CN103639420B - A kind of low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle - Google Patents
A kind of low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle Download PDFInfo
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- CN103639420B CN103639420B CN201310609893.5A CN201310609893A CN103639420B CN 103639420 B CN103639420 B CN 103639420B CN 201310609893 A CN201310609893 A CN 201310609893A CN 103639420 B CN103639420 B CN 103639420B
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Abstract
The present invention relates to a kind of low melt type ionic liquid electrodeposition altogether and prepare the method for copper nanoparticle, be mainly used in field of material preparation.First mix after Choline Chloride and urea vacuum drying, reaction prepares low melt type ionic liquid altogether, then adds copper presoma and mixes, obtain ionic liquid-mantoquita composite electrolyte; Under an inert atmosphere, make negative electrode with stainless steel, nickel sheet or titanium sheet, graphite or inert anode make anode, electro-deposition in ionic liquid-mantoquita composite electrolyte, can prepare the copper nanoparticle that particle diameter is 30 ~ 50nm at cathode surface finally.The present invention has cheapness, energy consumption of reaction is low, production procedure is short, pollution-free, technique simple, constant product quality and the advantage such as added value is high.
Description
Technical field
The present invention relates to a kind of low melt type ionic liquid electrodeposition altogether and prepare the method for copper nanoparticle, be mainly used in field of material preparation.
Background technology
Copper powder is with the chemical property of its excellence, and Chang Zuowei conducting resinl, electrically-conducting paint and electrode material are widely used in the fields such as machinery, metallurgy, chemical industry, Aero-Space; Copper nanoparticle has the characteristics such as small-size effect, skin effect, quantum size effect, macro electronic tunnel-effect and Dielectric confinement effect because of it, has greatly widened its conventional use.Recent study finds, copper nanoparticle can be used for making catalyst, lube oil additive, medical domain treatment osteoporosis, fracture etc.; Along with the development of electronics industry, the ultra-fine thick film ink prepared by copper nanoparticle will play an important role in large scale integrated circuit.Therefore, the development of copper nanoparticle is a key technology bringing copper revolutionary variation, has important theory significance and practical value.
At present, the preparation of copper nanoparticle mainly comprises mechanochemical reaction, gas phase steam method, liquid phase reduction, electrodeposition process etc.The powder that wherein prepared by mechanochemical reaction forms not easily even, and powder is easily reunited, and domain size distribution is wide, so lack realistic meaning; Gas phase steam method needed raw material gas price is expensive, and equipment is complicated, and cost is high.Current most study be liquid phase reduction, but liquid-phase reduction needs again the reducing agent using some severe toxicity, this all can work the mischief to researcher itself or environment.Electrochemical deposition method has that reaction condition gentleness, instrument and equipment are simple, the advantage of nontoxic pollution-free, is the effective means of nano materials.Traditional electrical depositing nano copper powder is produced and is carried out in aqueous, number of patent application discloses a kind of method of aqueous solution preparing nano-bronze powder using electric deposition for " 201210428910 ", the method adopts and adds mixed acid, the copper salt solution of surfactant is electrolyte, copper-base is positive electrode, stainless steel is negative pole, pass into direct current, depositing nano copper powder on negative electrode, take off copper nanoparticle and use distilled water and ethanol purge, then dry in a vacuum, copper nanoparticle can be obtained, the preparation of this copper nanoparticle need complete under higher current density, under this condition, the generation of liberation of hydrogen side reaction is inevitable, in addition, in order to obtain the deposited powder meeting quality requirements, the use of the additive for the purpose of anti-oxidant, anti-agglomeration etc. is indispensable.Wherein, additive therefor recipe ingredient is complicated, and not easy-regulating in use procedure, is also difficult in actual application ensure the stable of copper powder quality.The new method of research and development preparing nano-bronze powder using electric deposition is very necessary.
