is: the single bath voltage of first annual descends 0.24 volt, 1 year groove flattens and all descends 0.18 volt, descended 0.11 volt in the 3rd year, three annuals descend 0.15 volt, be caustic soda economize on electricity 100 degree per ton, reducing power consumption is 5%.Its every performance index of Raney Ni-Mo-Co activated cathode of the present invention all are better than Raney Ni activated cathode.Therefore, the reducing power consumption of Raney Ni-Mo-Co activated cathode and work-ing life all can be greater than Raney Ni activated cathodes.
(4) cost of the present invention is low, and processing method is simple.
Electrochemical properties of the present invention and stability are as follows:
1. electropotential is measured:
Polarization curve is measured in the groove in polarization, and concentration of lye is 15%NaOH, and 60 ℃ of groove temperature with thermostatic water-circulator bath and contact thermometer control, during measurement were inserted sample in the electrolyzer placement 30 minutes, then at 200mA/cm
2Current density under electrolysis made between electrode and solution in 20 minutes and reach balance, measure the steady-state polarization of negative electrode at last with galvanostatic method.Reference electrode is saturated Kcl mercurous chloride electrode, the equilibrium electrode potential of liberation of hydrogen is-1.075(V).Fig. 1 represents soft steel, the polarization curve contrast of Raney Ni and three kinds of negative electrodes of Raney Ni-Mo-Co.
As can be seen from Fig. 1, the soft steel negative electrode is with the increase of current density, and overpotential of hydrogen evolution increases rapidly, and the growth of Raney Ni and Raney Ni-Co-Mo is less.At current density 200mA/cm
2The time, the overpotential of hydrogen evolution of Raney Ni-Co-Mo of the present invention reduces by 340 millivolts than soft steel negative electrode, reduces by 30 millivolts than Raney Ni.In addition, increase with current density, the overpotential of hydrogen evolution difference of Raney Ni-Mo-Co and soft steel negative electrode increases.
2. stability is measured
(1) static stability
Static stability is meant that under the forward current effect, the overpotential of hydrogen evolution of activated cathode is with the Changing Pattern of hold-time.Fig. 2 represents the comparison of Raney Ni and Raney Ni-Mo-Co static stability.
As can be seen from Fig. 2, the overpotential of hydrogen evolution of Raney Ni rose very fast later at the 6th day, and the overpotential of hydrogen evolution of Raney Ni-Mo-Co then keeps relative stablizing.Show that the static stability of Raney Ni-Mo-Co of the present invention is better than the static stability of general Raney Ni.
(2) dynamic stability
Dynamic stability is meant that under forward and reverse galvanic action, the overpotential of hydrogen evolution of activated cathode is with the variation of circulation cycle.Fig. 3 is the comparison of Raney Ni and Raney Ni-Mo-Co dynamic stability.
As can be seen from Fig. 3, Raney Ni collinear slope is greater than the slope of Raney Ni-Mo-Co, in other words the degree that increases greater than Raney Ni-Mo-Co of the degree that increases with the circulation cycle of the overpotential of hydrogen evolution of Raney Ni.The ability that shows the anti-reversible circulation of Raney Ni-Mo-Co of the present invention is better than Raney Ni.
Provide specific embodiment of the present invention below.
A kind of low-hydrogen over-potential activated cathode is made up of matrix and top coat, and it is characterized in that: coating ingredients is: Ni-Al-Co-Mo; The structure of coating is: porous Raney Ni, and contain Co
3The Mo intermediate phase.The chemical constitution at coated composite powder end is: 45%Ni, and 45%Al, 5%Co, 5%Mo, powder size is: 250 orders, coat-thickness is: 200 μ m.A kind of manufacture method of low-hydrogen over-potential activated cathode comprises: derust → oil removing → activation or sandblast → prime coat → spraying → alkali soaks, it is characterized in that: be coated with above-mentioned Ni-Al-Mo-Co composite powder on matrix with plasma technology; In spraying coating process, the main system parameter of spraying is: (1) spray gun power: 20kw; (2) powder sending quantity: 15g/min; (3) spray distance: 150mm; In the alkali soaking technology, the condition flag that its alkali soaks Al is: concentration of lye: 20%(wt) NaOH, the etch temperature: 90 ℃, the time: 4～6 hours, boiling water boiled 4 hours.
The technical process of activated cathode preparation be derust → oil removing → activation or sandblast → prime coat → spraying → alkali soaks.For nickel cathode, oil removing can be used organic solvent, and as acetone etc., activation solution can use 20～50%(wt) hydrochloric acid, and for the soft steel negative electrode, sandblast can be directly carried out in pre-treatment.The used powder of prime coat is that Ni80Al20 fuses composite powder certainly, and thickness is 40～50 μ m, and powder size 200～300 orders are best.The used powder of cathode is the Ni-Al-Mo-Co composite powder, and content is 30～60%Ni, 35～50%Al, and 3～15%Co, 1～10%Mo, powder size is: 200～300 orders, coat-thickness are 150～250 μ m.Main system parameter is powder sending quantity 10～30g/min during spraying, spray distance 100～200mm.It is that cathode produces active important step that alkali soaks, and the preferable alkali condition of soaking is: 20%NaOH, and 90 ℃ of temperature, 6～8 hours time, boiling water boiled 4～6 hours.
The preparation of example 1 active soft steel negative electrode
Get thick mild steel plate of 2.5mm or soft steel silk screen, be of a size of 50 * 100(mm), at first carry out sandblasting, spray the thick Ni80A120 powder of 40 μ m then as transition layer, spray the Ni-Al-Mo-Co composite powder again, chemical constitution is 49%Ni, 40%Al, 6.5%Co, 4.5%Mo.Coat-thickness is 200 μ m.The system parameter of plasma spraying is: power 30kw, N
2The amount of sending into is 0.5m
3/ h, powder sending quantity 20g/min, spray distance 150mm.To spray good sample at last is placed in 20%NaOH, 90 ℃ the alkali lye etch and boiled 4 hours with boiling water after 4 hours.
