CN110129834A - A kind of preparation method of high Li content lithium alloy - Google Patents
A kind of preparation method of high Li content lithium alloy Download PDFInfo
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- CN110129834A CN110129834A CN201910560451.3A CN201910560451A CN110129834A CN 110129834 A CN110129834 A CN 110129834A CN 201910560451 A CN201910560451 A CN 201910560451A CN 110129834 A CN110129834 A CN 110129834A
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Abstract
A kind of preparation method of high Li content lithium alloy, sequentially includes the following steps: (1) under the conditions of argon atmosphere, is mixed urea powder and lithium salts powder to obtain molten salt electrolyte；(2) molten salt electrolyte is placed in electrolytic cell, under the conditions of argon atmosphere, carries out constant potential electro-deposition or constant current electro-deposition；(3) after constant potential electro-deposition or constant current electro-deposition, the cathode plate that surface is deposited with lithium alloy is taken out, after surface clean, then dries, high Li content lithium alloy is made in cathode plate surface.Present invention process process is short, and production temperature is low, and manufactured high lithium content lithium alloy can be directly used for preparing the lithium alloy of the different trades mark.
Description
Technical field
The invention belongs to low-temperature electrolytic metallurgical technology field, in particular to a kind of preparation method of high Li content lithium alloy.
Background technique
Lithium is metal most light in nature, and lithium metal is added in aluminium alloy, can reduce alloy density, improves alloy
Some column advantages such as elasticity modulus, specific strength, specific stiffness, corrosion resistance, be widely used in aerospace field；Magnesium lithium alloy
It is most light in structural metallic materials, is ideal structure with very high specific strength, specific stiffness and excellent anti-seismic performance etc.
Material.
The method of traditional mode of production lithium alloy is mainly ingot metallurgy method, is according to certain by lithium and other high pure metals than column
Melting, the method for direct pouring ingot are carried out under vacuum conditions；This method preparation the lithium alloy rate of recovery is low, process flow
Length, uneven components, with high costs, impurity content are limited by raw material.
Domestic and foreign scholars develop the method that molten-salt electrolysis prepares lithium alloy, contain lithium salts by electrolysis, do not need preparation gold
Belong to lithium and directly obtain lithium alloy, but electrolysis temperature is higher, high temperature chlorine severe corrosion to equipment.
Class ionic liquid is a kind of green solvent fast-developing in recent years, and type is new, type is more, can design, price is low
Many advantages, such as honest and clean, electrochemical window mouth width, conductivity are higher, synthesis is simple is led in catalysis, organic synthesis, dissolution, electrochemistry etc.
The application in domain is constantly expanded as the cognition of people is deepened；Since 21st century, lot of documents reports eutectic solvent
Middle electro-deposition prepares the application of metal and alloy, and metal has aluminium, iron, copper, silver, gallium, manganese, molybdenum etc., alloy include aluminium, platinum, chromium,
Zinc, manganese, magnesium etc., but since the sedimentation potential of lithium is relatively negative, most of solvent is just destroyed before lithium metal precipitation.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high Li content lithium alloy, and solvent is made with urea and lithium salts,
Under cryogenic, using constant potential or constant current electro-deposition, lithium alloy is made on cathode, simplifying technique reduces cost.
Method of the invention sequentially includes the following steps:
1, under the conditions of argon atmosphere, urea powder and lithium salts powder is mixed, are heated to 50~150 under agitation
DEG C, it is stirred continuously until to obtain transparency liquid, as molten salt electrolyte；Wherein the molar ratio of urea powder and lithium salts powder is 2
~5；
2, molten salt electrolyte is placed in electrolytic cell, under the conditions of argon atmosphere, carries out constant potential electro-deposition or constant current
Electro-deposition；When carrying out constant potential electro-deposition, cathode plate, anode plate and reference electrode plate are equipped in the groove body of electrolytic cell, wherein
Cathode plate material is aluminium, magnesium or copper, and reference electrode plate matter is lithium, and anode plate material is lithium, platinum, tungsten, silver or graphite；Work as progress
When constant current electro-deposition, cathode plate and anode plate are equipped in the groove body of electrolytic cell, wherein cathode plate material is aluminium, magnesium or copper, sun
Pole plate material is lithium, platinum, tungsten, silver or graphite；The temperature of constant potential electro-deposition or constant current electro-deposition is 50~150 DEG C, electrolysis
0.5~2h of time；
3, after constant potential electro-deposition or constant current electro-deposition, the cathode plate that surface is deposited with lithium alloy is taken out, warp
It after surface clean, then dries, high Li content lithium alloy is made in cathode plate surface.
