CN105671598A - Method for directly preparing aluminum foil through low temperature electrolysis - Google Patents
Method for directly preparing aluminum foil through low temperature electrolysis Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 96
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000011888 foil Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005868 electrolysis reaction Methods 0.000 title claims description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 22
- 238000004070 electrodeposition Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- -1 aluminum compound Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 125000005496 phosphonium group Chemical group 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 239000011149 active material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- AMFMJCAPWCXUEI-UHFFFAOYSA-M 1-ethylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC=C1 AMFMJCAPWCXUEI-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000011809 glassy carbon fiber Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021404 metallic carbon Inorganic materials 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
- C25D3/44—Aluminium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
本发明公开了一种在离子液体介质中低温下直接电解制备铝箔的方法，不仅解决了离子液体电沉积金属铝存在的沉积致密层难以剥脱的难题，也为铝箔的电化学制备提供了一条新的路径。本方法重要创新是利用金属铝在碳阴极上较高的成核过电位形成致密沉积层，同时金属铝与碳材料晶格匹配性较差，使得阴极表面的致密铝箔易于剥脱。本发明以低温离子液体为电解液，以表面光滑的碳材料为阴极，利用离子液体熔点低、不易挥发的特性，在25～100℃的低温范围内成功制备了金属铝箔。本发明的特点包括：操作温度低、工艺步骤简单易操作；易于实现连续生产，可显著降低铝及铝箔生产能耗和成本。本发明在低温电解金属铝及铝箔制备方面具有很好的应用前景。The invention discloses a method for directly electrolytically preparing aluminum foil at a low temperature in an ionic liquid medium, which not only solves the difficult problem that the deposited dense layer existing in ionic liquid electrodeposited metal aluminum is difficult to peel off, but also provides a new method for the electrochemical preparation of aluminum foil. path of. The important innovation of this method is to use the high nucleation overpotential of metal aluminum on the carbon cathode to form a dense deposition layer. At the same time, the lattice matching between metal aluminum and carbon materials is poor, so that the dense aluminum foil on the surface of the cathode is easy to peel off. The invention uses low-temperature ionic liquid as electrolyte, and smooth-surfaced carbon material as cathode, and utilizes the low melting point and non-volatile characteristics of ionic liquid to successfully prepare metal aluminum foil in the low temperature range of 25-100°C. The characteristics of the invention include: low operating temperature, simple and easy-to-operate process steps; easy realization of continuous production, and can significantly reduce energy consumption and cost of aluminum and aluminum foil production. The invention has good application prospects in the preparation of low-temperature electrolytic metal aluminum and aluminum foil.
Description
技术领域technical field
本发明属于电解领域，涉及一种低温电沉积制备铝箔的新方法。The invention belongs to the field of electrolysis and relates to a new method for preparing aluminum foil by low-temperature electrodeposition.
背景技术Background technique
铝工业是世界上最大的电化学工业之一，因其具有密度小、可塑性强等一系列优异的性能，原铝的产量和铝的循环使用量也在快速增长。截止到2014年底，世界电解铝年产量已达到5390万吨，中国电解铝的产量约占世界总产量的45％。因铝的还原电位较负(小于氢的析出电位)，不能像Cu、Zn、Pb等有色金属一样在水溶液中电解。在过去的一百多年里，原铝的生产都采用霍尔-埃鲁法(Hall-Héroult)，该方法是在950℃左右的温度下将氧化铝溶解于熔融的冰晶石中，并用直流电进行电解。电解槽阴极产物为铝液，阳极产物则是CO2、CO和HF等物质。尽管霍尔-埃鲁法存在着电解温度高、能耗高、污染重和产品质量低(～99.5％)等问题，该方法仍是目前工业上唯一的原铝制备方法。The aluminum industry is one of the largest electrochemical industries in the world. Because of its excellent properties such as low density and strong plasticity, the output of primary aluminum and the amount of recycled aluminum are also growing rapidly. By the end of 2014, the world's annual output of electrolytic aluminum had reached 53.9 million tons, and China's output of electrolytic aluminum accounted for about 45% of the world's total output. Because the reduction potential of aluminum is relatively negative (less than the precipitation potential of hydrogen), it cannot be electrolyzed in aqueous solution like Cu, Zn, Pb and other non-ferrous metals. In the past more than a hundred years, the production of primary aluminum has adopted the Hall-Héroult method (Hall-Héroult), which is to dissolve alumina in molten cryolite at a temperature of about 950 ° C, and use direct current to Perform electrolysis. The cathode product of the electrolytic cell is aluminum liquid, and the anode product is CO 2 , CO and HF. Although the Hall-Elu method has problems such as high electrolysis temperature, high energy consumption, heavy pollution and low product quality (~99.5%), this method is still the only primary aluminum production method in industry.
