CN107130264A - A kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy - Google Patents
A kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy Download PDFInfo
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Abstract
Field, the more particularly to a kind of method of nearly room temperature environment electrolytic preparation aluminium-based rare-earth alloy are extracted the invention belongs to low temperature electrochemical.A kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy, methods described is electrolysis, and electrolyte used in the electrolysis is made up of rare earth chloride and class ionic liquid, wherein, class ionic liquid accounts for the 96~98% of electrolyte gross mass, and rare earth chloride accounts for the 2%~4% of gross mass, the rare earth chloride is neodymium chloride, lanthanum chloride, cerium chloride, scandium chloride, yttrium chloride, praseodymium chloride, samarium trichloride, one kind in Europium chloride, gadolinium chloride, terbium chloride.The nearly room temperature electrolytic preparation aluminium-based rare-earth alloy technique of the present invention, it is simple to operate, it is with low cost.Technological reserve and theories integration are provided for the aluminium-based rare-earth alloy green of low cost.
Description
Technical field
Field, more particularly to a kind of nearly room temperature environment electrolytic preparation aluminium base rare earth are extracted the invention belongs to low temperature electrochemical
The method of alloy.
Background technology
Appropriate rare earth element is added in aluminium alloy has facilitation to refined aluminum.Rare earth element can improve field trash shape
State, purifies crystal boundary.1.5-2.5% rare earth elements are added in aluminium alloy, the high-temperature behavior, air-tightness and corrosion resistant of alloy can be improved
Corrosion, is widely used as aerospace material.With the development of science and technology, rare earth sciemtifec and technical sphere is expanded and extend, rare earth member
Element will have broader utilization space.
Existing aluminium-based rare-earth alloy production has (1) to the method for mixing；Required according to alloying component, pure rare-earth metals are added to height
In warm aluminium liquid, aluminium-based rare-earth alloy can be produced.And pure rare-earth metals are electrolysis production under high temperature, complex process, cost is high,
Equipment corrosion is serious, and scaling loss is larger.(2) high-temperature electric solution；This method is, in electrolytic aluminium, rare earth oxide to be added into electrolytic cell
Or rare earth salts, Electrowinning rare earth alloy.It is still and carries out at high temperature, alloying component fluctuation is larger, is difficult to control, in addition
Even whole electrolytic cells will be employed by producing aluminium-based rare-earth alloy in enormous quantities, be unfavorable for the production of fine aluminium ingot.
It is not only simple to operate to be easily controlled if rare earth and its alloy can be prepared electro-deposition under room temperature or nearly room temperature condition,
And the few cost of power consumption is low.Due to the activity of rare earth metal so that it is difficult to electrochemical deposition in aqueous.And using having
Machine solution system is inflammable, general poisonous, and electrical conductivity is relatively low, and soluble active metal raw material is generally organic metal, and
It is poor to their inorganic salts solvability.It is in room temperature or near room temperature temperature and ionic liquid is as a kind of low temperature molten salt
The material being made up of ion being in a liquid state under degree, is widely used in the every field of chemical research.With conventional organic solution
Liquid system compared to ionic liquid it is conductive it is good, difficult volatilize, burn, it is special dissolve and catalytic action, electrochemically stable electricity
The features such as position window is relatively wide.But it is difficult to carry out electro-deposition rare earth application that conventional ionic liquid, which is, because conventional ion liquid
Body electrochemical window can not meet the requirement of rare earth element sedimentation potential, and ionic liquid just divides before rare earth metal sedimentation potential
Solution has gone bad and has been difficult to recover.Small part ionic liquid such as [P2225][TFSA]、[N2225] [TFSA] etc. can deposit rare earth member
Element, but this ionic liquid synthesis technique complexity is prepared, exchange reaction is not thorough, and products therefrom needs more purification and separation,
And the raw material rare-earth salts used is organic salt RE (TFSA)3, significantly improve cost, no application advantage.