In above-mentioned step 2, when carrying out constant potential electro-deposition, cathode potential is 0~-0.5V.
In above-mentioned step 2, when carrying out constant current electro-deposition, current density is 1~500mA/cm2。
In above-mentioned step 3, surface clean is that surface is deposited with to the cathode plate of lithium alloy to be placed in ethylene carbonate,
At least 2h is impregnated under the conditions of 50~80 DEG C of temperature.
In above-mentioned step 3, drying is under the conditions of vacuum degree≤50Pa and 80~150 DEG C of temperature, and the time is at least for 24 hours.
Above-mentioned lithium salts powder is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, LiBF4, perchloric acid
Lithium, hexafluoroarsenate lithium, lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium or double trifluoromethanesulfonimide lithiums.
Above-mentioned lithium salts powder and urea powder are respectively dried to biodiversity percentage < 0.1% before use.
Above-mentioned cathode plate and anode plate uses preceding carry out surface preparation, including polishing, polishing and ultrasonic cleaning, wherein
Ultrasonic cleaning is that cathode plate/anode plate is placed in deionized water to apply ultrasonic wave, time at least 5min.
In the above method, when carrying out constant current electro-deposition, the electrolytic cell used is single-cell for electrolyzation or multi-chamber electrolysis slot；
The cathode plate of single-cell for electrolyzation is located in the middle part of electrolytic cell, and two anode plates are located at cathode plate two sides, cathode plate bottom edge and electrolytic cell
There is channel between bottom；Multiple cathode plates and multiple anode plates are equipped in multi-chamber electrolysis slot, each cathode plate is respectively positioned on adjacent
Between two anode plates, there is channel between cathode plate bottom edge and bottom of electrolytic tank, the space between two adjacent anode plates is made
For a tank house, quantity >=2 of tank house.
In the above method, when carrying out constant potential electro-deposition, the electrolytic cell used for single-cell for electrolyzation, single-cell for electrolyzation
Cathode plate is located in the middle part of electrolytic cell, and anode plate and reference electrode plate are located at cathode plate two sides, cathode plate bottom edge and electrolytic cell
There is channel between bottom.
In above-mentioned step 4, the high Li content lithium alloy of cathode plate surface contains Li 13~20% by mass percentage.
The invention has the benefit that
(1) process flow is short, and more traditional ingot metallurgy method, the production temperature of high temperature fused salt electrolysis method are low, substantially reduces energy
Consumption；
(2) in raw material selected by, urea is cheap, and cost can be effectively reduced in the type and additional amount for adjusting lithium salts；
Manufactured high lithium content lithium alloy can be directly used for preparing the lithium alloy of the different trades mark；
(3) constant potential electro-deposition is carried out in different metallic substrates, can obtain different lithium alloys；
(4) change technological parameter, the different alloy of pattern, size, thickness can be obtained.
Detailed description of the invention
Fig. 1 is the preparation method flow diagram of the high Li content lithium alloy in the embodiment of the present invention；
Fig. 2 is the X-ray diffractogram of cathode plate surface deposit in the embodiment of the present invention 1；
Fig. 3 is the single-cell for electrolyzation structural schematic diagram in the embodiment of the present invention 1；
Fig. 4 is the single-cell for electrolyzation structural schematic diagram in the embodiment of the present invention 9；
Fig. 5 is the multi-chamber electrolysis slot structure schematic diagram in the embodiment of the present invention 10；
In figure, 1, electrode guide rod, 2, single-cell for electrolyzation first anode plate, 3, single-cell for electrolyzation cathode plate, 4, single chamber electrolysis
Slot second plate plate, 5, single-cell for electrolyzation groove body, 6, molten salt electrolyte, 7, multi-chamber electrolysis slot anode plate, 8, multi-chamber electrolysis slot yin
Pole plate, 9, multi-chamber electrolysis slot groove body, 10, reference electrode.
Specific embodiment
The urea used in present example is market analytical pure reagents.