科学家们一直在不懈地探索铝生产的替代方法，这些方法主要包括碳热还原法、低温熔盐电解法和有机体系电解法。铝很难被还原，铝的碳热还原要在2000℃左右进行，低温熔盐法也要在700℃进行电解，这两种具有高温过程共同的问题，如能耗高、设备腐蚀严重、污染物排放量大、生产成本高等。有机体系电解法可以在一定程度上克服上述问题，但有机体系具有电化学窗口较窄，电导率低、易挥发、易燃等缺点，限制了该方法在金属铝制备方面的工业应用。Scientists have been relentlessly exploring alternative methods of aluminum production, mainly including carbothermal reduction, low-temperature molten salt electrolysis, and electrolysis of organic systems. Aluminum is difficult to be reduced. The carbothermal reduction of aluminum should be carried out at about 2000°C, and the low-temperature molten salt method should also be electrolyzed at 700°C. These two have common problems in high-temperature processes, such as high energy consumption, serious corrosion of equipment, and pollution. Large emissions and high production costs. The organic system electrolysis method can overcome the above problems to a certain extent, but the organic system has the disadvantages of narrow electrochemical window, low conductivity, volatile and flammable, which limit the industrial application of this method in the preparation of metal aluminum.
早在1948年，Hurley等在寻找电解氧化铝的电解质材料时，将N-乙基吡啶氯化物和AlCl3混合后得到了一种无色液体，这种液体即为氯铝酸型离子液体，也被称为第一代离子液体。离子液体是一种理想的室温液态电解质，它不挥发，不易燃，一般具有良好的导电性和较宽的电化学窗口，室温下可以进行电解铝、镁、钛等较活泼金属的反应，既克服了水溶液电解无法获得活泼金属的难题，也克服了高温熔盐对设备的强腐蚀，降低了电解过程的能耗和污染物的排放，有望实现冶金过程的绿色生产，使传统的电化学冶金技术发生革命性变化。As early as 1948, when Hurley et al. were looking for electrolyte materials for electrolytic alumina, they mixed N-ethylpyridinium chloride and AlCl3 to obtain a colorless liquid, which was a chloroaluminate-type ionic liquid, also Known as the first generation of ionic liquids. Ionic liquid is an ideal liquid electrolyte at room temperature. It is non-volatile and non-flammable. It generally has good conductivity and a wide electrochemical window. It can electrolyze aluminum, magnesium, titanium and other active metals at room temperature. It overcomes the problem that the electrolysis of aqueous solution cannot obtain active metals, and also overcomes the strong corrosion of high-temperature molten salt on equipment, reduces the energy consumption and pollutant discharge of the electrolysis process, and is expected to realize the green production of the metallurgical process, making the traditional electrochemical metallurgy Technology has revolutionized.
与传统霍尔法电解铝不同，因离子液体中电解铝反应温度较低(25℃～100℃)，铝产品以固态形式存在。固态的铝产品通常是以铝粉形式存在，铝粉与电解液的分离成为该工艺技术放大的难题。同时，铝在阴极的沉积过程中晶体生长容易产生枝晶，严重影响了长期电解过程的稳定性。Different from the traditional Hall method electrolytic aluminum, because the reaction temperature of electrolytic aluminum in ionic liquid is low (25℃～100℃), the aluminum product exists in solid form. Solid aluminum products usually exist in the form of aluminum powder, and the separation of aluminum powder and electrolyte has become a difficult problem for the scale-up of this process technology. At the same time, the crystal growth of aluminum in the cathode deposition process tends to produce dendrites, which seriously affects the stability of the long-term electrolysis process.
