CN104458851A - Porous three-dimensional electrode material and preparation method thereof - Google Patents
Porous three-dimensional electrode material and preparation method thereof Download PDFInfo
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- CN104458851A CN104458851A CN201410746620.XA CN201410746620A CN104458851A CN 104458851 A CN104458851 A CN 104458851A CN 201410746620 A CN201410746620 A CN 201410746620A CN 104458851 A CN104458851 A CN 104458851A
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Abstract
The invention discloses a porous three-dimensional electrode material and a preparation method thereof. The preparation method of the porous three-dimensional electrode material comprises the following steps: firstly arranging a foam metal material in a bismuth solution with the concentration of 0.5-500 mmol/L, and steeping, wherein the bismuth solution is formed by dissolving water soluble bismuth salt in water and alcohol; then adding hydrazine hydrate; and finally drying. The prepared porous three-dimensional electrode material is good in electrical conductivity and good in mass transfer effect. An electrochemical sensor prepared by the porous three-dimensional electrode material has low lead ion detection limit. The preparation method is simple and convenient, electrode fabricating cost is reduced, and raw materials are easily available.
Description
Technical field
The present invention relates to the technical field of electrode material, particularly relate to a kind of porous three-dimensional electrode material and preparation method thereof.
Background technology
In numerous detection methods, electrochemical sensor, with good, the easy microminiaturization of its selectivity, the feature such as easy and simple to handle, power consumption is little, cost is low, has been widely used in the fields such as food analysis, technical analysis and environment measuring.Traditional glass-carbon electrode electric conductivity is poor, and surface is difficult to functional modification, and specific surface area is lower, and thus lower to the sensitivity of biomolecule, selectivity is poor.Report, adopt and add the electric conductivity that the nano materials such as carbon nano-tube can increase glass-carbon electrode in the material.But there is preparation difficulty, high in cost of production defect in nano material.
Foamed metal material is that a kind of density is low, porosity is high and has the new function material of tridimensional network.It is widely used in the aspects such as battery electrode material, electric chemical super capacitor, catalyst support.And compared with nano material, nickel foam or foam copper cheap and easy to get, in the application of electrochemical sensor, the mechanical property of electrode, electric conductivity and mass transfer effect can be increased.Bismuth is electrode material gradually concerned in electrochemical analysis in recent years.It has too high overpotential, wider electrochemical window and good stability, has good sensitivity to metallic ion, but makes loaded down with trivial details due to bismuth film electrode, and exists and easily come off, detect the problems such as lower limit is high, causes and there is bottleneck in actual use.
In prior art, porous three-dimensional electrode material ubiquity electric conductivity is poor, causes the electrode assembling that obtains thus higher to electrochemical sensor accessible lead ion Monitoring lower-cut.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of electric conductivity better and the good porous three-dimensional electrode material of mass transfer performances, makes the electrochemical sensor be made up of this porous three-dimensional electrode material have lower lead ion Monitoring lower-cut.
A preparation method for porous three-dimensional electrode material, comprises the following steps:
(1) foam metal material being inserted concentration is flood in the bismuth solution of 0.5 ~ 500mmol/L, and described bismuth solution is formed by water-soluble bismuth salt is dissolved in the solvent be made up of water and alcohol;
(2) in described bismuth solution, add hydrazine hydrate, make foam metal material continue dipping;
(3) dry foam metal material after dipping, obtained porous three-dimensional electrode.
Above-mentioned preparation method, in step (1), water-soluble bismuth salt can be bismuth nitrate and/or bismuth chloride.Water-soluble bismuth salt dissolution mechanism can adopt ultrasonic dissolution, and ultrasonic disperse 5 ~ 60min under generation dissolving 500 ~ 800W, can adopt mechanical raking certainly, and its rotating speed stirred and time can regulate according to the dissolving situation of reality.The instantiation of foam metal material is except a kind of in nickel foam, foam copper, foamed aluminium, foamed iron, foam chromium, foam zinc, can also be binary or ternary alloy three-partalloy foam metal material, the three kinds of metallic elements be such as selected from the most in nickel, copper, aluminium, iron, chromium, zinc formed.The time of dipping is 2 ~ 24 hours;
In solvent, the volume ratio of water and alcohol is 1:(1/64 ~ 8), be preferably 1:3.Alcohol is preferably one in ethanol, isopropyl alcohol and ethylene glycol or at least two kinds, more preferably ethanol.