Lithium chloride, lithium fluoride, lithium bromide, lithium iodide, lithium nitrate, LiBF4, the high chlorine used in present example
Sour lithium, hexafluoroarsenate lithium, lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double trifluoromethanesulfonimide lithiums are
Market analytical pure reagents.
Lithium salts powder and urea powder in present example screen out -200 mesh of granularity before use, after drying and grinding
Part, be sealed in the glove box of argon atmosphere.
Lithium salts powder and urea powder are respectively dried to biodiversity percentage < 0.1% before use in present example.
The cathode plate used in present example is aluminium sheet, copper sheet or magnesium plate, purity >=99.99%.
Electrolytic liquid in present example is the preparation method comprises the following steps: under room temperature, urea powder is added in lithium salts powder
After stirring, 50~150 DEG C are warming up to, stirs at least 4h, stirring rate is 300~500r/min.
Cathode plate and anode plate are sealed in the glove box of argon atmosphere and are protected after surface preparation in present example
It deposits.
Cathode plate and anode plate are clear using preceding carry out surface preparation, including polishing, polishing and ultrasound in present example
It washes, wherein ultrasonic cleaning is that cathode plate/anode plate is placed in deionized water to apply ultrasonic wave, time at least 5min.
Reference electrode plate is the lithium plate of purity >=99.9% in present example, and surface oxide layer is scraped off before use, is exposed
Silvery white metallic luster.
In present example, when carrying out constant potential electro-deposition, cathode potential is 0~-0.5V (vs.Li/Li+)；It carries out permanent
When electric current electro-deposition, current density is 1~500mA/cm2。
The configuration of electrolyte and potentiostatic deposition process carry out in the glove box of argon atmosphere in present example.
The equipment that intermediate alloy ingredient uses is analyzed in the embodiment of the present invention emits light for 4300DV inductively coupled plasma
Spectrometer (ICP), the X-ray diffractometer for the MPDDY2094 that product Analysis of components is produced using Dutch Panaco company
(XRD)。
N cathode plate and n+1 anode plate, n > 1 are equipped in the embodiment of the present invention in multi-chamber electrolysis slot.
The material deposited on cathode plate is wiped off in the embodiment of the present invention, i.e. acquisition lithium alloy powder.
Process is as shown in Figure 1 in the embodiment of the present invention.
Embodiment 1
Under the conditions of argon atmosphere, urea powder and lithium salts powder are mixed, 100 DEG C is heated under agitation, holds
Continuous stirring is until obtain transparency liquid, as molten salt electrolyte；Wherein the molar ratio of urea powder and lithium salts powder is 3；Lithium salts
Powder is lithium chloride；
Molten salt electrolyte is placed in electrolytic cell, under the conditions of argon atmosphere, carries out constant potential electro-deposition, electrolytic cell is single
Room electrolytic cell, structure is as shown in figure 3, be equipped with single-cell for electrolyzation cathode plate 3, single-cell for electrolyzation first in single-cell for electrolyzation groove body 5
Anode plate 2 and reference electrode plate 10, single-cell for electrolyzation cathode plate 3 are located at 5 middle part of single-cell for electrolyzation groove body, the electrolytic cell first anode
Plate 2 and reference electrode plate 10 are located at 3 two sides of single-cell for electrolyzation cathode plate, 3 bottom edge of single-cell for electrolyzation cathode plate and single chamber electricity
Solution has channel between 5 bottom of slot groove body；3 material of single-cell for electrolyzation cathode plate is aluminium, and 10 plate matter of reference electrode plate is lithium, electrolysis
2 material of slot first anode plate is lithium；Each electrode is connect by electrode guide rod 1 with work station；Constant potential electro-deposition or constant current electricity
100 DEG C of the temperature of deposition, electrolysis time 1h；Cathode potential -0.5V；
After constant potential electro-deposition or constant current electro-deposition, the cathode plate that surface is deposited with lithium alloy is taken out, cathode
The X-ray diffractogram of plate surface deposit is soaked under the conditions of 80 DEG C of temperature as shown in Fig. 2, cathode plate is placed in ethylene carbonate
2h is steeped, is then dried under the conditions of vacuum degree≤50Pa and 100 DEG C of temperature for 24 hours, high Li content lithium is made in cathode plate surface and closes
Gold contains Li 15.98% by mass percentage, remaining is aluminium.
