CN101270491B - Galvano-chemistry preparation method for electrochromic magnesium-nickel alloy film - Google Patents
Galvano-chemistry preparation method for electrochromic magnesium-nickel alloy film Download PDFInfo
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- CN101270491B CN101270491B CN2008100939832A CN200810093983A CN101270491B CN 101270491 B CN101270491 B CN 101270491B CN 2008100939832 A CN2008100939832 A CN 2008100939832A CN 200810093983 A CN200810093983 A CN 200810093983A CN 101270491 B CN101270491 B CN 101270491B
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Abstract
The invention relates to an electrochemistry preparation method for an electrochromism magnesium-nickel alloy film. Firstly, an organic solvent N,N-dimethylformamide is dried for 48 hours by an activated 4 molecular sieve, then is decompressed and distilled to remove the impurities; then the main salt dehydrate and nickelous chloride as well as the lithium perchlorate supporting electrolyte are respectively dried for four hours under the vacuum with the temperature of 150 DEG C and then placed in an vacuum drying box for spare; then the nicks and the oil stains on the surface of a copper sheet are removed; the main salt and the organic solvent N,N-dimethylformamide used for supporting electrolyte are prepared into liquid with the concentration of 0.2mol/L of the dehydrate, the concentration of 0.2mol/L of the lithium perchlorate and the concentration of 0.02mol/L of the nickelous chloride; argon is pumped into the liquid so as to expel the oxygen dissolved in the N,N-dimethylformamide; finally the magnesium-nickel alloy film is obtained by carrying out electrochemistry deposition under the constant temperature and constant potential condition by a three-electrode system. The method is simple, needs no complex post treatment working procedures like heat treatment and can effectively control the light transmittance and the reflectivity of the film.
Description
Technical field
The present invention is the technology of preparing of function film, particularly a kind of electrochemical preparation method of electrochromism magnesium-nickel alloy film.
Background technology
Off-color material is widely used in each side such as electronics, information, the energy, building, according to the difference that causes the variable color condition, can be divided into electrochromic material, photochromic material, thermochromic material, gas-discoloration material etc.So-called electrochromism is meant that under impressed voltage or effect of electric field the optical property of material produces stable reversible change phenomenon, and external manifestation is the stable reversible change of the color of material or transparency.Electrochomeric films has good physicochemical property, optical property is adjustable continuously on a large scale, operating voltage is low, energy consumption is little, memory function is arranged, can keep colored state or vitreous state behind the open circuit, the restriction of no vision, working range are wide, be easy to large-area manufacturing, has a wide range of applications in fields such as display device, dimming glass, information storage.Especially aspect dimming glass, can regulate optical properties such as transmission, reflection, absorption according to the performance of optically variable films, electrochomeric glass of making thus or device can be widely used in each side such as building, space flight, traffic, and be all significant for energy-saving and environmental protection.Generally, indoor heat major part exchanges with extraneous by window.In the winter time, nearly 48% heat runs off by window, and in summer, nearly 71% energy is by in the window inlet chamber.Obviously the energy exchange of carrying out to the illumination in the inlet chamber with by window better controlled in addition just can be saved a large amount of energy.
1996, Huibertsol found the interesting hydrogen-inducing off-coloring phenomenon of rare earth metal yttrium, and promptly rare earth metal yttrium film shows different optical characteristics along with the quantity that absorbs hydrogen atom under the room temperature.By change hydrogen pressure or electrochemical means, but rare earth metal yttrium film can reflect the conductor attitude to transparent insulation attitude inverse conversion from height in very short time.The discovery of this material makes the transmittance of artificial control material become possibility, therefore causes investigators' extensive concern.Also opened up simultaneously the new Application Areas of this material.Although this mould material of being made by rare earth element has good transformation performance, the variation range of transmittance is very wide, because its selling at exorbitant prices has limited its application greatly.