The content of the invention
For it is above-mentioned existing the problem of, the present invention, which is provided, a kind of utilizes class ionic liquid (room temperature molten salt containing neutral ligand)
The method that low-temperature electrolytic rare earth chloride and aluminium chloride produce aluminium-based rare-earth alloy.With rare earth chloride (99.9%) for raw material, by it
The Short flow method that electro-deposition in aluminium chloride base class ionic liquid prepares aluminium-based rare-earth alloy is dissolved in, aluminium base is dilute efficiently preparing
Native alloy simultaneously, reduces energy consumption and production costs.Such ionic liquid is being remained outside the advantage of above conventional ionic liquid,
Also possess that conductance is high, viscosity is small, it is stable insensitive to water, cheap in air the characteristics of.
A kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy, methods described is electrolysis,
Electrolyte used in the electrolysis is made up of rare earth chloride and class ionic liquid, wherein, class ionic liquid accounts for electrolysis
The 96~98% of matter gross mass, rare earth chloride accounts for the 2%~4% of gross mass, and the rare earth chloride is neodymium chloride, lanthanum chloride, chlorine
Change one kind in cerium, scandium chloride, yttrium chloride, praseodymium chloride, samarium trichloride, Europium chloride, gadolinium chloride, terbium chloride,
Wherein, the class ionic liquid is made up of cation portion and anion portion,
The cation portion has following formulas：[AlCl2·nEC]+, wherein, EC is ethylene carbonate；N=2.67；
The anion portion is AlCl4 -。
" nearly room temperature " of the present invention refers to temperature for 55~75 DEG C.
The temperature in use of class ionic liquid of the present invention is 20~100 DEG C.
In above-mentioned technical proposal, the class ionic liquid is made as follows：At room temperature, by AlCl3Powder adds carbon
Stirred in vinyl acetate, both,
Wherein, AlCl3Mol ratio with ethylene carbonate is 0.75:1, mixing speed is 500r/min, mixing time
30min。
A kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy, methods described is electrolysis,
Electrolyte used in the electrolysis is made up of rare earth chloride and class ionic liquid, wherein, class ionic liquid accounts for electrolysis
The 96~98% of matter gross mass, rare earth chloride accounts for the 2%~4% of gross mass, and the rare earth chloride is neodymium chloride, lanthanum chloride, chlorine
Change one kind in cerium, scandium chloride, yttrium chloride, praseodymium chloride, samarium trichloride, Europium chloride, gadolinium chloride, terbium chloride,
The class ionic liquid is made as follows：At room temperature, by AlCl3Powder is added in ethylene carbonate and stirred,
Both,
Wherein, AlCl3Mol ratio with ethylene carbonate is 0.75:1, mixing speed is 500r/min, mixing time
30min。
The mechanism mechanism of involved reaction can be represented with below equation in the present invention：
2AlCl3+nEC→[AlCl2·nEC]++AlCl4 -
Wherein EC refers to ethylene carbonate.
Lewis acid AlCl of the present invention3Mol ratio with ethylene carbonate is 0.75:1.Such class in the case
Ionic liquid is stable in the air insensitive to water.
Further, it is 55~75 DEG C, decomposition voltage scope -3.2 that electrolyte system temperature is controlled in the electrolytic process
~-3.5V (vs Al).
" vs Al " refer to using aluminium electrode as reference electrode in voltage range -3.2~-3.5V (vs Al) of the present invention.
Further, it is preferable to the step of methods described includes supplement charging at least one times：In electrolytic process, to electrolyte
Middle addition rare earth chloride or/and additive,
Wherein, the rare earth chloride quality added is the 1% of initial electrolysis matter gross mass；The additive is dimethyl carbonate
Or/and rare earth oxide, the addition of the dimethyl carbonate is the 0.5% of initial electrolysis matter gross mass, the rare earth oxide
Addition is the 0.05% of initial electrolysis matter gross mass.
Above-mentioned supplement addition step can ensure the amount of rare earth chloride and guarantee system viscosity and conductance in electrolyte system
Rate, and then improve yield.