Embodiment 2
With embodiment 1, difference is method:
(1) 80 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 5；Lithium salts powder is lithium fluoride；
(2) cathode plate material is magnesium, and anode plate material is platinum；The temperature of electro-deposition is 80 DEG C, electrolysis time 2h；Cathode electricity
Position -0.5V；
(3) cathode plate taking-up be placed in ethylene carbonate, impregnate 3h under the conditions of 80 DEG C of temperature, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 80 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
16.54%, remaining is magnesium.
Embodiment 3
With embodiment 1, difference is method:
(1) 120 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 2；Lithium salts powder is lithium bromide；
(2) cathode plate material is copper, and anode plate material is tungsten；The temperature of electro-deposition is 120 DEG C, electrolysis time 0.5h；Yin
Electrode potential -0.3V；
(3) cathode plate taking-up is placed in ethylene carbonate, 2.5h is impregnated under the conditions of 80 DEG C of temperature, then in vacuum degree
It is dried for 24 hours under the conditions of≤50Pa and 90 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
17.23%, remaining is copper.
Embodiment 4
With embodiment 1, difference is method:
(1) 150 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 4；Lithium salts powder is lithium iodide；
(2) cathode plate material is aluminium, and anode plate material is silver；The temperature of electro-deposition is 150 DEG C, electrolysis time 2h；Cathode
Current potential -0.3V；
(3) cathode plate taking-up be placed in ethylene carbonate, impregnate 3h under the conditions of 80 DEG C of temperature, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 110 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
17.53%, remaining is aluminium.
Embodiment 5
With embodiment 1, difference is method:
(1) 50 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 2.5；Lithium salts powder is lithium nitrate；
(2) cathode plate material is magnesium, and anode plate material is graphite；The temperature of electro-deposition is 50 DEG C, electrolysis time 2h；Cathode
Current potential -0.3V；
(3) cathode plate taking-up be placed in ethylene carbonate, impregnate 3h under the conditions of 80 DEG C of temperature, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 120 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
15.79%, remaining is magnesium.
Embodiment 6
With embodiment 1, difference is method:
(1) 110 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 2；Lithium salts powder is LiBF4；
(2) cathode plate material is magnesium, and anode plate material is platinum；The temperature of electro-deposition is 110 DEG C, electrolysis time 2h；Cathode
Current potential -0.5V；
(3) cathode plate taking-up is placed in ethylene carbonate, 3.5h is impregnated under the conditions of 80 DEG C of temperature, then in vacuum degree
It is dried for 24 hours under the conditions of≤50Pa and 80 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
15.45%, remaining is magnesium.
Embodiment 7
With embodiment 1, difference is method:
(1) 130 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 3.5；Lithium salts powder is lithium perchlorate；
(2) cathode plate material is magnesium, and anode plate material is tungsten；The temperature of electro-deposition is 130 DEG C, electrolysis time 2h；Cathode
Current potential -0.5V；
(3) cathode plate taking-up be placed in ethylene carbonate, impregnate 3h under the conditions of 80 DEG C of temperature, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 130 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
19.52%, remaining is magnesium.
Embodiment 8
With embodiment 1, difference is method:
(1) 140 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 2.5；Lithium salts powder is hexafluoroarsenate lithium；
(2) cathode plate material is copper, and anode plate material is silver；The temperature of electro-deposition is 140 DEG C, electrolysis time 1.5h；Yin
Electrode potential -0.3V；
(3) cathode plate taking-up is placed in ethylene carbonate, 2.5h is impregnated under the conditions of 80 DEG C of temperature, then in vacuum degree
It is dried for 24 hours under the conditions of≤50Pa and 80 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
18.81%, remaining is copper.