Calendar year 2001, U.S.'s blog comes the laboratory to prepare a kind of thin-film material of gas-discoloration with magnesium and one or more transition metal, and wherein the most representative is magnesium nickel film.With respect to rare earth element, because magnesium and nickel is cheap, and the thin-film material for preparing with magnesium nickel can have better transmittance and range of application is more widely arranged.
Yet above-mentioned several thin-film materials only limit to several methods such as electron beam evaporation, magnetron sputtering on the preparation method.The processing condition height that these methods require, the equipment cost costliness has limited the application of this film.Therefore it is low, simple to operate to seek a kind of equipment requirements, and the lower-cost method for preparing the magnesium-nickel alloy film is necessary.
Summary of the invention
The electrochemical preparation method that the purpose of this invention is to provide a kind of electrochromism alloy firm overcomes the deficiency of prior art.
Concrete steps of the present invention are: at first with organic solvent N, and the dinethylformamide activatory
Behind the moisture that molecular sieve drying was removed wherein in 48 hours, again impurity is removed in its underpressure distillation; Be put in the vacuum drying oven standby after 4 hours 150 ℃ of following vacuum-dryings main salt magnesium perchlorate, nickelous chloride and supporting electrolyte lithium perchlorate respectively then; To carry out surface preparation as the copper sheet of matrix again, the cut on copper sheet surface and greasy dirt will be removed; With above-mentioned main salt and supporting electrolyte organic solvent N, dinethylformamide is mixed with the solution of following concentration: magnesium perchlorate concentration is that 0.2mol/L, lithium perchlorate concentration are that 0.2mol/L, nickelous chloride concentration are 0.02mol/L, and to the logical argon gas of this solution 30 minutes, drive out of and be dissolved in N, the oxygen in the dinethylformamide; Utilize three-electrode system to carry out electrochemical deposition at last under the condition of constant temperature constant potential, the constant potential electrodeposition time is 30S-60S.
Above-mentioned thermostat temperature carries out the constant potential galvanic deposit after selected between 10 ℃～40 ℃, best thermostat temperature is 30 ℃.
The scope of above-mentioned control constant potential-2.2V～-selected between the 2.8V, the best constant potential condition is-2.6V.
The present invention adopts electrochemical deposition technique to prepare the magnesium-nickel alloy film, low for equipment requirements, simple to operate, cost is lower, can effectively control the light transmission and the reflectivity of magnesium-nickel alloy film, will contribute for the further promotion and application of Mg-Ni alloy functional materials.
Description of drawings
Fig. 1 and Fig. 2 adopt the magnesium-nickel alloy film of fluorophotometer test and the intensity of reflected light curve of fine copper sheet.
Wherein a is the intensity of reflected light curve of fine copper sheet, and b is the intensity of reflected light curve of magnesium nickel film in the colour killing attitude, and c is the intensity of reflected light curve of magnesium nickel film at coloured state.
Fig. 3 is a basic structure synoptic diagram of the present invention, wherein, the 1st, magnesium nickel film, the 2nd, copper sheet.
Embodiment
The present invention is respectively to organic solvent N, dinethylformamide, main salt magnesium perchlorate and nickelous chloride and supporting electrolyte lithium perchlorate carry out drying treatment: with organic solvent N, dinethylformamide is used activatory 4A molecular sieve drying 48 hours, removes the small amount of moisture that wherein contains through underpressure distillation again.With main salt magnesium perchlorate and nickelous chloride and the supporting electrolyte lithium perchlorate crystal water that vacuum-drying was removed wherein in 4 hours under 150 ℃ of conditions, it is standby to put into vacuum drying oven then.Wherein used organic solvent, main salt and supporting electrolyte are commercially available analytical pure.
Above-mentioned copper sheet 2 surface pre-treating process: earlier through surperficial mechanical polishing as matrix, successively with deionized water wash-, 0.5mol/L sodium hydroxide solution is washed, the deionization washing, be 1: 1 hydrochloric acid activation with volume ratio again, again through the deionization washing, dehydrated alcohol is washed, and is standby behind the room temperature cold air drying at last.