One preferred technical scheme of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy of the present invention is：
Methods described includes following processing steps：
(1) at room temperature, by AlCl3Powder is added in ethylene carbonate and stirred, both, wherein, AlCl3With ethylene carbonate
Mol ratio be 0.75:1, mixing speed is 500r/min, mixing time 30min；
(2) inert gas is continuously passed through to electrolytic cell and discharges air therein and vapor, then adds class ionic liquid
Enter into electrolytic cell, add rare earth chloride, stirring is mixed to form electrolyte system in electrolytic cell, and control electrolyte system exists
55~75 DEG C, -3.2~-3.5V of decomposition voltage scope (vs Al)；
(3) in electrolytic process, chlorine in rare earth chloride or/and additive, control electrolytic cell is added after 30min into electrolytic cell
Change rare earth and account for the 2~4% of electrolyte gross mass,
Wherein, the rare earth chloride quality added is the 1% of initial electrolysis matter gross mass；The additive is dimethyl carbonate
Or/and rare earth oxide, the addition of the dimethyl carbonate is the 0.5% of initial electrolysis matter gross mass, the rare earth oxide
Addition is the 0.05% of initial electrolysis matter gross mass.
Further, the anode in the above method is high purity graphite rod (purity >=99.9%), and negative electrode is that high-purity aluminium sheet is (pure
Degree >=99.9%).
In the above method in step (2), inert gas is preferably high-purity argon gas, purity >=99.99%.
The inert gas of step (2) selects high-purity argon gas, purity >=99.99%, raw material neodymium chloride, chlorination in the above method
Magnesium and lithium chloride, purity are 99.99%.
Additive described in the above method (3) is that dimethyl carbonate (accounting for gross mass 0.5%) or/and rare earth oxide (account for total
Quality 0.05%) with improve current condition system viscosity and improve electrolyte system stability.
Further, this methods described also includes collecting the step of product and reprocessing (4) and (5), is specially：
(4) with the progress of electrolysis, aluminium-based rare-earth alloy formation, will be heavy on substrate every 60min on cathode base
Product thing is stored in atmosphere of inert gases for a period of time together with substrate collection processing；
(5) to collecting gained deposited material, reprocessing is handled as desired.
It is, more than 24 hours, to make alloy for a period of time that deposit, which needs to be stored in atmosphere of inert gases, in the above method (4)
The bad active metal reduction activity of change degree, alloying is complete as far as possible.
The present invention deposits Al rare earth alloy on solid-state aluminium flake and originated including two parts：
One is the result being co-deposited, and the deposition reduction reaction of wherein aluminium is:
2[AlCl2·nEC]++3e-→AlCl4 -+2nEC+Al
Rare earth metal reduction reaction is:
RE3++3e-=RE
The aluminium and rare earth being deposited are with atomic scale alloying, and forming core grows up to form aluminium-based rare-earth alloy.
Two be the rare earth element for the greater activity being deposited completely and the aluminium alloying that is deposited, but and solid-state
Aluminium substrate alloying is in aluminium flake negative electrode formation one aluminium-based rare-earth alloy layer.
Beneficial effects of the present invention are：With it is existing prepare the method for aluminium-based rare-earth alloy compared with, this method has following
Advantage：
(1) technological process is shortened, and significantly reduces energy consumption, reduces production cost；
(2) low-temperature ionic liquids electro-deposition is used, it is possible to decrease and eliminate using energy consumption during high temperature fused salt electrolysis matter is big, temperature
The serious shortcoming of high, equipment corrosion, improves operating environment；
(3) rare earth metal and aluminium-based rare-earth alloy can be prepared in different materials substrate, can be joined by changing technique
Sized materials needed for number is obtained；
The nearly room temperature electrolytic preparation aluminium-based rare-earth alloy technique of the present invention, it is simple to operate, it is with low cost.For the aluminium of low cost
Base rare earth alloy green, which is extracted, provides technological reserve and theories integration.
Brief description of the drawings
Fig. 1 is electrolyte system Posterior circle voltammogram after the dissolving neodymium chloride of embodiment 1, sweeps fast 0.1v/s.
Fig. 2 be embodiment 2 in aluminium minus plate products therefrom X-ray diffractogram.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
Rare earth chloride purity >=99.99% used in the embodiment of the present invention.
Electrolysis power and electrochemical measurement instrument are used as using Shanghai Chen Hua electrochemical workstation in the embodiment of the present invention.
