CN108166021A - A kind of method of the low-temperature electrolytic aluminium in depth congruent melting solvent - Google Patents
A kind of method of the low-temperature electrolytic aluminium in depth congruent melting solvent Download PDFInfo
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- CN108166021A CN108166021A CN201711447337.7A CN201711447337A CN108166021A CN 108166021 A CN108166021 A CN 108166021A CN 201711447337 A CN201711447337 A CN 201711447337A CN 108166021 A CN108166021 A CN 108166021A
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- congruent melting
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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
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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 the low-temperature electrolytic aluminium in depth congruent melting solvent.This method includes：By the hydrogen-bond donor and hydrogen bond receptor according to proportioning mixing, 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 that synthesis is simple, cheap and purity is high other than the general character with ionic liquid, is the ideal solvent of electrochemical deposition aluminium；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 easily comes off；In electrolytic process, no gas generates, non-environmental-pollution.
Description
Technical field
The invention belongs to Material Fields, are related to a kind of method of the low-temperature electrolytic aluminium in depth congruent melting solvent.
Background technology
Aluminium Industry is electrochemical industry maximum 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 methods, that is, cryolite-alumina electrolysis, this method was after the development of more than 100 years, increasingly
Maturation, but there are still the problems such as electrolysis temperature is high, energy consumption is big, seriously polluted, and the al deposition layer that technique obtains at present
It is thin, dendrite, powdered granule are easily formed in deposition process, it is easy to fall off, therefore be difficult to be formed and realize 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 hardly possible,
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 active metal can not be electrolysed in aqueous solution.But organic solvent exists as electrolyte
It is volatile during use, 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 it develops stable, cheap, viscous
The novel electrolytes for spending the advantages that small are extremely urgent.
Invention content
The object of the present invention is to provide a kind of methods of the low-temperature electrolytic aluminium in depth congruent melting solvent.
Application of the claimed depth congruent melting solvent in electrolytic metal.
In above 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, glycerine 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, including：By the hydrogen-bond donor and hydrogen bond receptor
According to proportioning mixing, the depth congruent melting solvent is obtained.
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：Before the mixing step, 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, including：
It is electrolyte that metal oxide is dissolved in the aforementioned depth congruent melting solvent gained system provided by the invention, with gold
Belong to or metal-base composites is anode, using stainless steel substrates or sheet metal as cathode, be electrolysed, i.e., 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 chip；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 the metal oxide and hydrogen-bond donor in depth congruent melting solvent is 0.1g：0.1-100mmol, 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 further includes：After the electrolysis step, the cathode that gained deposition has 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 absolute ethyl 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 purity is high, be 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 easily comes off；In electrolytic process, no gas generates, non-environmental-pollution；Electrolytic method
Easy to operate, manufacturing cost is low, can be mass-produced, gained al deposition layer, dense uniform
Description of the drawings
Fig. 1 is the schematic device of electrolytic aluminium；
Fig. 2 is the surface analysis design sketch 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 supplies, 2- cathodes, 3- anodes, 4- thermal resistances, 5- heating tubes, 6- water-baths.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiments.Institute
It is conventional method unless otherwise instructed to state method.The raw material can obtain unless otherwise instructed from open commercial sources.
Embodiment 1,
Prepare oxalic acid-polyethylene glycol depth congruent melting solvent, oxalic acid and the molar ratio of polyethylene glycol that number-average molecular weight is 200
It is 1:2、1:4、1:6、1:8, wherein the amount of fixed oxalic acid is 0.1mol., heating stirring 10min forms oxalic acid-poly- second 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 absolute ethyl alcohol and is impregnated, aluminium layer is removed after drying, is weighed, and computational efficiency.
Acquired results are：It is respectively 1 to prepare molar ratio: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
Prepare choline chloride-polyethylene glycol depth congruent melting solvent, oxalic acid rubbing for 200 polyethylene glycol with number-average molecular weight
You are than being 1:2、1:4 and 1:Heating stirring 10min forms choline chloride-polyethylene glycol depth congruent melting solvent at 6,30 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 absolute ethyl alcohol and is impregnated, aluminium layer is removed after drying, is weighed, and calculates effect
Rate.