With above-mentioned main salt and supporting electrolyte organic solvent N, it is that 0.2mol/L, lithium perchlorate concentration are that 0.2mol/L, nickelous chloride concentration are 0.02mol/L that dinethylformamide is mixed with magnesium perchlorate concentration, solution, logical exsiccant argon gas is 30 minutes in this solution, get rid of minimal amounts of dissolved oxygen in electrodeposition process to the sedimentary influence of magnesium.
Utilize three-electrode system to carry out electrochemical deposition in airtight electrolyzer under the condition of constant temperature constant potential: three electrodes are respectively that copper sheet is a working electrode, and platinized platinum is a supporting electrode, and saturated calomel electrode is a reference electrode.Between 10 ℃～40 ℃, carry out the constant potential galvanic deposit, the scope of CONTROLLED POTENTIAL-2.2V～-2.8V between (with respect to the current potential of saturated calomel electrode, used current potential all is the current potentials with respect to saturated calomel electrode among the present invention), electrodeposition time is between 30 seconds～60 seconds, obtains the good magnesium nickel film 2 of electrochromic property at last.The too short discoloration good film that all can not get of overlong time.
The magnesium-nickel alloy film is the electrochromic property check of magnesium nickel film 2: will contain the substrate that deposits film and put into the 0.5mol/L sodium hydroxide solution as negative pole, platinized platinum is switched under the volts DS of 5V as positive pole; Exchange the positive and negative electrode energising then.Before and after the exchange positive and negative electrode, the color of alloy film changes, and changes obviously, but can be between coloured state and colour killing attitude inverse conversion.
Under identical voltage, magnesium nickel film 2 is identical with fringe time from the colour killing attitude to coloured state from coloured state to the colour killing attitude.Fringe time changes with the change of energising voltage in addition, and promptly there are following relation conduction time and magnesium nickel film 2 color transitions and time in sodium hydroxide solution:
When voltage was 5V, the time of magnesium nickel film 2 color transitions was 1-2 second.
When voltage was 4V, the time of magnesium nickel film 2 color transitions was 5 seconds.
When voltage was 3V, the time of magnesium nickel film 2 color transitions was 20 seconds.
When voltage was 2V, the time of magnesium nickel film 2 color transitions was 60 seconds.
When voltage was 1V, the time of magnesium nickel film 2 color transitions was 200 seconds.
As seen along with the reduction of energising voltage, the color transition time of magnesium nickel film 2 increases.And when coloured state and colour killing attitude, the transmittance of alloy film has very big variation.Show as that alloy film is black when coloured state, covered the color of copper sheet matrix; When the colour killing attitude, alloy film is a vitreous state, can demonstrate the color of matrix copper sheet.By testing the catoptrical variation of three samples (the fine copper sheet is the negative pole energising with the copper sheet that deposits film, serves as anodal energising with the copper sheet that deposits film), the also change of film light transmission as can be seen.Test result as shown in Figure 1, 2.Fig. 1,2 is respectively the reflection strength curve of lambda1-wavelength three samples when being 500nm and 700nm, and the result shows that when colour killing attitude b, film has good light transmission; When coloured state c, the transmittancy of film is lower.The measurement result of lambda1-wavelength in other visible-ranges and Fig. 1,2 similar.This explanation, the transmittancy difference of film in visible-range is very big under the two states, demonstrates good electrochromic property.
In magnesium perchlorate concentration is that 0.2mol/L, lithium perchlorate concentration are that 0.2mol/L, nickelous chloride concentration are the N of 0.02mol/L, in the dinethylformamide solution, CONTROLLED POTENTIAL is-during 2.4V, temperature is respectively 20 ℃, 40 ℃, all can obtain the good magnesium-nickel alloy film of electrochromic property behind the energising 60S.