The additive is dimethyl carbonate or/and rare earth oxide, and the addition of the dimethyl carbonate is initial electrolysis
The 0.5% of matter gross mass, the addition of the rare earth oxide is the 0.05% of initial electrolysis matter gross mass.
The inert gas used in the embodiment of the present invention for purity >=99.99% high-purity argon gas.
It is all the 1% of initial electrolysis matter gross mass to add rare earth chloride quality in the embodiment of the present invention every time.
The deposit thing of the embodiment of the present invention 1,2,3 is mutually detected using XRD (X-ray diffraction technology) and proved.
(inductively coupled plasma is former using ICP for all embodiments of the invention electro-deposition product aluminium and rare earth element content
Sub- Emission Spectroscopy) detection.
In following embodiments, the class ionic liquid is made as follows：At room temperature, by AlCl3Powder adds carbonic acid
Stirred in vinyl acetate, both, wherein, AlCl3Mol ratio with carbonic ester is 0.75:1, mixing speed is 500r/min, stirring
Time 30min, gained class ionic liquid is referred to as aluminum chloride-based ethylene carbonate esters ionic liquid.
Embodiment 1
It is neodymium chloride and aluminum chloride-based ethylene carbonate esters ionic liquid to prepare electrolyte raw material, and wherein class ionic liquid is accounted for
The 98% of electrolyte gross mass, neodymium chloride accounts for the 2% of electrolyte gross mass.Inert gas discharge is continuously passed through to electrolytic cell wherein
Air and vapor, then class ionic liquid is added in electrolytic cell, neodymium chloride is added, in electrolytic cell stir mixing
Form electrolyte system, 55 DEG C of control electrolyte system constant temperature.Using graphite rod as anode, aluminium flake is negative electrode, decomposition voltage for-
3.2V(vs Al).Once fed neodymium chloride operation after electrolysis 30min, and neodymium chloride quality is all initial electrolysis matter gross mass
1%, and add the Nd of initial electrolysis matter gross mass 0.05%2O3；It is electrolysed after 60min and preserves substrate together with deposit collection
And reprocessing is handled as desired to collecting gained deposit.XRD detections prove that the phase structure of institute's deposit is Al2Nd, ICP
It is 97.66% to detect electro-deposition product aluminium and rare earth neodymium constituent content sum.
Embodiment 2
It is neodymium chloride and aluminum chloride-based ethylene carbonate esters ionic liquid to prepare electrolyte raw material, and wherein class ionic liquid is accounted for
The 97% of electrolyte gross mass, neodymium chloride accounts for the 3% of electrolyte gross mass.Inert gas discharge is continuously passed through to electrolytic cell wherein
Air and vapor, then class ionic liquid is added in electrolytic cell, neodymium chloride is added, in electrolytic cell stir mixing
Form electrolyte system, 65 DEG C of control electrolyte system constant temperature.Using graphite rod as anode, aluminium flake is negative electrode, decomposition voltage for-
3.3V(vs Al).Once fed neodymium chloride operation after electrolysis 30min, and neodymium chloride quality is all initial electrolysis matter gross mass
1%；It is electrolysed after 60min and preserves substrate and to collecting gained deposit as desired at reprocessing together with deposit collection
Reason.XRD detections prove that the phase structure of institute's deposit is Al2Nd, and ICP detection electro-deposition product aluminium and rare earth element neodymium element contain
It is 98.56% to measure sum.
Embodiment 3
It is neodymium chloride and aluminium chloride ethylene carbonate esters ionic liquid to prepare electrolyte raw material, and wherein class ionic liquid accounts for electricity
The 96% of matter gross mass is solved, neodymium chloride accounts for the 4% of electrolyte gross mass.Inert gas discharge is continuously passed through to electrolytic cell therein
Class ionic liquid, is then added in electrolytic cell, adds neodymium chloride by air and vapor, the stirring mixing shape in electrolytic cell
Into electrolyte system, 75 DEG C of control electrolyte system constant temperature.Using tungsten bar as anode, aluminium flake is negative electrode, and decomposition voltage is -3.5V
(vs Al).Once fed neodymium chloride operation after electrolysis 30min, and neodymium chloride quality is all initial electrolysis matter gross mass
1%, and add the dimethyl carbonate of initial electrolysis matter gross mass 0.5%；It is electrolysed after 60min and protects substrate together with deposit collection
Deposit and reprocessing is handled as desired to collecting gained deposit.XRD detections prove that the phase structure of institute's deposit is Al2Nd,
ICP detects that electro-deposition product aluminium and rare earth neodymium constituent content sum are 99.75%.