Embodiment 9
With embodiment 1, difference is method:
(1) 150 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 4.5；Lithium salts powder is lithium hexafluoro phosphate；
(2) constant current electro-deposition is carried out；The electrolytic cell used is single-cell for electrolyzation, and structure is as shown in figure 4, multi-chamber electrolysis slot
Cathode plate 3 is located at 5 middle part of single-cell for electrolyzation groove body, and single-cell for electrolyzation first anode plate 2 and single-cell for electrolyzation second plate plate 4 divide
Not Wei Yu 3 two sides of multi-chamber electrolysis slot cathode plate, have between 3 bottom edge of multi-chamber electrolysis slot cathode plate and 5 bottom of single-cell for electrolyzation groove body
Channel；Cathode plate and two anode plates pass through electrode guide rod 1 respectively and connect with work station；Cathode plate material is aluminium, anode sheet material
Matter is lithium；The temperature of constant current electro-deposition is 150 DEG C, electrolysis time 2h；Current density 1mA/cm2；
(3) cathode plate taking-up is placed in ethylene carbonate, 3.5h is impregnated under the conditions of 80 DEG C of temperature, then in vacuum degree
It is dried for 24 hours under the conditions of≤50Pa and 150 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contains by mass percentage
Li 13.44%, remaining is aluminium.
Embodiment 10
With embodiment 1, difference is method:
(1) 95 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 3.5；Lithium salts powder is di-oxalate lithium borate；
(2) constant current electro-deposition is carried out；The electrolytic cell used is multi-chamber electrolysis slot, and structure is as shown in figure 5, multi-chamber electrolysis slot
6 multi-chamber electrolysis slot cathode plates 8 and 7 multi-chamber electrolysis slot anode plates 7 are equipped in groove body 9, each multi-chamber electrolysis slot cathode plate 8 is
Between two adjacent multi-chamber electrolysis slot anode plates 7,8 bottom edge of multi-chamber electrolysis slot cathode plate and 9 bottom of multi-chamber electrolysis slot groove body
There is channel between portion, the space between two adjacent multi-chamber electrolysis slot anode plates 7 is as a tank house, the quantity of tank house
=6；Each cathode plate and each anode plate pass through electrode guide rod 1 respectively and connect to power supply；Cathode plate material is magnesium, and anode plate material is
Graphite；The temperature of constant current electro-deposition is 95 DEG C, electrolysis time 2h；Current density 20mA/cm2；
(3) cathode plate taking-up be placed in ethylene carbonate, impregnate 3h under the conditions of 80 DEG C of temperature, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 85 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
14.17%, remaining is magnesium.
Embodiment 11
With embodiment 1, difference is method:
(1) 105 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 3.5；Lithium salts powder is difluorine oxalic acid boracic acid lithium；
(2) constant current electro-deposition is carried out；For single-cell for electrolyzation, cathode plate is located in the middle part of electrolytic cell the electrolytic cell used, and two
A anode plate is located at cathode plate two sides, has channel between cathode plate bottom edge and bottom of electrolytic tank；Cathode plate material is copper, anode plate
Material is graphite；The temperature of constant current electro-deposition is 105 DEG C, electrolysis time 2h；Current density 200mA/cm2；
(3) cathode plate taking-up be placed in ethylene carbonate, 4h is impregnated under the conditions of temperature 70 C, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 145 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
16.33%, remaining is copper.
Embodiment 12
With embodiment 1, difference is method:
(1) 125 DEG C are heated under agitation after urea powder and the mixing of lithium salts powder, urea powder and lithium salts powder
Molar ratio be 4；Lithium salts powder is double trifluoromethanesulfonimide lithiums；
(2) constant current electro-deposition is carried out；The electrolytic cell used is multi-chamber electrolysis slot, and structure is as shown in figure 4, multi-chamber electrolysis slot
Interior to be equipped with n cathode plate and n+1 anode plate, each cathode plate is respectively positioned between two adjacent anode plates, cathode plate bottom edge
There is channel between bottom of electrolytic tank, the space between two adjacent anode plates is as a tank house, the quantity of tank house
=n；Cathode plate material is copper, and anode plate material is graphite；The temperature of constant current electro-deposition is 125 DEG C, electrolysis time 2h；Electric current
Density 500mA/cm2；
(3) cathode plate taking-up be placed in ethylene carbonate, 6h is impregnated under the conditions of temperature 60 C, then vacuum degree≤
It is dried for 24 hours under the conditions of 50Pa and 135 DEG C of temperature, high Li content lithium alloy is made in cathode plate surface, contain Li by mass percentage
18.93%, remaining is copper.