Document (synthetic chemistry, 2010,18 (4), 497-500) reports in Choline Chloride ionic liquid, adopts sacrificial anode protection directly to prepare from metallic copper the copper particulate that particle diameter is about 30nm at 80 DEG C.But the method: 1) a certain amount of anhydrous CuCl need dissolved in advance
2carry out under the condition of inductive anode copper continuous-dissolution, due to anhydrous CuCl
2strong moisture absorption make to introduce moisture unavoidably in experimental implementation process, thus bring the interference of liberation of hydrogen; 2) adopt the method for sacrificing copper anode can the copper ion that consumed by cathodic deposition of supply, but at ionic liquid Anodic copper dissolution by electrochemical control, and cathodic deposition obtain copper powder reaction and control by diffusion.Under this condition, the carrying out of electrode reaction will cause anodic dissolution rate much larger than cathodic deposition speed, thus copper ion concentration accumulation in solution is increased, this will be conducive to the agglomeration of copper powder in continuous electro-deposition process, causes gained copper powder particle size skewness.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides in a kind of low melt type ionic liquid altogether with cuprous oxide is mantoquita presoma, and the new method that particle diameter is the copper nanoparticle of 30 ~ 50nm is prepared in electro-deposition.The present invention has cheapness, energy consumption of reaction is low, production procedure is short, pollution-free, technique simple, constant product quality and the advantage such as added value is high, and the present invention is achieved through the following technical solutions.
Technology path provided by the invention is: using low melt type ionic liquid altogether as electrolyte, copper presoma is dissolved into wherein (when having verified 50 DEG C, the saturation solubility of cuprous oxide in low melt type ionic liquid is altogether not less than 0.80g/100g, electrolysis demand can be met), negative electrode is made with stainless steel, graphite or inert anode make anode, carry out electrolysis under an inert atmosphere.
A kind of low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle, its concrete steps are as follows: first by Choline Chloride and urea after drying under 80 DEG C of vacuum according to mol ratio 1:(2 ~ 4) mixing, and under 80 DEG C of heated at constant temperature conditions, react 2h can prepare low melt type ionic liquid altogether; Then in the low melt type ionic liquid altogether prepared, add copper presoma to mix, obtain ionic liquid-mantoquita composite electrolyte; It is last that make negative electrode with stainless steel, nickel sheet or titanium sheet, graphite or inert anode make anode under an inert atmosphere, temperature be 30 ~ 50 DEG C, stir speed (S.S.) is 100 ~ 300r/min, control flume voltage be 2.0 ~ 2.5V or current density is 2 ~ 8mA ﹒ cm
-2electro-deposition 1 ~ 3h under condition, in ionic liquid-mantoquita composite electrolyte, can prepare copper nanoparticle at cathode surface.
Described copper presoma is cuprous oxide, and wherein low the volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:(300 ~ 800) ml/mg.
Above-mentioned low melt type ionic liquid (ChCl-Urea) is altogether the low melt type ionic liquid altogether of water white transparency, and its water content, lower than 100ppm, does not contain other impurity.
The invention has the beneficial effects as follows: (1) electro-deposition gained of the present invention copper nanoparticle particle size range is 30 ~ 50nm, uniform particles and not easily reuniting, without the need to adding any additive, because system is not moisture, electrodeposition process disturbs without liberation of hydrogen; The present invention has cheapness, energy consumption of reaction is low, production procedure is short, pollution-free, technique simple, constant product quality and the advantage such as added value is high.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 electro-deposition products therefrom;
Fig. 2 is TEM and the grain size distribution of the embodiment of the present invention 1 electro-deposition products therefrom;
Fig. 3 is TEM and the grain size distribution of the embodiment of the present invention 2 electro-deposition products therefrom;
Fig. 4 is the TEM figure of the embodiment of the present invention 3 electro-deposition products therefrom.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
This low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle, its concrete steps are as follows: the first drying under 80 DEG C of vacuum by Choline Chloride and urea, react 2h and can prepare low melt type ionic liquid altogether under being then incorporated in 80 DEG C of heated at constant temperature conditions according to mol ratio 1:2 is mixed; In the low melt type ionic liquid altogether of the 50mL prepared, add copper presoma mix, prepare ionic liquid-mantoquita composite electrolyte, wherein copper presoma is cuprous oxide, and the low volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:300ml/mg; Under an inert atmosphere, negative electrode is made with stainless steel (1.0cm × 1.0cm × 0.2cm), graphite makes anode, die opening is 1cm, temperature be 30 DEG C, stir speed (S.S.) is 100r/min, control flume voltage be 2.5V condition under, in ionic liquid-mantoquita composite electrolyte electro-deposition 2h, copper nanoparticle can be prepared at cathode surface.