ReddyR.G.等研究发现，将电极的背面以不导电的胶带覆盖，从而对电极进行修饰，可通过氯铝酸离子液体中电沉积法在铜基底上产生致密的沉积层。ChangeJ.K.等报道了在镁合金表面，通过离子液体低温电沉积也可以获得致密的沉积铝层。ZhangS.J.等研究发现通过合适的有机物添加，可以通过离子液体低温沉积方法在铜阴极或不锈钢阴极上获得镜面光亮的铝沉积层。值得注意的是，上述方法获得的致密沉积层都是在金属表面，由于金属阴极与铝沉积层晶格匹配较好，沉积层很难从基底上剥脱，因此该方法仅适合用于金属表面的修饰，很难用于以铝产品为目的的电解或精炼过程。Research by Reddy R.G. et al. found that the back of the electrode is covered with a non-conductive tape to modify the electrode, and a dense deposition layer can be produced on the copper substrate by electrodeposition in chloroaluminate ionic liquid. Change J.K. et al. reported that on the surface of magnesium alloy, a dense deposited aluminum layer can also be obtained by low-temperature electrodeposition of ionic liquid. Zhang S.J. et al. found that through the addition of appropriate organic substances, a mirror-bright aluminum deposition layer can be obtained on a copper cathode or a stainless steel cathode by an ionic liquid low-temperature deposition method. It is worth noting that the dense deposition layer obtained by the above method is all on the metal surface. Since the metal cathode and the aluminum deposition layer have a good lattice match, the deposition layer is difficult to peel off from the substrate, so this method is only suitable for the metal surface. Modification, difficult to use in electrolysis or refining process for the purpose of aluminum products.
本发明的重要创新是将光滑的碳阴极引入单质铝的电沉积过程，首先与在铝阴极上的本体沉积不同，本发明的研究发现铝在碳阴极表面较高的成核过电位(附图1)，会在碳电极上产生致密的沉积层；同时，由于非金属碳与金属铝晶格结构差距较大，使得二者的表面结合力较弱，方便了致密沉积层从光滑的碳电极表面剥脱，使产品与电极的分离变得容易。本发明在25～100℃，成功制备了直径为1cm，厚度在10～100μm的光亮铝箔。The important innovation of the present invention is that smooth carbon cathode is introduced into the electrodeposition process of elemental aluminum. At first, it is different from the bulk deposition on the aluminum cathode. The research of the present invention finds that the higher nucleation overpotential of aluminum on the carbon cathode surface (accompanying drawing 1), a dense deposition layer will be produced on the carbon electrode; at the same time, due to the large gap between the non-metallic carbon and the metal aluminum lattice structure, the surface bonding force of the two is weak, which facilitates the dense deposition layer from the smooth carbon electrode. Exfoliation of the surface makes it easy to separate the product from the electrode. The invention successfully prepares a bright aluminum foil with a diameter of 1 cm and a thickness of 10-100 μm at 25-100 DEG C.
发明内容Contents of the invention
本发明提供了一种在离子液体介质中低温下直接电解制备铝箔的方法，其核心技术创新是利用金属铝在碳阴极上较高的成核过电位形成致密沉积层，同时金属铝与碳材料晶格匹配性较差，使得阴极表面的致密铝箔与碳电极附着力较弱，铝箔易于与电极分离。该方法具有电解温度低、工艺步骤简单易操作、易于实现连续生产，可显著降低铝及铝箔生产能耗和成本等优点。具体的技术方案如下：The invention provides a method for directly electrolytically preparing aluminum foil at low temperature in an ionic liquid medium. The core technological innovation is to use the high nucleation overpotential of metal aluminum on the carbon cathode to form a dense deposition layer, and at the same time, metal aluminum and carbon materials The poor lattice matching makes the adhesion between the dense aluminum foil on the cathode surface and the carbon electrode weak, and the aluminum foil is easy to separate from the electrode. The method has the advantages of low electrolysis temperature, simple and easy-to-operate process steps, easy realization of continuous production, and can significantly reduce energy consumption and cost of aluminum and aluminum foil production, and the like. The specific technical scheme is as follows:
在25℃～100℃下直接电解制备铝箔的方法，首先将化合态的铝源溶解在离子液体体系中，以表面光滑的碳材料为阴极，惰性电极或高纯金属铝为阳极，进行恒压和恒流电沉积，电沉积产物从电极表面剥离后经有机物清洗分离后得到铝箔。The method of directly electrolytically preparing aluminum foil at 25°C to 100°C, first dissolves the combined aluminum source in the ionic liquid system, uses a smooth carbon material as the cathode, and an inert electrode or high-purity metal aluminum as the anode, and conducts constant voltage. And constant current electrodeposition, the electrodeposition product is peeled off from the electrode surface, and then the aluminum foil is obtained after the organic matter is cleaned and separated.
本发明制备铝箔的方法，所述的溶于离子液体的铝化合物是无水AlCl3和无水AlBr3中的一种，其在离子液体电解液中的浓度为0.9M～2.7M。In the method for preparing aluminum foil of the present invention, the aluminum compound dissolved in the ionic liquid is one of anhydrous AlCl 3 and anhydrous AlBr 3 , and its concentration in the ionic liquid electrolyte is 0.9M-2.7M.