Claims (10)
1. a kind of preparation method of high Li content lithium alloy, it is characterised in that sequentially include the following steps:
(1) under the conditions of argon atmosphere, urea powder and lithium salts powder is mixed, are heated to 50~150 DEG C under agitation,
It is stirred continuously until to obtain transparency liquid, as molten salt electrolyte；Wherein the molar ratio of urea powder and lithium salts powder is 2~5；
(2) molten salt electrolyte is placed in electrolytic cell, under the conditions of argon atmosphere, carries out constant potential electro-deposition or constant current electricity is heavy
Product；When carrying out constant potential electro-deposition, cathode plate, anode plate and reference electrode plate are equipped in the groove body of electrolytic cell, wherein cathode
Plate matter is aluminium, magnesium or copper, and reference electrode plate matter is lithium, and anode plate material is lithium, platinum, tungsten, silver or graphite；It is permanent electric when carrying out
When galvanic electricity deposits, cathode plate and anode plate are equipped in the groove body of electrolytic cell, wherein cathode plate material is aluminium, magnesium or copper, anode plate
Material is lithium, platinum, tungsten, silver or graphite；The temperature of constant potential electro-deposition or constant current electro-deposition is 50~150 DEG C, electrolysis time
0.5~2h；
(3) after constant potential electro-deposition or constant current electro-deposition, the cathode plate that surface is deposited with lithium alloy is taken out, through surface
It after cleaning, then dries, high Li content lithium alloy is made in cathode plate surface.
2. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (2), into
When row constant potential electro-deposition, cathode potential is 0~-0.5V.
3. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (2), into
When row constant current electro-deposition, current density is 1~500mA/cm2。
4. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (3), table
Face cleaning is that surface is deposited with to the cathode plate of lithium alloy to be placed in ethylene carbonate, is dipped under the conditions of 50~80 DEG C of temperature
Few 2h.
5. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (3), dry
Dry is under the conditions of vacuum degree≤50Pa and 80~150 DEG C of temperature, and the time is at least for 24 hours.
6. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that the lithium salts powder
End is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, hexafluoro phosphorus
Sour lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium or double trifluoromethanesulfonimide lithiums.
7. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that the cathode plate
Use preceding carry out surface preparation with anode plate, including polishing, polishing and ultrasonic cleaning, wherein ultrasonic cleaning be by cathode plate/
Anode plate, which is placed in deionized water, applies ultrasonic wave, time at least 5min.
8. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (2), when
When carrying out constant current electro-deposition, the cathode plate of the single-cell for electrolyzation of use is located in the middle part of electrolytic cell, and two anode plates are located at cathode
There are channel in plate two sides between cathode plate bottom edge and bottom of electrolytic tank；Multiple cathode plates and multiple anodes are equipped in multi-chamber electrolysis slot
Plate, each cathode plate are respectively positioned between two adjacent anode plates, there is channel between cathode plate bottom edge and bottom of electrolytic tank, adjacent
Two anode plates between space as a tank house, quantity >=2 of tank house.
9. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (2), when
When carrying out constant potential electro-deposition, for single-cell for electrolyzation, the cathode plate of single-cell for electrolyzation is located in the middle part of electrolytic cell the electrolytic cell used,
Anode plate and reference electrode plate are located at cathode plate two sides, have channel between cathode plate bottom edge and bottom of electrolytic tank.
