CN108166021B - A method of the low-temperature electrolytic aluminium in depth congruent melting solvent - Google Patents
A method of the low-temperature electrolytic aluminium in depth congruent melting solvent Download PDFInfo
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- CN108166021B CN108166021B CN201711447337.7A CN201711447337A CN108166021B CN 108166021 B CN108166021 B CN 108166021B CN 201711447337 A CN201711447337 A CN 201711447337A CN 108166021 B CN108166021 B CN 108166021B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/18—Electrolytes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
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Abstract
The invention discloses a kind of methods of low-temperature electrolytic aluminium in depth congruent melting solvent.This method comprises: the hydrogen-bond donor and hydrogen bond receptor are mixed according to the proportion, after obtaining the depth congruent melting solvent, metal oxide is dissolved in depth congruent melting solvent, using the system as electrolyte, is electrolysed.The advantage of the invention is that depth congruent melting solvent is as electrolyte, it also has synthesis simple, cheap and with high purity, is the ideal solvent of electrochemical deposition aluminium other than the general character with ionic liquid；And electrolytic aluminium at room temperature is realized, the al deposition layer of bright, uniform densification has been obtained, has improved the adhesive ability of al deposition layer, avoid the generation of dendrite aluminium, solve the problems, such as that current sedimentary is easy to fall off；In electrolytic process, no gas is generated, non-environmental-pollution.
Description
Technical field
The invention belongs to Material Fields, are related to a kind of method of low-temperature electrolytic aluminium in depth congruent melting solvent.
Background technique
Aluminium Industry is maximum electrochemical industry in the world, under the promotion of China's sustained economic development, domestic oxygen
Change aluminium, Aluminum Electrolysis Production are rapidly developed, and production capacity and actual production are also in sustainable growth.Modern aluminum industry produces aluminium master
To use Hall-H é roult method, that is, cryolite-alumina electrolysis method, this method was after development in more than 100 years, increasingly
Maturation, but there are still electrolysis temperatures it is high, energy consumption is high, seriously polluted the problems such as, and the al deposition layer that technique obtains at present
Thin, dendrite easy to form, powdered granule, easy to fall off in deposition process, therefore is difficult to be formed and realizes that metallic aluminium is good in substrate
Plating.Therefore, electrolysis temperature is more mild, the higher new process of efficiency of energy utilization is very necessary for exploitation.
Since the standard deposition current potential of aluminium is -1.66V, from the aqueous solution deposition of aluminium salt go out aluminium be it is almost impossible,
There is research to be electrolysed AlCl in organic solvent and ionic liquid in recent years3, some achievements of acquirement, electrolysis temperature is remarkably decreased,
Energy consumption is reduced, and overcomes the problem that can not be electrolysed active metal in aqueous solution.But organic solvent exists as electrolyte
It is volatile in use process, cause secondary pollution；And existing ionic liquid is because its viscosity is big, expensive, unknown product
The drawbacks such as generation also limit industrial applications of this electrolyte in electrolytic aluminium.So developing stable, cheap, viscous
The novel electrolytes for spending the advantages that small are extremely urgent.
Summary of the invention
The object of the present invention is to provide a kind of methods of low-temperature electrolytic aluminium in depth congruent melting solvent.
Application of the claimed depth congruent melting solvent in electrolytic metal.
In above-mentioned application, the depth congruent melting solvent is made of hydrogen-bond donor and hydrogen bond receptor；
The metal is selected from least one of aluminium, silicon and calcium.
Specifically, the hydrogen-bond donor in carboxylic acid compound, choline and amides compound extremely
Few one kind；
More specifically, the carboxylic acid compound be selected from oxalic acid, malonic acid, succinic acid, glutaric acid, citric acid, furancarboxylic acid and
At least one of benzoic acid；
The choline is selected from least one of choline chloride, choline bromide, choline iodide and guanidine hydrochloride；
The amides compound is selected from least one of urea, methylurea, thiocarbamide and methylthiourea；
The hydrogen bond receptor is polyethylene glycols hydrogen bond receptor；It is chosen in particular from polyethylene glycol, glycerol and crown ether at least
It is a kind of；
The number-average molecular weight of the polyethylene glycol is specially 200-4000.