Acquired results are：It is respectively 1 to prepare molar ratio:2、1:4 and 1:6 choline chlorides-polyethylene glycol depth congruent melting solvent.
In choline chloride-polyethylene glycol depth congruent melting solvent (molar ratio 1:2) electrolytic efficiency of aluminium is 97% in, 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
The molar ratio of preparation urea-polyethylene glycol depth congruent melting solvent, 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 is impregnated in water-ethanol, aluminium layer is removed after drying, is weighed, and computational efficiency.
Acquired results are：It is respectively 1 to prepare molar ratio: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 (10)
1. application of the depth congruent melting solvent in electrolytic metal.
2. application according to claim 1, it is characterised in that：The depth congruent melting solvent is by hydrogen-bond donor and hydrogen bond receptor
Composition；
The metal is selected from least one of aluminium, silicon and calcium.
3. application according to claim 2, it is characterised in that：The hydrogen-bond donor is selected from carboxylic acid compound, choline
At least one of compound and amides compound；
The carboxylic acid compound is chosen in particular from oxalic acid, malonic acid, succinic acid, glutaric acid, citric acid, furancarboxylic acid and benzoic acid
It is at least one；
The choline is chosen in particular from least one of choline chloride, choline bromide, choline iodide and guanidine hydrochloride；
The amides compound is chosen in particular 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 least one of polyethylene glycol, glycerine and crown ether；
The number-average molecular weight of the polyethylene glycol is specially 200-4000.
4. the application according to Claims 2 or 3, it is characterised in that：The molar ratio of the hydrogen-bond donor and hydrogen bond receptor is
1:2~1:8、1:4 or 1:6.
5. a kind of method for preparing any depth congruent melting solvent in claim 1-4, including：By the hydrogen-bond donor and hydrogen
Key receptor obtains the depth congruent melting solvent according to proportioning mixing.
6. according to the method described in claim 5, it is characterized in that：In the mixing step, temperature is 20~80 DEG C；Time is
10-30min。
7. a kind of method of electrolytic metal, including：
It is electrolyte that metal oxide is dissolved in system obtained by any depth congruent melting solvent in claim 1-4, with metal
Or metal-base composites is anode, using stainless steel substrates or sheet metal as cathode, is electrolysed, i.e., is obtained in the cathode surface
Metal deposition layer.
8. according to the method described in claim 7, it is characterized in that：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 chip；
Described that metal oxide is dissolved in the depth congruent melting solvent step, solution temperature is 30~90 DEG C；Time for 1~
4h；
The amount ratio of the metal oxide and hydrogen-bond donor in depth congruent melting solvent is 0.1g：0.1-100mmol, specially
0.1g：10mmol.
9. method according to claim 7 or 8, it is characterised in that：In the electrolysis step, temperature is room temperature；
Current density is 60-200mAcm-2；
Operating voltage is 1.8-2.0V；
Time is 0.5~8h.
10. according to the method any in claim 6-9, it is characterised in that：The method further includes：In the electrolysis step
After rapid, the cathode that gained deposition has metal deposition layer is placed in solvent and is impregnated, the metal deposition layer on surface is removed after drying；
The solvent is chosen in particular from least one of absolute ethyl alcohol, isopropanol and acetone.
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| CN201711447337.7A CN108166021B (en) | 2017-12-27 | 2017-12-27 | A method of the low-temperature electrolytic aluminium in depth congruent melting solvent |
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| CN201711447337.7A CN108166021B (en) | 2017-12-27 | 2017-12-27 | A method of the low-temperature electrolytic aluminium in depth congruent melting solvent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699707A (en) * | 2019-11-11 | 2020-01-17 | 曹大平 | Normal temperature aluminum electrolysis process |
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| US20120156519A1 (en) * | 2010-12-16 | 2012-06-21 | 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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| 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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| US20120156519A1 (en) * | 2010-12-16 | 2012-06-21 | Honeywell International Inc. | Methods for producing a high temperature oxidation resistant coating on superalloy substrates and the coated superalloy substrates thereby produced |
| 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110699707A (en) * | 2019-11-11 | 2020-01-17 | 曹大平 | Normal temperature aluminum electrolysis process |
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