In step (2), the time of described dipping is 2 ~ 8 hours.The mass concentration of hydrazine hydrate is 2 ~ 20wt%, and the volume ratio of hydrazine hydrate and bismuth solution is 5 ~ 25:200.The effect of bismuth is to the activation to electrode material.Drying can be carried out in an oven, and its temperature is 40 ~ 120 DEG C, is preferably 60 DEG C; The dry time is 1 ~ 48 hour, is preferably 8h.
In order to remove the impurity of hydrazine hydrate residual on electrode, after treating step (2) dipping, adopt solvent to foam metal material washing 1 ~ 10 time, more preferably 3 times.
What deserves to be explained is, flood adopted maceration extract in this method, namely bismuth solution (comprising the bismuth solution after adding hydrazine hydrate) temperature is 0 ~ 80 DEG C, and the pH of maceration extract is 2 ~ 10.
Another aspect of the invention provides a kind of porous three-dimensional electrode, this porous three-dimensional electrode conductivuty comparatively, mass transfer effect, make the electrochemical sensor be made up of this porous three-dimensional electrode material have lower lead ion Monitoring lower-cut.
A kind of porous three-dimensional electrode porous three-diemsnional electrode material adopted as above-mentioned preparation method obtains.Preferably, its structure three-dimensional netted metallic framework that is 300 ~ 700 μm by aperture and be attached to the bismuth particle that the particle diameter of metallic framework is 0.5 ~ 5 μm and formed.
Further aspect of the present invention provides a kind of electrochemical sensor, and this chemical sensor has lower lead ion Monitoring lower-cut.
Detect an electrochemical sensor for lead ion, comprise the electrode be made up of above-mentioned porous three-dimensional electrode material.
Another aspect of the invention provides the purposes of porous three-dimensional electrode material, and this porous three-dimensional electrode material is applied to the electrode of energy storage device.
In the preparation method of porous three-dimensional electrode material of the present invention, first flood in the bismuth solution formed in foam metal material to be inserted concentration be 0.5 ~ 500mmol/L and alcohol water-soluble by water-soluble bismuth salt, then hydrazine hydrate is added, final drying, porous three-dimensional electrode material electric conductivity obtained is thus better, mass transfer effect good, makes the electrochemical sensor be made up of this porous three-dimensional electrode material have lower lead ion Monitoring lower-cut.In addition this preparation method is easy, reduce electrode fabrication cost, and raw material is easy to get.
Accompanying drawing explanation
Fig. 1 is SEM figure under the obtained porous three-dimensional electrode material low range of the embodiment of the present invention 1;
Fig. 2 is SEM figure under the obtained porous three-dimensional electrode material high magnification of the embodiment of the present invention 1.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment 1
0.15g bismuth nitrate or bismuth chloride are dissolved in 200 ml waters and ethanol (volume ratio is 1:1) mixed solvent, ultrasonic dissolution half an hour.By above-mentioned solution complete submergence 10cm*10cm nickel foam in a square container, flood 8 hours.Add the hydrazine hydrate that 5ml concentration is 10%, static placement, make to continue dipping 4 hours.The temperature of above-mentioned maceration extract is 25 DEG C, and pH is 7.After to be impregnated, take out nickel foam, respectively wash three times with water and ethanol, insert in 60 DEG C of dry 8h in thermostatic drying chamber, the porous three-dimensional nickel electrode that obtained bismuth is modified.