Embodiment 4
Method be the same as Example 1, difference is that electrolyte raw material used is lanthanum chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is lanthanum chloride raw material and adds the La of initial electrolysis matter gross mass 0.05%2O3.ICP detects electro-deposition
Product aluminium and rare-earth elements of lanthanum constituent content sum are 97.72%.
Embodiment 5
Method be the same as Example 2, difference is that electrolyte raw material used is lanthanum chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is lanthanum chloride material.ICP detects that electro-deposition product aluminium and rare-earth elements of lanthanum constituent content sum are
98.46%.
Embodiment 6
Method be the same as Example 3, difference is that electrolyte raw material used is lanthanum chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation lanthanum chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and rare-earth elements of lanthanum constituent content sum are 99.77%.
Embodiment 7
Method be the same as Example 1, difference is that electrolyte raw material used is cerium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is cerium chloride raw material and adds the cerium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and rare-earth element cerium constituent content sum are 97.42%.
Embodiment 8
Method be the same as Example 2, difference is that electrolyte raw material used is cerium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is cerium chloride material.ICP detects that electro-deposition product aluminium and rare-earth element cerium constituent content sum are
98.66%.
Embodiment 9
Method be the same as Example 3, difference is that electrolyte raw material used is cerium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation cerium chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and rare-earth element cerium constituent content sum are 99.65%.
Embodiment 10
Method be the same as Example 1, difference is that electrolyte raw material used is praseodymium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is praseodymium chloride raw material and adds the praseodymium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and Rare Earth Elements of Praseodymium constituent content sum are 97.47%.
Embodiment 11
Method be the same as Example 2, difference is that electrolyte raw material used is praseodymium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is praseodymium chloride material.ICP detects that electro-deposition product aluminium and Rare Earth Elements of Praseodymium constituent content sum are
98.69%.
Embodiment 12
Method be the same as Example 3, difference is that electrolyte raw material used is praseodymium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation praseodymium chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and Rare Earth Elements of Praseodymium constituent content sum are 99.55%.
Embodiment 13
Method be the same as Example 1, difference is that electrolyte raw material used is samarium trichloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is samarium trichloride raw material and adds the samarium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and Samarium Nitrate constituent content sum are 96.98%.
Embodiment 14
Method be the same as Example 2, difference is that electrolyte raw material used is samarium trichloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is samarium trichloride material.ICP detects that electro-deposition product aluminium and Samarium Nitrate constituent content sum are
98.64%.
Embodiment 15
Method be the same as Example 3, difference is that electrolyte raw material used is samarium trichloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation samarium trichloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and Samarium Nitrate constituent content sum are 99.75%.
Embodiment 16
Method be the same as Example 1, difference is that electrolyte raw material used is Europium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is Europium chloride raw material and adds the europium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and rare earth elements europium constituent content sum are 96.88%.
Embodiment 17
Method be the same as Example 2, difference is that electrolyte raw material used is Europium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is Europium chloride material.ICP detects that electro-deposition product aluminium and rare earth elements europium constituent content sum are
98.84%.
Embodiment 18
Method be the same as Example 3, difference is that electrolyte raw material used is Europium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation Europium chloride material simultaneously adds the dimethyl carbonate of initial electrolysis matter gross mass 0.5%.ICP detection electricity is heavy
Product product aluminium and rare earth elements europium constituent content sum are 99.15%.
Embodiment 19
Method be the same as Example 1, difference is that electrolyte raw material used is gadolinium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is gadolinium chloride raw material and adds the gadolinium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and rare-earth element gadolinium constituent content sum are 96.98%.