本发明制备铝箔的方法，所述离子液体阳离子为咪唑型、吡啶型、季铵型、季鏻型、吡咯型、哌啶型、吗啉型和锍盐型，其结构中的取代基为烷基，烷氧基、氟或氢中的一种；阴离子为F-、Cl-、Br-、I-、BF4 -、PF6 -和[N(CF3SO2)2]-。In the method for preparing aluminum foil in the present invention, the ionic liquid cations are imidazole type, pyridine type, quaternary ammonium type, quaternary phosphonium type, pyrrole type, piperidine type, morpholine type and sulfonium salt type, and the substituents in the structure are alkyl group, one of alkoxy, fluorine or hydrogen; the anion is F - , Cl - , Br - , I - , BF 4 - , PF 6 - and [N(CF 3 SO 2 ) 2 ] - .
本发明制备铝箔的方法，所述的离子液体中电沉积铝箔体系中阴极为表面光滑的石墨、玻碳、碳纤维等碳材料，其表面粗糙度应不大于0.5μm；所述的阳极中惰性阳极为玻碳电极和铂电极中的一种，活性阳极为高纯铝。In the method for preparing aluminum foil of the present invention, the cathode in the electrodeposited aluminum foil system in the ionic liquid is carbon materials such as graphite, glassy carbon, and carbon fiber with a smooth surface, and its surface roughness should not be greater than 0.5 μm; the inert anode in the anode It is one of glassy carbon electrodes and platinum electrodes, and the active anode is high-purity aluminum.
本发明制备铝箔的方法，所述沉积方法中恒电流沉积时的电流密度为1.0～6.5A/dm2，恒电压沉积时，电压范围为-1.5V～-3.2V。In the method for preparing aluminum foil of the present invention, in the deposition method, the current density during constant current deposition is 1.0-6.5A/dm 2 , and during constant voltage deposition, the voltage range is -1.5V to -3.2V.
本发明制备铝箔的方法，所述电沉积获得的铝箔与阴极机械分离后首先用DMF清洗分离表面的离子液体，再用冷氮气吹干。In the method for preparing aluminum foil of the present invention, after the aluminum foil obtained by electrodeposition is mechanically separated from the cathode, the ionic liquid on the separated surface is first cleaned with DMF, and then dried with cold nitrogen.
本发明制备铝箔的方法，其优选的条件是在50℃的含有1.5MAlCl3的氯化1-丁基-3-甲基咪唑[BmimCl]离子液体中，采用表面粗糙度小于0.5μm的玻碳作为阴极，恒定电流密度4.0A/dm2电解2h，产物进行多次洗涤得到光亮的铝箔，其形貌和组成见附图2和附图3。The method for preparing aluminum foil of the present invention, its preferred condition is in the chlorinated 1-butyl- 3 -methylimidazolium [BmimCl] ionic liquid containing 1.5MAlCl 50 ℃, adopts the glassy carbon that surface roughness is less than 0.5 μ m As a cathode, electrolyze at a constant current density of 4.0A/dm 2 for 2 hours, and the product is washed several times to obtain a bright aluminum foil, whose morphology and composition are shown in Figure 2 and Figure 3 .
附图说明Description of drawings
图1不同阴极上沉积过程的的计时电位曲线Fig.1 Chronopotential curves of deposition processes on different cathodes
图2直径1cm玻碳阴极上沉积的铝箔Figure 2 Aluminum foil deposited on glassy carbon cathode with a diameter of 1cm
图350℃下4A/dm2下的沉积1hSEM图Figure 1h SEM image of deposition at 4A/dm2 at 350°C
具体实施方式detailed description
实施例1Example 1
将AlCl3溶解在[BMIMCl]离子液体中，活性物质浓度为0.9M，阴极为直径是3mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒压电沉积，工作电压为-1.5V，温度为25℃，经过3h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [BMIMCl] ionic liquid, the active material concentration is 0.9M, the cathode is a glassy carbon disc electrode with a diameter of 3mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant voltage electrodeposition, the working voltage is -1.5V, the temperature is 25°C, after 3 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is washed with dichloromethane for many times to ensure the cleaning of the ionic liquid Clean, then dry the product with cold nitrogen.