The molar ratio of the hydrogen-bond donor and hydrogen bond receptor is 1:2~1:8,1:4 or 1:6.
The method provided by the invention for preparing the depth congruent melting solvent, comprising: by the hydrogen-bond donor and hydrogen bond receptor
It mixes according to the proportion, obtains the depth congruent melting solvent.
In the mixing step of the above method, temperature is 20~80 DEG C, specially 30 DEG C, 35 DEG C or 40 DEG C；Time is 10-
30min。
The above method may also include that before the mixing step, and water removal is dried in polyethylene glycol；It such as can be in vacuum
Dry water removal 1 hour in drying box.
The method of electrolytic metal provided by the invention, comprising:
It is electrolyte that metal oxide, which is dissolved in system obtained by the aforementioned depth congruent melting solvent provided by the invention, with gold
Belong to or metal-base composites is that anode is electrolysed using stainless steel substrates or sheet metal as cathode, i.e., is obtained in the cathode surface
To metal deposition layer.
In the above method, the metal is aluminium, silicon or calcium；
The metal oxide is aluminium oxide, silica or calcium oxide；
The sheet metal is aluminium flake or silicon wafer；When being electrolysed to silicon, cathode is stainless steel substrates；
Described that metal oxide is dissolved in the depth congruent melting solvent step, solution temperature is 30~90 DEG C；Time is 1
~4h；
The amount ratio of hydrogen-bond donor is 0.1g:0.1-100mmol in the metal oxide and depth congruent melting solvent, specifically
For 0.1g:10mmol.
In the electrolysis step, temperature is room temperature, specially 25 DEG C；
Current density is 60-200mAcm-2；Specially 80mAcm-2、100mA·cm-2Or 180mAcm-2；
Operating voltage is 1.8-2.0V；
Time is 0.5~8h.
Electrode spacing concretely 1.5cm.
The method also includes: after the electrolysis step, the cathode that gained is deposited with metal deposition layer is placed in molten
It is impregnated in agent, the metal deposition layer on surface is removed after drying；
The solvent is chosen in particular from least one of dehydrated alcohol, isopropanol and acetone.
The advantage of the invention is that depth congruent melting solvent is as electrolyte, it other than the general character with ionic liquid,
Also have many advantages, such as that synthesis is simple, cheap and with high purity, is the ideal solvent of electrochemical deposition aluminium；And it realizes electric at room temperature
Aluminium is solved, the al deposition layer of bright, uniform densification has been obtained, has improved the adhesive ability of al deposition layer, avoid dendrite aluminium
It generates, solves the problems, such as that current sedimentary is easy to fall off；In electrolytic process, no gas is generated, non-environmental-pollution；Electrolytic method
Easy to operate, preparation cost is low, can be mass-produced, gained al deposition layer, dense uniform
Detailed description of the invention
Fig. 1 is the schematic device of electrolytic aluminium；
Fig. 2 is the surface analysis effect picture of gained al deposition layer in embodiment 2；
Fig. 3 is the X-ray energy spectrogram of gained al deposition layer in embodiment 2.
In figure, 1- D.C. regulated power supply, 2- cathode, 3- anode, 4- thermal resistance, 5- heating tube, 6- water-bath.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
Embodiment 1,
Prepare oxalic acid-polyethylene glycol depth congruent melting solvent, the molar ratio for the polyethylene glycol that oxalic acid is 200 with number-average molecular weight
For 1:2,1:4,1:6,1:8, wherein the amount of fixed oxalic acid is 0.1mol., heating stirring 10min forms the poly- second of oxalic acid-at 40 DEG C
Glycol depth congruent melting solvent.It weighs 0.1g aluminium oxide to be dissolved in oxalic acid-polyethylene glycol depth congruent melting solvent, heating stirring, with this
System is electrolyte, and using soluble aluminum based composites as anode, stainless steel substrates are cathode, and fixed electrode spacing is 1.5cm, into
Row electrolysis.In electrolytic process temperature be 25 DEG C, current density 60-100mAcm-2And operating voltage is 1.8-2V.Electrolysis
After 0.5h is electrolysed, copper sheet is placed in dehydrated alcohol and is impregnated, removed aluminium layer after drying, weighing, and computational efficiency.
