CN106906493A - A kind of preparation method of metal and alloy powder - Google Patents
A kind of preparation method of metal and alloy powder Download PDFInfo
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- CN106906493A CN106906493A CN201710096336.6A CN201710096336A CN106906493A CN 106906493 A CN106906493 A CN 106906493A CN 201710096336 A CN201710096336 A CN 201710096336A CN 106906493 A CN106906493 A CN 106906493A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
Abstract
The preparation method of a kind of metal and alloy powder, comprises the steps of：Oxide or several hopcalite powder or compressing tablet are combined as negative electrode with metal collector; with graphite as anode; it is electrolyte with the melting alkaline-earth halide or alkali halide or the two mixture that with the addition of excessive correspondence alkaline earth oxide or alkali metal oxide; in protective atmosphere; 400 ~ 900 DEG C of electrolysis temperature; 1.4 ~ 3.2V of decomposition voltage; electrolysis 1 ~ 5 hour; taken out after being cooled to normal temperature; then washed in distilled water, diluted acid or organic solvent, metal or alloy powder are obtained after vacuum drying.The present invention provides the preparation method of a kind of metal and alloy powder, and the method particle size is controllable, so as to realize the direct preparation of metal and alloy powder.
Description
Technical field
The invention belongs to metal and its preparation method of alloy powder, more particularly to refractory metal and its alloy powder system
Preparation Method.
Background technology
Metal and alloy have critical role in national economy, are widely used in chemical industry, metallurgy, ship, automobile, aviation
The fields such as aerospace industry, defense technology.Refractory metal particularly with titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, tungsten, molybdenum as representative and
Its alloy, occupies critical role in national economy, especially has indispensable critical role in leading-edge field.At present, work
The preparation method of industry simple metal mainly has carbothermic method, metallothermic processes, electrothermal way and electrolysis etc..Prepare alloy main
There is high temperature to mixing the methods such as congruent melting and powder metallurgy, the former will generally be well mixed after two kinds of metal meltings, prepared by then condensation
Alloy, this is the most frequently used method for preparing alloy.The advantage of powder metallurgy be by the treatment to powder, can composition,
Level higher is reached in the uniformity and crystal grain refinement of granularity, has the disadvantage that the pure metal powder for wanting use cost very high is original
Material.Petered out with CO2 emission due to fossil energy the influence to global climate the problems such as be on the rise, many industry
The production technology of simple metal and alloy is generally considered to need to improve, particularly pertinent problem is that process is complicated, technological process is long,
Energy resource consumption is big, pollute environment etc., and such problem also results in the metal of some function admirables, the price of alloy occupies height not
Under, limit its application in every field.
Molten-salt electrolysis solid metal oxide is a kind of new method for preparing metal and alloy, and its advantage for protruding can be
Alloy is directly prepared by the mixture of two or more metal oxides.From the principle, as long as several oxide raw materials are mixed
It is compressing after closing uniformly to apply certain voltage between cathode and anode as negative electrode, make negative electrode that oxygen ionized reaction, oxygen to occur
Ion diffuses to anode and is oxidized via fused salt, and the metal obtained in cathodic reduction is bound to each other to form alloy, you can by mixing
Oxide directly obtains required alloy powder through one-step electrolysis, resulting alloy powder both can melting, also can be directly used for
Powder metallurgy.But because electrolytic process operating temperature is high, and cause the metal being continuously generated with electrolytic process or conjunction
Gold sintering is serious, particle increase, causes product to turn into fine and close metal derby, hardly results in metal or alloy powder.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides the preparation method of a kind of metal and alloy powder, the method particle
Size is controllable, so as to realize the direct preparation of metal and alloy powder.
The technical scheme is that：By oxide or several hopcalite powder or compressing tablet and metal afflux
Bluk recombination as negative electrode, with graphite as anode, with the addition of the molten of excessive correspondence alkaline earth oxide or alkali metal oxide
It is electrolyte to melt alkaline-earth halide or alkali halide or the two mixture, in protective atmosphere, electrolysis temperature 400
~ 900 DEG C, 1.4 ~ 3.2V of decomposition voltage is electrolysed 1 ~ 5 hour, is taken out after being cooled to normal temperature, then in distilled water, diluted acid or organic
Washed in solvent, metal or alloy powder are obtained after vacuum drying.