Above-mentioned electrode, cut into the bar material of 0.1cm*1cm, be that contrast electrode, platinum filament are for electrode assembling electrochemical sensor as working electrode, Ag/AgCl, adopt Square wave anodic stripping voltammetry method, measure lead ion in water respectively, detecting lower limit is 0.07ppb, and this illustrates that this three-diemsnional electrode has good sensitivity.After electrode is deposited 24 hours, 48 hours and 96 hours respectively, again detect lead ion, detect lower limit and be respectively 0.07ppb, 0.09ppb and 0.11ppb, this illustrates that above-mentioned electrode has good stability.
Embodiment 2
0.11g bismuth nitrate or bismuth chloride are dissolved in 200 ml waters and ethanol (1:4) mixed solution, ultrasonic dissolution half an hour.By above-mentioned solution complete submergence 10cm*10cm nickel foam in a square container, flood 18 hours.Add the hydrazine hydrate that 5ml concentration is 10%, static placement, make to continue dipping 4 hours.The temperature of above-mentioned maceration extract is 25 DEG C, and pH is 7.After to be impregnated, then take out nickel foam, respectively wash three times with water and ethanol, then in thermostatic drying chamber in 60 DEG C of dry 8h, the three-dimensional nickel electrode of porous porous that obtained bismuth is modified.
Above-mentioned electrode, cut into the bar material of 0.1cm*1cm, be that contrast electrode, platinum filament are for electrode assembling electrochemical sensor as working electrode, Ag/AgCl, adopt Square wave anodic stripping voltammetry method, measure lead ion in water respectively, detecting lower limit is 0.15ppb, and this illustrates that this three-diemsnional electrode has good sensitivity.After electrode is deposited 24 hours, 48 hours and 96 hours respectively, again detect lead ion, detect lower limit and be respectively 0.16ppb, 0.22ppb and 0.18ppb this illustrate that above-mentioned electrode has good stability.
Embodiment 3
0.25g bismuth nitrate or bismuth chloride are dissolved in 200 ml waters and ethanol (volume ratio is 1:4) mixed solution, ultrasonic dissolution half an hour.With above-mentioned solution complete submergence 10cm*10cm foam copper in a square container, flood 18 hours.Add the hydrazine hydrate that 5ml concentration is 10%, static placement, make it to continue dipping 4 hours.The temperature of above-mentioned maceration extract is 25 DEG C, and pH is 7.After to be impregnated, then take out nickel foam, respectively wash three times with water and ethanol, then in thermostatic drying chamber in 60 DEG C of dry 8h, the three-dimensional copper electrode of porous porous that obtained bismuth is modified.
Above-mentioned electrode, cut into the bar material of 0.1cm*1cm, be that contrast electrode, platinum filament are for electrode assembling electrochemical sensor as working electrode, Ag/AgCl, adopt Square wave anodic stripping voltammetry method, measure lead ion in water respectively, detecting lower limit is 0.09ppb, and this illustrates that this three-diemsnional electrode has good sensitivity.After electrode is deposited 24 hours, 48 hours and 96 hours respectively, again detect lead ion, detect lower limit and be respectively 0.05ppb, 0.03ppb and 0.9ppb, this illustrates that above-mentioned electrode has good stability.
As illustrated in fig. 1 and 2, the porous three-dimensional electrode material be respectively obtained by embodiment 1 is schemed in low range and powerful SEM.Can obviously be found out by Fig. 1, it has metallic framework that is three-dimensional netted, porous structure, and this aperture is 300 ~ 700 μm.Can obviously be found out by Fig. 1, its particle diameter that bismuth particle is attached to metallic framework is 0.5 ~ 5 μm.
Although the numerical range of each technological parameter involved in the present invention can not all embody in the above-described embodiments, as long as but those skilled in the art can imagine any numerical value fallen in this numerical range above-mentioned completely all can implement the present invention, certainly also comprise the combination in any of occurrence in some numerical ranges.Herein, for the consideration of length, eliminate the embodiment providing occurrence in certain one or more numerical range, should not be considered as at this understanding claimed formula of technical scheme of the present invention and processing range being lacked to the support of sufficient embodiment.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for porous three-dimensional electrode material, is characterized in that, comprises the following steps:
(1) foam metal material being inserted concentration is flood in the bismuth solution of 0.5 ~ 500mmol/L, and described bismuth solution is formed by water-soluble bismuth salt is dissolved in the solvent be made up of water and alcohol;
(2) in described bismuth solution, add hydrazine hydrate, make foam metal material continue dipping;
(3) dry foam metal material after dipping, obtained porous three-dimensional electrode material.