Acquired results are as follows: preparing molar ratio is respectively 1:2,1:4,1:6 and 1:8 oxalic acid-polyethylene glycol depth congruent melting solvent,
Experiment condition and result such as table 1.
Table 1, experiment condition
Embodiment 2
Choline chloride-polyethylene glycol depth congruent melting solvent is prepared, the polyethylene glycol that oxalic acid is 200 with number-average molecular weight rubs
You are than being 1:2,1:4 and 1:6, and heating stirring 10min forms choline chloride-polyethylene glycol depth congruent melting solvent at 30 DEG C, wherein
The amount of fixed choline chloride is 0.1mol.It weighs 0.1g aluminium oxide to be dissolved in choline chloride-polyethylene glycol depth congruent melting solvent, add
Thermal agitation, using the system as electrolyte, using soluble aluminum based composites as anode, stainless steel substrates are cathode, between fixed electrode
Away from for 1.5cm, it is electrolysed.In electrolytic process temperature be 25 DEG C, current density 160-200mAcm-2And operating voltage
For 1.8-2V.After being electrolysed 4h, copper sheet is placed in dehydrated alcohol and is impregnated, by aluminium layer removing, weighing after drying, and calculates effect
Rate.
Acquired results are as follows: preparing molar ratio is respectively 1:2,1:4 and 1:6 choline chloride-polyethylene glycol depth congruent melting solvent.
The electrolytic efficiency of aluminium is 97% in choline chloride-polyethylene glycol depth congruent melting solvent (molar ratio 1:2), obtains fine and close aluminium
Coating has uniform morphology (Fig. 2), and the purity of the figure layer aluminium is up to 99% (Fig. 3).Other experiment conditions and result such as table
2。
Table 2, experiment condition
Embodiment 3
Prepare urea-polyethylene glycol depth congruent melting solvent, the molar ratio of oxalic acid and polyethylene glycol is 1:2,1:4 and 1:6,35
Heating stirring 10min forms urea-polyethylene glycol depth congruent melting solvent at DEG C, wherein the amount of fixed urea is 0.1mol.It weighs
0.1g aluminium oxide is dissolved in urea-polyethylene glycol depth congruent melting solvent, heating stirring, using the system as electrolyte, with solubility
Aluminum matrix composite is anode, and stainless steel substrates are cathode, and fixed electrode spacing is 1.5cm, is electrolysed.Temperature in electrolytic process
For 25 DEG C, current density 80-100mAcm-2And operating voltage is 1.8-2V.After being electrolysed 8h, copper sheet is placed in nothing
It impregnates, removes aluminium layer after drying, weighing, and computational efficiency in water-ethanol.
Acquired results are as follows: preparing molar ratio is respectively 1:2,1:4 and 1:6 urea-polyethylene glycol depth congruent melting solvent, experiment
Condition and result such as table 3.
Table 3, experiment condition
Claims (13)
1. application of the depth congruent melting solvent in electrolytic metal；
The depth congruent melting solvent is made of hydrogen-bond donor and hydrogen bond receptor；
The metal is aluminium；
The hydrogen-bond donor is selected from least one of carboxylic acid compound, choline and amides compound；
The hydrogen bond receptor is polyethylene glycols hydrogen bond receptor.
2. application according to claim 1, it is characterised in that: the carboxylic acid compound is selected from oxalic acid, malonic acid, fourth two
At least one of acid, glutaric acid, citric acid, furancarboxylic acid and benzoic acid；
The choline is selected from least one of choline chloride, choline bromide and choline iodide；
The amides compound is selected from least one of urea and methylurea；
The hydrogen bond receptor is polyethylene glycol.