The alkaline-earth halide is the mixture of one or several compositions of Mg, Ca, Sr or Ba halide.
The alkali halide is the mixture of one or several compositions of Li, Na, K, Rb or Cs halide.
The halide is one kind of Cl or F or both mixture.
The metal collector be fusing point higher than the titanium of the thread, netted of reaction temperature, sheet or foam-like, stainless steel,
Molybdenum, tungsten or nickel.
The oxide is Ta, Nb, Ti, Zr, Hf, V, Fe, Co, Ni, Cu, Sn, Cr, W, Al, Si, Ga, Mn or group of the lanthanides oxygen
One or more in compound.
The compressing tablet is that oxide powder is suppressed under 2 ~ 20MPa of pressure, is sintered at 600 ~ 900 DEG C of temperature and formed.
Principle of the invention is：By above-mentioned oxide or hopcalite, electrification is carried out in molten electrolyte
Reduction is learned, the oxygen of oxide reduction removing combines to form corresponding oxide with alkali metal or alkaline-earth metal ions.Due to electricity
Xie Zhizhong originally there is excessive corresponding alkali metal or alkaline earth oxide, the new alkali metal or alkaline earth oxide for being formed
Cannot be dissolved in electrolyte, so as to be separated out in cathode oxidation composition granule precipitated in situ, the shape between cathode reduction products particle
Prevent from oxide from reducing the reunion sintering between gained metallic particles into physics cut-off to grow up.Therefore, successfully prepared by oxide
While metal and alloy, the control of product particle size is realized.
Brief description of the drawings
Fig. 1 is the Ta powder XRD spectrums of the embodiment of the present invention 1.
Fig. 2 is the Ta powder TEM collection of illustrative plates of the embodiment of the present invention 1.
Fig. 3 is the LaNi of the embodiment of the present invention 95Powder XRD spectrum.
Fig. 4 is the LaNi of the embodiment of the present invention 95Powder SEM spectrum.
Specific implementation method
The present invention is further described with reference to the accompanying drawings and examples.These descriptions are intended merely to that the present invention is better described,
Rather than limitation of the present invention.
Embodiment 1
By commercially available 0.1 ~ 0.2 μm of Ta2O5Powder takes 2g, and diameter 20mm, the test piece of thickness 3mm, in sky are pressed under 8MPa
600 DEG C sinter 3 hours in gas, the Ta for obtaining2O5Test piece.By test piece with molybdenum net tight after, then be wound in molybdenum filament with thin molybdenum filament
On as negative electrode, with graphite rod as anode, to melt mol ratio 2:1 MgCl2With the mixing of NaCl and excessive addition magnesia
Thing is electrolyte, and in argon gas atmosphere, temperature is 600 DEG C, and voltage is 1.4V, is electrolysed 5 hours, proposes negative electrode after the completion of electrolysis
Fused salt liquid level simultaneously takes out product after being cooled to normal temperature in a cell, is obtained after being cleaned through 0.1N watery hydrochloric acid and in 60 DEG C of vacuum dryings
To metal Ta powder.Fig. 1 is XRD spectrum；Fig. 2 is TEM photos.As seen from Figure 2, gained powder size is respectively less than 50nm.
Embodiment 2
By commercially available 0.1 ~ 0.2 μm of TiO2Powder takes 3g, with foam nickel sheet tight after, then be wound in stainless steel wire stainless
As negative electrode on steel wire, with graphite rod as anode, to melt CaCl2And the mixture of excessive addition calcium oxide is electrolyte,
In argon gas atmosphere, temperature be 850 DEG C, voltage is 3.2V, be electrolysed 4 hours, after the completion of electrolysis by negative electrode propose fused salt liquid level and
Product is taken out after normal temperature is cooled in electrolytic cell, is cleaned through distilled water, and in 60 DEG C of vacuum dryings, obtain metal Ti powder.