Above-mentioned copper nanoparticle average-size is 28 ± 7nm, as illustrated in fig. 1 and 2.
Embodiment 2
This low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle, its concrete steps are as follows: the first drying under 80 DEG C of vacuum by Choline Chloride and urea, react 2h and can prepare low melt type ionic liquid altogether under being then incorporated in 80 DEG C of heated at constant temperature conditions according to mol ratio 1:4 is mixed; In the low altogether melt type ionic liquid preparing 50ml, add copper presoma mix, prepare ionic liquid-mantoquita composite electrolyte, wherein copper presoma is cuprous oxide, and the low volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:600ml/mg; Under an inert atmosphere, negative electrode is made with nickel sheet (1.0cm × 1.0cm × 0.2cm), graphite makes anode, die opening is 1cm, temperature be 30 DEG C, stir speed (S.S.) is 300r/min, control flume voltage be 2.2V condition under, in the ionic liquid prepared-mantoquita composite electrolyte electro-deposition 2h, copper nanoparticle can be prepared at cathode surface.
Above-mentioned copper nanoparticle average-size is 57 ± 6nm, as shown in Figure 3.
Embodiment 3
This low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle, its concrete steps are as follows: first by Choline Chloride and urea after drying under 80 DEG C of vacuum according to mol ratio 1:3 mixing, and under 80 DEG C of heated at constant temperature conditions, react 2h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid preparing 50ml, add copper presoma mix, prepare ionic liquid-mantoquita composite electrolyte, wherein copper presoma is cuprous oxide, and the low volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:500ml/mg; Then under an inert atmosphere, take graphite as anode, nickel sheet (1.0cm × 1.0cm × 0.2cm) makes negative electrode, and die opening is 1cm, above-mentioned low altogether melt type ionic liquid is electrolyte, temperature be 50 DEG C, stir speed (S.S.) is 300r/min, control current density is 5mA ﹒ cm
-2electro-deposition 2h under condition, can prepare copper nanoparticle at cathode surface.
Above-mentioned copper nanoparticle average-size is 30 ± 5nm, as shown in Figure 4.
Embodiment 4
This low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle, its concrete steps are as follows: first by Choline Chloride and urea after drying under 80 DEG C of vacuum according to mol ratio 1:2 mixing, and under 80 DEG C of heated at constant temperature conditions, react 2h can prepare low melt type ionic liquid altogether; Then in the low melt type ionic liquid altogether prepared, add copper presoma to mix, obtain ionic liquid-mantoquita composite electrolyte, wherein copper presoma is cuprous oxide, and the low volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:300ml/mg; Under an inert atmosphere finally, negative electrode is made with titanium sheet (1.0cm × 1.0cm × 0.2cm), anode made by platinized platinum (1.0cm × 1.0cm × 0.2cm), die opening is 1cm, temperature be 50 DEG C, stir speed (S.S.) is 300r/min, control flume voltage be 2.5V condition under, in ionic liquid-mantoquita composite electrolyte electro-deposition 1h, copper nanoparticle can be prepared at cathode surface.