10. a kind of preparation method of high Li content lithium alloy according to claim 1, it is characterised in that in step (4), yin
The high Li content lithium alloy of polar board surface contains Li13~20% by mass percentage.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560451.3A CN110129834B (en) | 2019-06-26 | 2019-06-26 | Preparation method of high-Li-content lithium alloy |
| PCT/CN2019/094872 WO2020258366A1 (en) | 2019-06-26 | 2019-07-05 | Method for preparing high-li-content lithium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560451.3A CN110129834B (en) | 2019-06-26 | 2019-06-26 | Preparation method of high-Li-content lithium alloy |
Publications (2)
| Publication Number | Publication Date |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109090A (en) * | 2007-07-24 | 2008-01-23 | 哈尔滨工程大学 | Method for producing out-phase compositive magnesium lithium alloy with low-temperature electrolyzing |
| CN101368281A (en) * | 2008-09-27 | 2009-02-18 | 东北大学 | Method for aluminum lithium alloy preparation by fused salt electrolysis process |
| CN101376992A (en) * | 2008-09-27 | 2009-03-04 | 东北大学 | Method for preparing magnesium lithium alloy by fused salt electrolysis process |
| CN101643921A (en) * | 2009-09-09 | 2010-02-10 | 哈尔滨工程大学 | Method for producing aluminium-lithium alloy with high lithium content by low-temperature molten salt electrolysis |
| CN101698951A (en) * | 2008-09-27 | 2010-04-28 | 东北大学 | Method for preparing magnesium-lithium alloy by molten salt electrolysis |
| CN103031568A (en) * | 2011-10-08 | 2013-04-10 | 中国科学院青岛生物能源与过程研究所 | Preparation method of lithium metal through electrolysis |
| CN105040032A (en) * | 2015-04-08 | 2015-11-11 | 东北大学 | Method of preparing transition metal and alloy thereof through low temperature molten salt electro-deposition |
| CN105112963A (en) * | 2015-10-10 | 2015-12-02 | 东北大学 | Fused salt electrodeposition method for preparing metallic aluminum and metallic aluminum alloys |
| CN106967998A (en) * | 2017-05-19 | 2017-07-21 | 东北大学 | The method that Al Li foundry alloys are prepared as the nearly room temperature electro-deposition of raw material using lithia |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130106029A1 (en) * | 2011-10-27 | 2013-05-02 | Infinite Power Solutions, Inc. | Fabrication of High Energy Density Battery |
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
-
2019
- 2019-06-26 CN CN201910560451.3A patent/CN110129834B/en active Active
- 2019-07-05 WO PCT/CN2019/094872 patent/WO2020258366A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109090A (en) * | 2007-07-24 | 2008-01-23 | 哈尔滨工程大学 | Method for producing out-phase compositive magnesium lithium alloy with low-temperature electrolyzing |
| CN101368281A (en) * | 2008-09-27 | 2009-02-18 | 东北大学 | Method for aluminum lithium alloy preparation by fused salt electrolysis process |
| CN101376992A (en) * | 2008-09-27 | 2009-03-04 | 东北大学 | Method for preparing magnesium lithium alloy by fused salt electrolysis process |
| CN101698951A (en) * | 2008-09-27 | 2010-04-28 | 东北大学 | Method for preparing magnesium-lithium alloy by molten salt electrolysis |
| CN101643921A (en) * | 2009-09-09 | 2010-02-10 | 哈尔滨工程大学 | Method for producing aluminium-lithium alloy with high lithium content by low-temperature molten salt electrolysis |
| CN103031568A (en) * | 2011-10-08 | 2013-04-10 | 中国科学院青岛生物能源与过程研究所 | Preparation method of lithium metal through electrolysis |
| CN105040032A (en) * | 2015-04-08 | 2015-11-11 | 东北大学 | Method of preparing transition metal and alloy thereof through low temperature molten salt electro-deposition |
| CN105112963A (en) * | 2015-10-10 | 2015-12-02 | 东北大学 | Fused salt electrodeposition method for preparing metallic aluminum and metallic aluminum alloys |
| CN106967998A (en) * | 2017-05-19 | 2017-07-21 | 东北大学 | The method that Al Li foundry alloys are prepared as the nearly room temperature electro-deposition of raw material using lithia |
Non-Patent Citations (5)
| Title |
|---|
| BAOGUO ZHANG等: ""Electrodeposition of Al, Al-Li Alloy, and Li from an Al-Containing Solvate Ionic Liquid under Ambient Conditions"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| CHAO-CHEN YANG等: ""The Electrical Conductivity of the Molten Binary Systems CO(NH2)2-MNO3(M=Li,Na,NH4)"", 《ZEITSCHRIFT FUR NATURFORSCHUNG SECTION A-A JOURNAL OF PHYSICAL SCIENCES》 * |
| H.SANO等: ""Observation of electrodeposited lithium by optical microscope in room temperature ionic liquid-based electrolyte"", 《JOURNAL OF POWER SOURCES》 * |
| MIN LI等: ""Electrodeposition behavior of aluminum from urea-acetamide-lithium halide low-temperature molten salts"", 《ELECTROCHIMICA ACTA》 * |
| O.A. LAMBRI等: ""Obtaining of single phase Cu-Li alloy through an electrodeposition process"", 《MATERIALS LETTERS》 * |
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