In magnesium perchlorate concentration is that 0.2mol/L, lithium perchlorate concentration are that 0.2mol/L, nickelous chloride concentration are the N of 0.02mol/L, in the dinethylformamide solution, CONTROLLED POTENTIAL is-during 2.8V, temperature is respectively 20 ℃, 40 ℃, all can obtain the good magnesium-nickel alloy film of electrochromic property behind the energising 50S.
Embodiment 3
In magnesium perchlorate concentration is that 0.2mol/L, lithium perchlorate concentration are that 0.2mol/L, nickelous chloride concentration are the N of 0.02mol/L, in the dinethylformamide solution, CONTROLLED POTENTIAL is-during 2.6V, temperature is 30 ℃, is respectively 60 seconds conduction time 120 seconds, 30 seconds, 20 seconds.Confirm after testing, all can obtain the good alloy film of discolouration when galvanic deposit 30 seconds and 1 minute, electrodeposition time is that the equal electrochromic property of alloy firm of 120 seconds and 20 seconds is not obvious.
Claims (3)
1. the electrochemical preparation method of an electrochromism magnesium-nickel alloy film is characterized in that: at first with organic solvent N, and the dinethylformamide activatory
Behind the moisture that molecular sieve drying was removed wherein in 48 hours, again impurity is removed in its underpressure distillation; Be put in the vacuum drying oven standby after 4 hours 150 ℃ of following vacuum-dryings main salt magnesium perchlorate, nickelous chloride and supporting electrolyte lithium perchlorate respectively then; To carry out surface preparation as the copper sheet of matrix again, the cut on copper sheet surface and greasy dirt will be removed; With above-mentioned main salt and supporting electrolyte organic solvent N, it is that 0.2mol/L, lithium perchlorate concentration are that 0.2mol/L, nickelous chloride concentration are the solution of 0.02mol/L that dinethylformamide is mixed with magnesium perchlorate concentration, and to the logical argon gas of this solution 30 minutes, drive out of and be dissolved in N, the oxygen in the dinethylformamide; Utilize three-electrode system under the condition of constant temperature constant potential, to carry out electrochemical deposition at last, and the constant potential electrodeposition time is 30s-60s; Above-mentioned thermostat temperature between 10 ℃～40 ℃, the scope of above-mentioned constant potential-2.2V～-2.8V between.
2. the electrochemical preparation method of electrochromism magnesium-nickel alloy film as claimed in claim 1, the thermostat temperature that it is characterized in that above-mentioned the best is 30 ℃.
3. the electrochemical preparation method of electrochromism magnesium-nickel alloy film as claimed in claim 1 is characterized in that above-mentioned best constant potential condition is-2.6V.
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| CN103422123B (en) * | 2013-08-30 | 2016-03-30 | 昆明理工大学 | A kind of method of electro-deposition of magnesium nickel alloy in ionic liquid |
| CN106248596B (en) * | 2016-08-18 | 2020-01-07 | 上海交通大学 | In-situ spectrum ventilation testing device for hydrogen-induced color-changing functional film |
| CN107887609B (en) * | 2017-09-27 | 2020-08-25 | 姚乃元 | Method for preventing anode attenuation of fuel cell and anode material |
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| US6647166B2 (en) * | 2000-08-17 | 2003-11-11 | The Regents Of The University Of California | Electrochromic materials, devices and process of making |
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| US6647166B2 (en) * | 2000-08-17 | 2003-11-11 | The Regents Of The University Of California | Electrochromic materials, devices and process of making |
Non-Patent Citations (2)
| Title |
|---|
| 王建朝.二甲基甲酰胺中电沉积镁镍合金的研究.青海师范大学学报(自然科学版) 2.2003,(2),48-50. |
| 王建朝.二甲基甲酰胺中电沉积镁镍合金的研究.青海师范大学学报(自然科学版) 2.2003,(2),48-50. * |
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