Embodiment 5
This low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle, its concrete steps are as follows: first by Choline Chloride and urea after drying under 80 DEG C of vacuum according to mol ratio 1:4 mixing, and under 80 DEG C of heated at constant temperature conditions, react 2h can prepare low melt type ionic liquid altogether; Then in the low melt type ionic liquid altogether prepared, add copper presoma to mix, obtain ionic liquid-mantoquita composite electrolyte, wherein copper presoma is cuprous oxide, and the low volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:800ml/mg; Under an inert atmosphere finally, negative electrode is made with stainless steel (1.0cm × 1.0cm × 0.2cm), anode made by platinized platinum (1.0cm × 1.0cm × 0.2cm), and die opening is 1cm, temperature be 50 DEG C, stir speed (S.S.) be 100r/min, control current density be 6mA ﹒ cm
-2electro-deposition 1h under condition, in ionic liquid-mantoquita composite electrolyte, can prepare copper nanoparticle at cathode surface.
Claims (1)
1. the one kind low method being total to melt type ionic liquid electrodeposition and preparing copper nanoparticle, it is characterized in that concrete steps are as follows: first by Choline Chloride and urea after drying under 80 DEG C of vacuum according to mol ratio 1:(2 ~ 4) mixing, and under 80 DEG C of heated at constant temperature conditions, react 2h can prepare low melt type ionic liquid altogether; Then in the low melt type ionic liquid altogether prepared, add copper presoma to mix, obtain ionic liquid-mantoquita composite electrolyte; It is last that make negative electrode with stainless steel, nickel sheet or titanium sheet, graphite or inert anode make anode under an inert atmosphere, temperature be 30 ~ 50 DEG C, stir speed (S.S.) is 100 ~ 300r/min, control flume voltage be 2.0 ~ 2.5V or current density is 2 ~ 8mA ﹒ cm
-2electro-deposition 1 ~ 3h under condition, in ionic liquid-mantoquita composite electrolyte, can prepare copper nanoparticle at cathode surface;
Described copper presoma is cuprous oxide, and wherein low the volume of melt type ionic liquid and the mass ratio of cuprous oxide are altogether 100:(300 ~ 800) ml/mg.
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| CN104141151A (en) * | 2014-08-06 | 2014-11-12 | 哈尔滨工业大学 | Method for forming metal simple substance through ionic liquid in electrolytic deposition mode |
| CN104485459B (en) * | 2014-11-13 | 2017-05-10 | 昆明理工大学 | Method for preparing copper foil for lithium ion battery through low eutectic type ionic liquid electro-deposition |
| CN104562090A (en) * | 2014-12-30 | 2015-04-29 | 昆明理工大学 | Method for preparing nano-porous copper through in-situ electrolysis of eutectic ionic liquid |
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| CN104947136B (en) * | 2015-07-07 | 2017-04-12 | 昆明理工大学 | Method for preparing cuprous chloride nanocube electrode material by eutectic type ionic liquid electrolysis |
| CN108660483A (en) * | 2018-06-08 | 2018-10-16 | 上海大学 | A kind of preparation method of corronil |
| CN109609974A (en) * | 2019-01-29 | 2019-04-12 | 长江师范学院 | Conducive to the method for reducing Zinc electrolysis tank voltage and energy consumption |
| CN110205651B (en) * | 2019-07-11 | 2021-03-09 | 昆明理工大学 | Method for preparing vanadium metal by electrochemically reducing vanadium oxide at low temperature |
| CN110629252B (en) * | 2019-09-29 | 2021-05-04 | 昆明理工大学 | Method for preparing metal copper by electrolytic refining |
| CN114378300B (en) * | 2022-01-21 | 2023-10-20 | 重庆科技学院 | Method for preparing nanometer copper powder by taking copper oxide as raw material |
| CN114406280B (en) * | 2022-01-21 | 2023-10-24 | 重庆科技学院 | Method for preparing nanometer copper powder by taking chalcopyrite as raw material |
| CN114540886B (en) * | 2022-02-15 | 2022-12-27 | 中国石油大学(北京) | Method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition |
| CN114774993B (en) * | 2022-04-25 | 2023-06-27 | 嘉兴学院 | Method for preparing nanometer copper powder by electrodeposition |
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