The preparation of example 2 active nickel negative electrodes
Get 2mm thick nickel plate or nickel screen, be of a size of 50 * 100(mm), at first deoil and use 20%(wt with acetone) hydrochloric acid plate front activating and handle, spray the thick Ni80A120 powder of 40 μ m then as transition layer, spray the Ni-Al-Mo-Co composite powder again, chemical constitution is 45%Ni, 45%Al, it is 200 μ m that 5%Co, 5%Mo are coated with depth.The system parameter of plasma spraying is: power 30Kw, N
2The amount of sending into is 0.5m
3/ h, powder sending quantity 20g/min, spray distance 150mm.To spray good sample at last is placed in 20%NaOH, 90 ℃ the alkali lye etch and boiled 4 hours with boiling water after 4 hours.
Claims (3)
1, a kind of low-hydrogen over-potential activated cathode is made up of matrix and top coat, and it is characterized in that: coating ingredients is: Ni-Al-Co-Mo; The structure of coating is: porous RaneyNi, and contain the Co3Mo intermediate phase.
2, low-hydrogen over-potential activated cathode according to claim 1, it is characterized in that: the chemical constitution at coated composite powder end is: 30～60%Ni, 35～50%Al, 3～15%Co, 1～10%Mo, powder size is: 200～300 orders, coat-thickness is: 150～250 μ m.
3, a kind of manufacture method of low-hydrogen over-potential activated cathode comprises: derust → oil removing → activation or sandblast → prime coat → spraying → alkali soaks, it is characterized in that: be coated with above-mentioned Ni-Al-Mo-Co composite powder on matrix with plasma technology; In spraying coating process, the main system parameter of spraying is: (1) spray gun power: 15～30kw; (2) powder sending quantity: 10～30g/min; (3) spray distance: 100～200mm; In the alkali soaking technology, the condition flag that its alkali soaks Al is: concentration of lye: 20%(wt) NaOH, the etch temperature: 90 ℃, the time: 4～6 hours, boiling water boiled 4 hours.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100459236C (en) * | 2006-09-29 | 2009-02-04 | 天津大学 | Anode material for lithium water cell and sodium water cell |
| CN101597766B (en) * | 2009-05-07 | 2012-08-22 | 新奥科技发展有限公司 | Cathode catalyst used for producing hydrogen from organic waste water and preparation method thereof |
| CN104372374A (en) * | 2014-07-21 | 2015-02-25 | 胡松 | Cathode catalyst and cathode structure of membrane electrode electrolysis ozone generator |
| CN105350015A (en) * | 2015-10-28 | 2016-02-24 | 派新（上海）能源技术有限公司 | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole |
| CN106191916A (en) * | 2016-07-06 | 2016-12-07 | 天津市大陆制氢设备有限公司 | A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof |
| CN107557806A (en) * | 2017-08-28 | 2018-01-09 | 天津市大陆制氢设备有限公司 | A kind of Co O high efficiency composition hydrogen-precipitating electrodes being covered on Co Mo O and preparation method thereof |
| CN110137514A (en) * | 2019-04-15 | 2019-08-16 | 南京晓庄学院 | A kind of Al-Co-Mo nanocrystalline composite material and its preparation method and application |
| CN110760875A (en) * | 2019-10-30 | 2020-02-07 | 广东省新材料研究所 | All-solid-state rapid preparation method of alkaline electrolytic water electrode |
| CN110804697A (en) * | 2019-10-23 | 2020-02-18 | 金川集团股份有限公司 | Waste printed nickel screen stripping method |
-
1993
- 1993-11-19 CN CN 93114575 patent/CN1104687A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100459236C (en) * | 2006-09-29 | 2009-02-04 | 天津大学 | Anode material for lithium water cell and sodium water cell |
| CN101597766B (en) * | 2009-05-07 | 2012-08-22 | 新奥科技发展有限公司 | Cathode catalyst used for producing hydrogen from organic waste water and preparation method thereof |
| CN104372374A (en) * | 2014-07-21 | 2015-02-25 | 胡松 | Cathode catalyst and cathode structure of membrane electrode electrolysis ozone generator |
| CN105350015A (en) * | 2015-10-28 | 2016-02-24 | 派新（上海）能源技术有限公司 | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole |
| CN106191916A (en) * | 2016-07-06 | 2016-12-07 | 天津市大陆制氢设备有限公司 | A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof |
| CN107557806A (en) * | 2017-08-28 | 2018-01-09 | 天津市大陆制氢设备有限公司 | A kind of Co O high efficiency composition hydrogen-precipitating electrodes being covered on Co Mo O and preparation method thereof |
| CN107557806B (en) * | 2017-08-28 | 2019-01-15 | 天津市大陆制氢设备有限公司 | A kind of Co-O high efficiency composition hydrogen-precipitating electrode and preparation method thereof being covered on Co-Mo-O |
| CN110137514A (en) * | 2019-04-15 | 2019-08-16 | 南京晓庄学院 | A kind of Al-Co-Mo nanocrystalline composite material and its preparation method and application |
| CN110804697A (en) * | 2019-10-23 | 2020-02-18 | 金川集团股份有限公司 | Waste printed nickel screen stripping method |
| CN110760875A (en) * | 2019-10-30 | 2020-02-07 | 广东省新材料研究所 | All-solid-state rapid preparation method of alkaline electrolytic water electrode |
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