Embodiment 3
Commercially available 0.1 ~ 0.2 μm of NiO powder is taken into 5g, diameter 20mm is pressed under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with stainless (steel) wire tight after, then be wound in stainless steel with stainless steel wire
As negative electrode on silk, with graphite rod as anode, to melt mol ratio 1:1 LiCl, KCl simultaneously add excessive Li2The mixture of O is
Electrolyte, in argon gas atmosphere, temperature is 600 DEG C, and voltage is 2.8V, is electrolysed 3 hours, and negative electrode is proposed into fused salt after the completion of electrolysis
Liquid level simultaneously takes out product after being cooled to normal temperature in a cell, is cleaned through distilled water, and obtain W metal in 60 DEG C of vacuum dryings
Powder.
Embodiment 4
By commercially available 0.1 ~ 0.2 μm of Al2O3Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with titanium silk tight after, then be wound in titanium silk on as negative electrode, with stone
Inker is anode, to melt mol ratio 1:1:1 CaCl2, NaCl, KCl and excessive addition calcium oxide mixture be electrolyte,
In argon gas atmosphere, temperature is 600 DEG C, and voltage is 3.0V, is electrolysed 2 hours, and negative electrode is proposed into fused salt liquid level simultaneously after the completion of electrolysis
Product is taken out after being cooled to normal temperature in a cell, is cleaned through acetone, and metal Al powder is obtained in 60 DEG C of vacuum dryings.
Embodiment 5
By commercially available 0.1 ~ 0.2 μm of V2O5Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with leaf tight after, then with tungsten filament wind on as negative electrode, with stone
Inker is anode, to melt mol ratio 1:1:1 CaCl2, RbCl, CsCl and with the addition of the CaCl of excess amount of Ca O2It is electrolyte,
In argon gas atmosphere, temperature be 900 DEG C, voltage is 3.2V, be electrolysed 1 hour, after the completion of electrolysis by negative electrode propose fused salt liquid level and
Product is taken out after normal temperature is cooled in electrolytic cell, is cleaned through distilled water, and in obtaining metal V powder after 60 DEG C of vacuum dryings.
Embodiment 6
By commercially available 0.1 ~ 0.2 μm of ZrO2Powder takes 1g, is pressed into diameter 20mm under 15MPa, thickness 2mm test piece,
800 DEG C sinter 1 hour in argon gas atmosphere.Test piece is wrapped up with nickel sheet and then is wound as negative electrode with molybdenum filament, be sun with graphite rod
Pole, to melt mol ratio 3:1 CaCl2、CaF2And the mixture of excessive addition calcium oxide is electrolyte, in argon gas atmosphere, temperature
It is 800 DEG C to spend, and voltage is 3.1V, is electrolysed 3 hours, proposes negative electrode after the completion of electrolysis fused salt liquid level and to be cooled in a cell
Product is taken out after normal temperature, through washes of absolute alcohol, and metal Zr powder is obtained in 60 DEG C of vacuum dryings.
Embodiment 7
By commercially available 0.1 ~ 0.2 μm of Nb2O5Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with stainless (steel) wire tight after, then be wound in stainless steel with stainless steel wire
It is electrolyte with the mixture for melting LiCl, KF with graphite rod as anode as negative electrode on silk, in argon gas atmosphere, temperature is
600 DEG C, voltage is 2.4V, is electrolysed 4 hours, proposes negative electrode after the completion of electrolysis fused salt liquid level and to be cooled to normal temperature in a cell
After take out product, cleaned through distilled water, and obtain metal Nb powder in 60 DEG C of vacuum dryings.