Embodiment 20
Method be the same as Example 2, difference is that electrolyte raw material used is gadolinium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is gadolinium chloride material.ICP detects that electro-deposition product aluminium and rare-earth element gadolinium constituent content sum are
98.14%.
Embodiment 21
Method be the same as Example 3, difference is that electrolyte raw material used is gadolinium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation gadolinium chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and rare-earth element gadolinium constituent content sum are 99.11%.
Embodiment 22
Method be the same as Example 1, difference is that electrolyte raw material used is terbium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is terbium chloride raw material and adds the terbium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and rare earth element terbium constituent content sum are 96.91%.
Embodiment 23
Method be the same as Example 2, difference is that electrolyte raw material used is terbium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is terbium chloride material.ICP detects that electro-deposition product aluminium and rare earth element terbium constituent content sum are
98.13%.
Embodiment 24
Method be the same as Example 3, difference is that electrolyte raw material used is terbium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation terbium chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and rare earth element terbium constituent content sum are 99.17%.
Embodiment 25
Method be the same as Example 1, difference is that electrolyte raw material used is scandium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is scandium chloride raw material and adds the scandium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and rare earth Sc constituent content sum are 98.25%.
Embodiment 26
Method be the same as Example 2, difference is that electrolyte raw material used is scandium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is scandium chloride material.ICP detects that electro-deposition product aluminium and rare earth Sc constituent content sum are
98.83%.
Embodiment 27
Method be the same as Example 3, difference is that electrolyte raw material used is scandium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation scandium chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and rare earth Sc constituent content sum are 99.88%.
Embodiment 28
Method be the same as Example 1, difference is that electrolyte raw material used is yttrium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is yttrium chloride raw material and adds the yittrium oxide of initial electrolysis matter gross mass 0.05%.ICP detection electricity is heavy
Product product aluminium and rare earth element yttrium constituent content sum are 97.91%.
Embodiment 29
Method be the same as Example 2, difference is that electrolyte raw material used is yttrium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation is yttrium chloride material.ICP detects that electro-deposition product aluminium and rare earth element yttrium constituent content sum are
98.83%.
Embodiment 30
Method be the same as Example 3, difference is that electrolyte raw material used is yttrium chloride and aluminum chloride-based ethylene carbonate esters
Ionic liquid, charging operation yttrium chloride material and the dimethyl carbonate for adding initial electrolysis matter gross mass 0.5%.ICP detection electricity
Sedimentation products aluminium and rare earth element yttrium constituent content sum are 99.67%.
Claims (6)
1. a kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy, it is characterised in that：Methods described is electrolysis,
Electrolyte used in the electrolysis is made up of rare earth chloride and class ionic liquid, wherein, it is total that class ionic liquid accounts for electrolyte
The 96~98% of quality, rare earth chloride accounts for the 2%~4% of electrolyte gross mass, and the rare earth chloride is neodymium chloride, lanthanum chloride,
One kind in cerium chloride, scandium chloride, yttrium chloride, praseodymium chloride, samarium trichloride, Europium chloride, gadolinium chloride, terbium chloride,
Wherein, the class ionic liquid is made up of cation portion and anion portion,
The cation portion has following formulas：[AlCl2·nEC]+, wherein, EC is ethylene carbonate；N=2.67；
The anion portion is AlCl4 -。
2. according to the method described in claim 1, it is characterised in that：The class ionic liquid is made as follows：At room temperature,
By AlCl3Powder is added in ethylene carbonate and stirred, both,
Wherein, AlCl3Mol ratio with ethylene carbonate is 0.75:1, mixing speed is 500r/min, mixing time 30min.
3. according to the method described in claim 1, it is characterised in that：It is 55 that electrolyte system temperature is controlled in the electrolytic process
~75 DEG C, -3.2~-3.5V of decomposition voltage scope (vs Al).
4. according to the method described in claim 1, it is characterised in that：The step of methods described includes supplement charging at least one times：
In electrolytic process, rare earth chloride or/and additive are added into electrolyte,
Wherein, the rare earth chloride quality added is the 1% of initial electrolysis matter gross mass；The additive be dimethyl carbonate or/
And rare earth oxide, the addition of the dimethyl carbonate is the 0.5% of initial electrolysis matter gross mass, the addition of the rare earth oxide
Measure as the 0.05% of initial electrolysis matter gross mass.