实施例2Example 2
将AlCl3溶解在[PP14Cl]离子液体中，活性物质浓度为1.3M，阴极为直径是3mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒压电沉积，工作电压为-1.8V，温度为50℃，经过3h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [PP 14 Cl] ionic liquid, the active material concentration is 1.3M, the cathode is a glassy carbon disc electrode with a diameter of 3mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant voltage electrodeposition, the working voltage is -1.8V, the temperature is 50°C, after 3 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is washed with dichloromethane for many times to ensure the cleaning of the ionic liquid Clean, then dry the product with cold nitrogen.
实施例3Example 3
将AlCl3溶解在[N2222Cl]离子液体中，活性物质浓度为1.5M，阴极为直径是3mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒压电沉积，工作电压为-2.3V，温度为25℃，经过2h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [N 2222 Cl] ionic liquid, the active material concentration is 1.5M, the cathode is a glassy carbon disc electrode with a diameter of 3mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant voltage electrodeposition, the working voltage is -2.3V, the temperature is 25°C, after 2 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is washed with dichloromethane for many times to ensure the cleaning of the ionic liquid Clean, then dry the product with cold nitrogen.
实施例4Example 4
将AlCl3溶解在[S444Cl]离子液体中，活性物质浓度为2.0M，阴极为直径是10mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒压电沉积，工作电压为-2.5V，温度为40℃，经过2h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [S 444 Cl] ionic liquid, the active material concentration is 2.0M, the cathode is a glassy carbon disc electrode with a diameter of 10mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant voltage electrodeposition, the working voltage is -2.5V, the temperature is 40°C, after 2 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is first washed with dichloromethane for many times to ensure the cleaning of the ionic liquid Clean, then dry the product with cold nitrogen.
实施例5Example 5
将AlCl3溶解在[BMIMCl]离子液体中，活性物质浓度为2.3M，阴极为直径是10mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒压电沉积，工作电压为-3.2V，温度为50℃，经过2h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [BMIMCl] ionic liquid, the active material concentration is 2.3M, the cathode is a glassy carbon disc electrode with a diameter of 10mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant voltage electrodeposition, the working voltage is -3.2V, the temperature is 50 ℃, after 2 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is washed with dichloromethane for many times to ensure the cleaning of the ionic liquid Clean, then dry the product with cold nitrogen.
实施例6Example 6
将AlCl3溶解在[Py14Cl]离子液体中，活性物质浓度为2.7M，阴极为直径是3mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒电流沉积，电流密度为1.0A/dm2，温度为60℃，经过4h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [Py 14 Cl] ionic liquid, the active material concentration is 2.7M, the cathode is a glassy carbon disc electrode with a diameter of 3mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant current deposition, the current density is 1.0A/dm 2 , the temperature is 60°C, after 4 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is first washed with dichloromethane multiple times to ensure that the ionic liquid Clean and dry the product with cold nitrogen.
实施例7Example 7
将AlCl3溶解在[N4441Cl]离子液体中，活性物质浓度为2.7M，阴极为直径是10mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒电流沉积，电流密度为3.0A/dm2，温度为80℃，经过4h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [N 4441 Cl] ionic liquid, the active material concentration is 2.7M, the cathode is a glassy carbon disc electrode with a diameter of 10mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant current deposition, the current density is 3.0A/dm 2 , the temperature is 80°C, after 4 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is first washed with dichloromethane several times to ensure that the ionic liquid Clean and dry the product with cold nitrogen.
实施例8Example 8
将AlCl3溶解在[PP13Cl]离子液体中，活性物质浓度为2.7M，阴极为直径是10mm的玻碳圆盘电极，阳极为惰性玻碳电极，参比电极为铝丝。恒电流沉积，电流密度为6.5A/dm2，温度为100℃，经过2h电沉积在阴极表面获得致密铝箔，电沉积铝箔从阴极表面剥离后，先经过二氯甲烷多次洗涤以保证离子液体清洗干净，再用冷氮气将产品吹干。Dissolve AlCl 3 in [PP 13 Cl] ionic liquid, the active material concentration is 2.7M, the cathode is a glassy carbon disc electrode with a diameter of 10mm, the anode is an inert glassy carbon electrode, and the reference electrode is an aluminum wire. Constant current deposition, the current density is 6.5A/dm 2 , the temperature is 100 ℃, after 2 hours of electrodeposition on the surface of the cathode to obtain dense aluminum foil, after the electrodeposited aluminum foil is peeled off from the surface of the cathode, it is first washed with dichloromethane for many times to ensure that the ionic liquid Clean and dry the product with cold nitrogen.
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