3. application according to claim 2, it is characterised in that: the number-average molecular weight of the polyethylene glycol is 200-4000.
4. application according to any one of claim 1-3, it is characterised in that: the hydrogen-bond donor and hydrogen bond receptor rub
You are than being 1:2 ~ 1:8.
5. application according to claim 4, it is characterised in that: the molar ratio of the hydrogen-bond donor and hydrogen bond receptor is 1:4
Or 1:6.
6. application according to any one of claim 1-3, it is characterised in that: the depth congruent melting solvent is by including such as
What the method for lower step was prepared: the hydrogen-bond donor and hydrogen bond receptor being mixed according to the proportion, obtain the depth congruent melting
Solvent.
7. application according to claim 6, it is characterised in that: in the mixing step, temperature is 20 ~ 80 DEG C；Time is
10-30 min。
8. a kind of method of electrolytic metal, comprising:
It is electrolyte that metal oxide, which is dissolved in system obtained by depth congruent melting solvent, is sun with metal or metal-base composites
Pole is electrolysed using sheet metal as cathode, i.e., obtains metal deposition layer in the cathode surface；
The depth congruent melting solvent is identical as depth congruent melting solvent described in claim any one of 1-7.
9. according to the method described in claim 8, it is characterized by: the metal is aluminium；
The metal oxide is aluminium oxide；
The sheet metal is aluminium flake or stainless steel substrates；
Described that metal oxide is dissolved in the depth congruent melting solvent step, solution temperature is 30 ~ 90 DEG C；Time is 1 ~ 4
h；
The amount ratio of hydrogen-bond donor is 0.1g:0.1-100 mmol in the metal oxide and depth congruent melting solvent.
10. according to the method described in claim 9, it is characterized by: the metal oxide and hydrogen bond in depth congruent melting solvent
The amount ratio of donor is 0.1g:10 mmol.
11. the method according to any one of claim 8-10, it is characterised in that: in the electrolysis step, temperature is room
Temperature；
Current density is 60-200 mAcm-2；
Operating voltage is 1.8-2.0 V；
Time is 0.5 ~ 8 h.
12. according to the method any in claim 8-10, it is characterised in that: the method also includes: in the electrolysis
After step, the cathode that gained is deposited with metal deposition layer is placed in solvent and is impregnated, the metal deposit on surface is removed after drying
Layer.
13. according to the method for claim 12, it is characterised in that: the solvent is selected from dehydrated alcohol, isopropanol and acetone
At least one of.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839403A (en) * | 2012-09-10 | 2012-12-26 | 太原理工大学 | Method for electroplating aluminum in ionic liquid |
| CN105671598A (en) * | 2016-04-08 | 2016-06-15 | 中国科学院过程工程研究所 | Method for directly preparing aluminum foil through low temperature electrolysis |
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| US8778164B2 (en) * | 2010-12-16 | 2014-07-15 | Honeywell International Inc. | Methods for producing a high temperature oxidation resistant coating on superalloy substrates and the coated superalloy substrates thereby produced |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839403A (en) * | 2012-09-10 | 2012-12-26 | 太原理工大学 | Method for electroplating aluminum in ionic liquid |
| CN105671598A (en) * | 2016-04-08 | 2016-06-15 | 中国科学院过程工程研究所 | Method for directly preparing aluminum foil through low temperature electrolysis |
Non-Patent Citations (3)
| Title |
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| processing metal oxides using ionic liquids;A.P.Abbott等;《Mineral Processing and Extractive Metallurgy》;20130718;实验部分、表1、结论 * |
| 电沉积法制备纳米铜粉的研究;汪瑞等;《矿冶》;20151025;第24卷(第5期);第1节试验方案 * |
| 绿色化学导论第二版;李进军等;《绿色化学导论第二版》;武汉大学出版社;20150831;第81页 * |
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