5. according to the method described in claim 1, it is characterised in that：Methods described includes following processing steps：
(1) at room temperature, by AlCl3Powder is added in ethylene carbonate and stirred, both, wherein, AlCl3With rubbing for ethylene carbonate
You are than being 0.75:1, mixing speed is 500r/min, mixing time 30min；
(2) inert gas is continuously passed through to electrolytic cell and discharges air therein and vapor, then class ionic liquid is added to
In electrolytic cell, add rare earth chloride, stirring is mixed to form electrolyte system in electrolytic cell, control electrolyte system 55~
75 DEG C, -3.2~-3.5V of decomposition voltage scope (vs Al)；
(3) in electrolytic process, chlorination in rare earth chloride or/and additive, control electrolytic cell is added after 30min into electrolytic cell dilute
Soil accounts for the 2~4% of electrolyte gross mass,
Wherein, the rare earth chloride quality added is the 1% of initial electrolysis matter gross mass；The additive be dimethyl carbonate or/
And rare earth oxide, the addition of the dimethyl carbonate is the 0.5% of initial electrolysis matter gross mass, the addition of the rare earth oxide
Measure as the 0.05% of initial electrolysis matter gross mass.
6. according to the method described in claim 1, it is characterised in that：Anode in the above method for high purity graphite rod (purity >=
99.9%), negative electrode is high-purity aluminium sheet (purity >=99.9%).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112590A (en) * | 2018-10-12 | 2019-01-01 | 东北大学 | A kind of method that low temperature electrochemical deposition prepares metal thulium film |
| CN109136990A (en) * | 2018-10-12 | 2019-01-04 | 东北大学 | A method of lanthanoid metal is prepared by raw material Low-temperature electro-deposition of lanthanum chloride |
| CN109208043A (en) * | 2018-10-12 | 2019-01-15 | 东北大学 | A kind of method that electro-deposition prepares rare earth metal gadolinium film |
| CN109208034A (en) * | 2018-10-12 | 2019-01-15 | 东北大学 | A kind of method that low-temperature electrolytic neodymium chloride prepares rare earth metal neodymium |
| CN109208033A (en) * | 2018-10-12 | 2019-01-15 | 东北大学 | A kind of method of low cost electrolysis praseodymium chloride production metal praseodymium |
| CN109338423A (en) * | 2018-10-12 | 2019-02-15 | 东北大学 | A kind of method that Low-cost electric chemical deposition prepares rare earth metal Tb film |
| CN109537008A (en) * | 2019-01-11 | 2019-03-29 | 沈阳大学 | A kind of room temperature electro-deposition prepares aluminium lanthanum alloy film method |
| CN113755894A (en) * | 2021-10-13 | 2021-12-07 | 东北大学 | Method for preparing aluminum magnesium alloy by utilizing room-temperature molten salt electrodeposition |
| CN113913882A (en) * | 2021-11-12 | 2022-01-11 | 东北大学 | Method for preparing aluminum-titanium alloy by taking titanium oxycarbide as raw material through low-temperature electrodeposition |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN1410599A (en) * | 2002-12-03 | 2003-04-16 | 中国铝业股份有限公司 | Method of producing aluminium scandium alloy by electrolysis |
| CN1514042A (en) * | 2003-08-21 | 2004-07-21 | 中国铝业股份有限公司 | Production method of high purity aluminium scandium alloy |
| CN1556252A (en) * | 2004-01-08 | 2004-12-22 | 包头铝业股份有限公司 | Method of directly preparing aluminium cerium internediate alloy using fused salt elactrolysis method |
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| CN102108529A (en) * | 2011-01-13 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing aluminum-gadolinium-samarium alloy by fused salt electrolysis |