2. preparation method according to claim 1, is characterized in that, in step (1), described water-soluble bismuth salt is bismuth nitrate and/or bismuth chloride;
Preferably, described water-soluble bismuth salt dissolution mechanism is ultrasonic disperse 5 ~ 60min under 500 ~ 800W;
Preferably, described foam metal material is a kind of for be selected from nickel foam, foam copper, foamed aluminium, foamed iron, foam chromium, foam zinc, or is selected from binary or ternary alloy three-partalloy foam metal material that three kinds of metallic elements in nickel, copper, aluminium, iron, chromium, zinc form at the most;
Preferably, the time of described dipping is 2 ~ 24 hours;
Preferably, the volume ratio of described water and alcohol is 1:(1/64 ~ 8);
Preferably, described alcohol is one in ethanol, isopropyl alcohol and ethylene glycol or at least two kinds.
3. preparation method according to claim 1, is characterized in that, in step (2), the time of described dipping is 2 ~ 8 hours;
Preferably, the mass concentration of described hydrazine hydrate is 2 ~ 20wt%, and the volume ratio of hydrazine hydrate and bismuth solution is 5 ~ 25:200.
4. preparation method according to claim 1, is characterized in that, is 40 ~ 120 DEG C in temperature dry described in step (3), and the dry time is 1 ~ 48 hour.
5. preparation method according to claim 1, is characterized in that, also comprises with described solvent foam metal material washing 1 ~ 10 time between step (2) and step (3).
6. preparation method according to claim 1, is characterized in that, in step (1) and step (2), the maceration extract temperature of described dipping is 0 ~ 80 DEG C;
Preferably, the pH of maceration extract is 2 ~ 10.
7. one kind adopts the porous three-dimensional electrode material as preparation method as described in any one in claim 1-6 obtains.
8. porous three-dimensional electrode material according to claim 7, is characterized in that, the three-dimensional netted metallic framework that its structure is 300 ~ 700 μm by aperture and be attached to the bismuth particle that the particle diameter of metallic framework is 0.5 ~ 5 μm and formed.
9. can detect an electrochemical sensor for lead ion, it is characterized in that, comprise the electrode be made up of porous three-dimensional electrode material described in claim 7.
10. a purposes for porous three-dimensional electrode material as claimed in claim 7, it is characterized in that, this porous three-dimensional electrode material is applied to the electrode of energy storage device.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961199A (en) * | 2015-06-23 | 2015-10-07 | 广西大学 | Preparation method of Pd-Fe/foamed nickel three-dimensional particle electrodes |
| CN106048705A (en) * | 2016-07-19 | 2016-10-26 | 中国科学院青海盐湖研究所 | Foam chromium and preparation method thereof |
| CN110061191A (en) * | 2019-05-05 | 2019-07-26 | 国联汽车动力电池研究院有限责任公司 | A kind of 3-dimensional metal cathode of lithium and the preparation method and application thereof |
-
2014
- 2014-12-09 CN CN201410746620.XA patent/CN104458851B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961199A (en) * | 2015-06-23 | 2015-10-07 | 广西大学 | Preparation method of Pd-Fe/foamed nickel three-dimensional particle electrodes |
| CN106048705A (en) * | 2016-07-19 | 2016-10-26 | 中国科学院青海盐湖研究所 | Foam chromium and preparation method thereof |
| CN110061191A (en) * | 2019-05-05 | 2019-07-26 | 国联汽车动力电池研究院有限责任公司 | A kind of 3-dimensional metal cathode of lithium and the preparation method and application thereof |
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| CN104458851B (en) | 2018-07-06 |
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