Embodiment 8
By commercially available 0.1 ~ 0.2 μm of Co2O3Powder 5g, is pressed into diameter 20mm under 10MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in air.By test piece with stainless (steel) wire tight after, then be wound in stainless steel wire with stainless steel wire
On as negative electrode, with graphite rod as anode, with melt mol ratio 3:1:1 LiCl, BaCl2、SrCl2And excessive addition is aoxidized
The mixture of lithium is electrolyte, and in argon gas atmosphere, temperature is 700 DEG C, and voltage is 2.6V, is electrolysed 4 hours, will after the completion of electrolysis
Negative electrode proposes fused salt liquid level and takes out product after being cooled to normal temperature in a cell, cleaned through distilled water, and dried in 60 DEG C of vacuum
It is dry to obtain Co powder.
Embodiment 9
By commercially available 0.1 ~ 0.2 μm of La2O3, NiO powder press LaNi mol ratios 1:5 take 3g, and diameter is pressed under 10MPa
20mm, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with stainless (steel) wire tight after, then
It is wound on stainless steel wire as negative electrode with stainless steel wire, with graphite rod as anode, to melt CaCl2It is electricity with excessive oxidation calcium
Xie Zhi, in argon gas atmosphere, temperature is 900 DEG C, and voltage is 2.8V, is electrolysed 4 hours, and negative electrode is proposed into liquid fused salt after the completion of electrolysis
Product is simultaneously taken out after being cooled to normal temperature in a cell in face, is cleaned through distilled water, and obtain LaNi in 60 DEG C of vacuum dryings5Alloy
Powder.Fig. 3 is XRD spectrum；Fig. 4 is SEM photograph.
Embodiment 10
By commercially available 0.1 ~ 0.2 μm of SiO2、Fe2O3Powder presses SiFe mol ratios 1:1 takes 3g, and diameter is pressed under 10MPa
20mm, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with stainless (steel) wire tight after, then
It is wound on stainless steel wire as negative electrode with stainless steel wire, with graphite rod as anode, to melt CaCl2It is electricity with excessive oxidation calcium
Xie Zhi, in argon gas atmosphere, temperature is 900 DEG C, and voltage is 2.8V, is electrolysed 4 hours, and negative electrode is proposed into liquid fused salt after the completion of electrolysis
Product is simultaneously taken out after being cooled to normal temperature in a cell in face, is cleaned through distilled water, and obtain SiFe alloys in 60 DEG C of vacuum dryings
Powder.
Embodiment 11
By commercially available 0.1 ~ 0.2 μm of Nb2O5、HfO2、TiO2Powder presses Nb:Hf:Ti mol ratios 1:10:1 takes 3g, is pushed in 10MPa
Diameter 20mm is made, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.Test piece is tight with stainless (steel) wire
After parcel, then it is wound on stainless steel wire as negative electrode with stainless steel wire, with graphite rod as anode, to melt CaCl2And excess
Calcium oxide is electrolyte, and in argon gas atmosphere, temperature is 900 DEG C, and voltage is 2.8V, is electrolysed 4 hours, by negative electrode after the completion of electrolysis
Propose fused salt liquid level and take out product after being cooled to normal temperature in a cell, cleaned through distilled water, and obtained in 60 DEG C of vacuum dryings
To Nb-10Hf-1Ti alloy powders.
Embodiment 12
By commercially available 0.1 ~ 0.2 μm NiO, MnO2、Ga2O3Powder presses Ni:Mn:Ga mol ratios 2:1:1 takes 3g, is suppressed under 10MPa
Into diameter 20mm, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with molybdenum net tight after,
It is wound on stainless steel wire as negative electrode with molybdenum filament again, with graphite rod as anode, to melt CaCl2It is electrolysis with excessive oxidation calcium
Matter, in argon gas atmosphere, temperature is 900 DEG C, and voltage is 2.8V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis
And product is taken out after being cooled to normal temperature in a cell, cleaned through distilled water, and Ni is obtained in 60 DEG C of vacuum dryings2MnGa alloys
Powder.