| CN102352519A (en) * | 2011-10-10 | 2012-02-15 | 哈尔滨工程大学 | Method for preparing aluminum gadolinium samarium intermediate alloy from gadolinium carbonate and samaric carbonate through molten salt electrolysis |
| CN104775137A (en) * | 2014-01-13 | 2015-07-15 | 赣州飞腾轻合金有限公司 | Method for preparing aluminum-samarium interalloy through liquid-state cathode salt fusion electrolysis method |
| CN105811003A (en) * | 2014-12-29 | 2016-07-27 | 张家港市国泰华荣化工新材料有限公司 | Low temperature electrolyte |
| KR20170010232A (en) * | 2015-07-17 | 2017-01-26 | 재단법인 포항산업과학연구원 | Method for producing aluminum-scandium alloy with high purity |
-
2017
- 2017-05-19 CN CN201710359083.7A patent/CN107130264B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN1410599A (en) * | 2002-12-03 | 2003-04-16 | 中国铝业股份有限公司 | Method of producing aluminium scandium alloy by electrolysis |
| CN1514042A (en) * | 2003-08-21 | 2004-07-21 | 中国铝业股份有限公司 | Production method of high purity aluminium scandium alloy |
| CN1556252A (en) * | 2004-01-08 | 2004-12-22 | 包头铝业股份有限公司 | Method of directly preparing aluminium cerium internediate alloy using fused salt elactrolysis method |
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| CN102108529A (en) * | 2011-01-13 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing aluminum-gadolinium-samarium alloy by fused salt electrolysis |
| CN102352519A (en) * | 2011-10-10 | 2012-02-15 | 哈尔滨工程大学 | Method for preparing aluminum gadolinium samarium intermediate alloy from gadolinium carbonate and samaric carbonate through molten salt electrolysis |
| CN104775137A (en) * | 2014-01-13 | 2015-07-15 | 赣州飞腾轻合金有限公司 | Method for preparing aluminum-samarium interalloy through liquid-state cathode salt fusion electrolysis method |
| CN105811003A (en) * | 2014-12-29 | 2016-07-27 | 张家港市国泰华荣化工新材料有限公司 | Low temperature electrolyte |
| KR20170010232A (en) * | 2015-07-17 | 2017-01-26 | 재단법인 포항산업과학연구원 | Method for producing aluminum-scandium alloy with high purity |
Non-Patent Citations (2)
| Title |
|---|
| MIN LI等: "AlCl3/amide ionic liquids for electrodeposition of aluminum", 《J SOLID STATE ELECTROCHEM》 * |
| 努丽燕娜等: "碳酸乙烯酯添加剂对BMImBF4离子液体作为镁沉积—溶解电解液的改性研究", 《化学学报》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112590B (en) * | 2018-10-12 | 2020-04-21 | 东北大学 | Method for preparing metal thulium film through low-temperature electrochemical deposition |
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| CN109112590A (en) * | 2018-10-12 | 2019-01-01 | 东北大学 | A kind of method that low temperature electrochemical deposition prepares metal thulium film |
| CN109338423A (en) * | 2018-10-12 | 2019-02-15 | 东北大学 | A kind of method that Low-cost electric chemical deposition prepares rare earth metal Tb film |
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| CN109136990B (en) * | 2018-10-12 | 2020-04-28 | 东北大学 | Method for preparing metal lanthanum by taking lanthanum chloride as raw material through low-temperature electrodeposition |
| CN109208043B (en) * | 2018-10-12 | 2020-04-21 | 东北大学 | Method for preparing rare earth metal gadolinium film through electrodeposition |
| CN109208034B (en) * | 2018-10-12 | 2020-04-28 | 东北大学 | Method for preparing rare earth metal neodymium by electrolyzing neodymium chloride at low temperature |
| CN109537008A (en) * | 2019-01-11 | 2019-03-29 | 沈阳大学 | A kind of room temperature electro-deposition prepares aluminium lanthanum alloy film method |
| CN113755894A (en) * | 2021-10-13 | 2021-12-07 | 东北大学 | Method for preparing aluminum magnesium alloy by utilizing room-temperature molten salt electrodeposition |
| CN113755894B (en) * | 2021-10-13 | 2022-09-23 | 东北大学 | Method for preparing aluminum magnesium alloy by utilizing room-temperature molten salt electrodeposition |
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