Embodiment 13
By commercially available 0.1 ~ 0.2 μm TiO2, WO3Powder presses Ti:W mol ratios 1:1 takes 3g, and diameter 20mm is pressed under 10MPa,
In the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with molybdenum net tight after, then twined with molybdenum filament
It is around on stainless steel wire as negative electrode, with graphite rod as anode, to melt CaCl2It is electrolyte with excessive oxidation calcium, in argon gas
In atmosphere, temperature is 900 DEG C, and voltage is 2.8V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level and in electrolysis after the completion of electrolysis
Product is taken out after normal temperature is cooled in groove, is cleaned through distilled water, and TiW alloy powders are obtained in 60 DEG C of vacuum dryings.
Embodiment 14
By commercially available 0.1 ~ 0.2 μm of Nb2O5、SnO2Powder presses Nb:Sn mol ratios 3:1 takes 3g, and diameter is pressed under 10MPa
20mm, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with molybdenum net tight after, then use molybdenum
Silk is wound on stainless steel wire as negative electrode, with graphite rod as anode, to melt CaCl2It is electrolyte with excessive oxidation calcium,
In argon gas atmosphere, temperature be 900 DEG C, voltage is 2.8V, be electrolysed 4 hours, after the completion of electrolysis by negative electrode propose fused salt liquid level and
Product is taken out after normal temperature is cooled in electrolytic cell, is cleaned through distilled water, and Nb is obtained in 60 DEG C of vacuum dryings3Sn alloy powders.
Embodiment 15
By commercially available 0.1 ~ 0.2 μm of Ce2O3, NiO, CuO powder press Ce:Ni:Cu mol ratios 1:4:1 takes 3g, is suppressed under 10MPa
Into diameter 20mm, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with molybdenum net tight after,
It is wound on stainless steel wire as negative electrode with molybdenum filament again, with graphite rod as anode, to melt CaCl2It is electrolysis with excessive oxidation calcium
Matter, in argon gas atmosphere, temperature is 900 DEG C, and voltage is 2.8V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis
And product is taken out after being cooled to normal temperature in a cell, cleaned through distilled water, and CeNi is obtained in 60 DEG C of vacuum dryings4Cu alloys
Powder.
Embodiment 16
By commercially available 0.1 ~ 0.2 μm of ZrO2、Cr2O3Powder presses Zr:Cr mol ratios 1:2 take 3g, and diameter is pressed under 10MPa
20mm, in the common two panels of test piece of 5mm, 600 DEG C sinter 2 hours thickness in air.By test piece with molybdenum net tight after, then use molybdenum
Silk is wound on stainless steel wire as negative electrode, with graphite rod as anode, to melt CaCl2It is electrolyte with excessive oxidation calcium,
In argon gas atmosphere, temperature be 900 DEG C, voltage is 2.8V, be electrolysed 4 hours, after the completion of electrolysis by negative electrode propose fused salt liquid level and
Product is taken out after normal temperature is cooled in electrolytic cell, is cleaned through distilled water, and ZrCr is obtained in 60 DEG C of vacuum dryings2Alloy powder.
Claims (7)
1. the preparation method of a kind of metal and alloy powder, it is characterized in that comprising the steps of：By oxide or several oxygen
The mix powder or compressing tablet of compound are compound with metal collector as negative electrode, with graphite as anode, with the addition of excessive correspondence
The melting alkaline-earth halide or alkali halide or the two mixture of alkaline earth oxide or alkali metal oxide be
Electrolyte, in protective atmosphere, 400 ~ 900 DEG C of electrolysis temperature, 1.4 ~ 3.2V of decomposition voltage is electrolysed 1 ~ 5 hour, is cooled to often
Taken out after temperature, then washed in distilled water, diluted acid or organic solvent, metal or alloy powder are obtained after vacuum drying.
2. the preparation method of metal according to claim 1 and alloy powder, it is characterized in that the metal collector is molten
Point is higher than titanium, stainless steel, molybdenum, tungsten or the nickel of the thread, netted of reaction temperature, sheet or foam-like.
3. the preparation method of metal according to claim 1 and alloy powder, it is characterized in that the alkaline-earth halide
It is the mixture of one or several compositions of Mg, Ca, Sr or Ba halide.
4. the preparation method of metal according to claim 1 and alloy powder, it is characterized in that the alkali halide is
The mixture of one or several compositions of Li, Na, K, Rb or Cs halide.
5. metal according to claim 2,3 or 4 and the preparation method of alloy powder, it is characterized in that the halide is Cl
Or one kind of F or both mixture.
6. the preparation method of metal according to claim 1 and alloy powder, it is characterized in that the oxide be Ta, Nb,
One or more in Ti, Zr, Hf, V, Fe, Co, Ni, Cu, Sn, Cr, W, Al, Si, Ga, Mn or lanthanide oxide.
7. the preparation method of metal according to claim 1 and alloy powder, it is characterized in that the compressing tablet is by oxide
Powder is suppressed under 2 ~ 20MPa of pressure, is sintered at 600 ~ 900 DEG C of temperature and formed.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012476A (en) * | 2017-02-15 | 2017-08-04 | 广东省稀有金属研究所 | A kind of preparation method of composite oxides |
| CN108555298A (en) * | 2018-05-30 | 2018-09-21 | 江苏师范大学 | A kind of electronic industrial products heat sink material |
| CN108893751A (en) * | 2018-06-13 | 2018-11-27 | 华中科技大学 | A kind of preparation method and application of titanium-based oxide |
| CN109732187A (en) * | 2019-01-29 | 2019-05-10 | 东北大学 | A kind of method of melten salt electriochemistry assistant metal welding |
| CN110106369A (en) * | 2019-05-06 | 2019-08-09 | 清华大学 | Elemental lithium extracting method and device based on lithium ion solid electrolyte |
| CN110311107A (en) * | 2019-06-25 | 2019-10-08 | 中南大学 | A kind of lithium metal alloy and the preparation method and application thereof |
| CN114196863A (en) * | 2021-11-14 | 2022-03-18 | 中国长江三峡集团有限公司 | Alloy powder material, preparation method thereof and application of alloy powder material in seawater corrosion resistant laser cladding material |
| CN114293230A (en) * | 2022-01-18 | 2022-04-08 | 郑文 | Method for preparing ferrotungsten powder by molten salt electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107012476A (en) * | 2017-02-15 | 2017-08-04 | 广东省稀有金属研究所 | A kind of preparation method of composite oxides |
| CN108555298A (en) * | 2018-05-30 | 2018-09-21 | 江苏师范大学 | A kind of electronic industrial products heat sink material |
| CN108893751A (en) * | 2018-06-13 | 2018-11-27 | 华中科技大学 | A kind of preparation method and application of titanium-based oxide |
| CN108893751B (en) * | 2018-06-13 | 2020-07-10 | 华中科技大学 | Preparation method and application of titanium-based oxide |
| CN109732187A (en) * | 2019-01-29 | 2019-05-10 | 东北大学 | A kind of method of melten salt electriochemistry assistant metal welding |
| CN109732187B (en) * | 2019-01-29 | 2020-07-21 | 东北大学 | Method for electrochemically assisting metal welding through molten salt |
| CN110106369A (en) * | 2019-05-06 | 2019-08-09 | 清华大学 | Elemental lithium extracting method and device based on lithium ion solid electrolyte |
| CN110106369B (en) * | 2019-05-06 | 2020-10-16 | 清华大学 | Lithium ion solid electrolyte-based lithium element extraction method and device |
| CN110311107A (en) * | 2019-06-25 | 2019-10-08 | 中南大学 | A kind of lithium metal alloy and the preparation method and application thereof |
| CN114196863A (en) * | 2021-11-14 | 2022-03-18 | 中国长江三峡集团有限公司 | Alloy powder material, preparation method thereof and application of alloy powder material in seawater corrosion resistant laser cladding material |
| CN114293230A (en) * | 2022-01-18 | 2022-04-08 | 郑文 | Method for preparing ferrotungsten powder by molten salt electrolysis |
| CN114293230B (en) * | 2022-01-18 | 2023-09-26 | 郑文 | Method for preparing ferrotungsten alloy powder by fused salt electrolysis |
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Application publication date: 20170630 |