CN110205651A - A kind of method that low temperature electrochemical reduction barium oxide prepares vanadium metal - Google Patents
A kind of method that low temperature electrochemical reduction barium oxide prepares vanadium metal Download PDFInfo
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- CN110205651A CN110205651A CN201910624805.6A CN201910624805A CN110205651A CN 110205651 A CN110205651 A CN 110205651A CN 201910624805 A CN201910624805 A CN 201910624805A CN 110205651 A CN110205651 A CN 110205651A
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- barium oxide
- vanadium metal
- vanadium
- low temperature
- electrochemical reduction
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- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 title claims abstract description 118
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000002608 ionic liquid Substances 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- -1 wherein Substances 0.000 claims abstract description 7
- 239000004020 conductor Substances 0.000 claims abstract description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 230000005496 eutectics Effects 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid group Chemical group C(CC(=O)O)(=O)O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 229960001231 choline Drugs 0.000 description 9
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- VYWQTJWGWLKBQA-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;chloride Chemical compound Cl.NC(N)=O VYWQTJWGWLKBQA-UHFFFAOYSA-N 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- SNBDGFZQPKCZTO-UHFFFAOYSA-N propanedioic acid;hydrochloride Chemical compound Cl.OC(=O)CC(O)=O SNBDGFZQPKCZTO-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides the methods that a kind of low temperature electrochemical reduction barium oxide prepares vanadium metal, the method may include following steps: barium oxide being added in electrolyte, using metallic matrix as cathode, inactive, conductive material is anode, in temperature 60 C~100 DEG C, it carries out electro-deposition under conditions of voltage 2.0V~4.5V, after deposition, takes out cathode product, obtain vanadium metal, wherein, the electrolyte is ionic liquid, and solubility of the barium oxide in ionic liquid is greater than 10mmol/L.Method of the invention electrochemical reduction barium oxide can deposit to obtain vanadium metal under cryogenic, vanadium metal preparation flow can significantly be shortened, reduce production cost and operation temperature, reduce equipment corrosion, current efficiency is improved, can be realized the green production of vanadium metal.
Description
Technical field
The present invention relates to vanadium metal preparation fields, more particularly, are related to a kind of low temperature electrochemical reduction barium oxide system
The method of standby vanadium metal.
Background technique
Vanadium is a kind of rare metal with own strategic significance, because of the characteristics such as its fusing point is high, hardness is big, thermal conductivity is good,
It is widely used in the leading-edge fields such as steel, battery energy storage, aerospace and nuclear industry.
Various countries are increasing to the demand of vanadium metal and its alloy in recent years, and production technology at this stage has been unable to satisfy
Its demand, therefore, the exploitation of metal extraction process of vanadium obtain the great attention of people.Since vanadium metal can not pass through aqueous solution electricity
Solution obtains, and presently mainly using vanadium oxide or vanadium chloride as raw material, passes through metallothermic processes (such as calcium, aluminium, magnesium), hydrogen reduction
Method or vacuum carbon reduction method realize the preparation of vanadium metal, but at this time in vanadium metal also containing impurity elements such as carbon, oxygen, nitrogen, hydrogen, need
Further to purify refining can be only achieved product standard.In addition, fused salt electrolysis process, which prepares vanadium metal, also becomes Recent study
A kind of emerging extraction process that persons focus.However, there are process flow length, high production cost and operation temperatures for fused salt electrolysis process
Height, equipment seriously corroded, impurity are difficult to the problems such as separating, and significantly limit the application of vanadium metal and its alloy.
Summary of the invention
It is above-mentioned existing in the prior art it is an object of the present invention to solving for the deficiencies in the prior art
One or more problems.For example, can be gone back at a lower temperature one of the objects of the present invention is to provide a kind of equipment requirement is low
The method that former barium oxide prepares vanadium metal.
To achieve the goals above, the present invention provides the sides that a kind of low temperature electrochemical reduction barium oxide prepares vanadium metal
Method, the method may include following steps: barium oxide being added in electrolyte, using metallic matrix as cathode, inertia is conductive
Material is anode, carries out electro-deposition under conditions of temperature 60 C~100 DEG C, voltage 2.0V~4.5V, after deposition, is taken out
Cathode product obtains vanadium metal, wherein the electrolyte is ionic liquid.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The ionic liquid can be one or more of eutectic solvent, glyoxaline ion liquid and pyridine ionic liquid
Combination.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The electrolyte can be the electrolyte that can dissolve barium oxide, and solubility can be greater than 10mmol/L.Further, described
Solubility can be greater than 30mmol/L.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The method can also include that additive is added into the electrolyte, and the additive is malonic acid, ascorbic acid or bigcatkin willow
The combination of one or more of acid.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The barium oxide can be one or more of vanadic anhydride, vanadium trioxide, vanadium dioxide and hypovanadous oxide group
It closes.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The barium oxide can be powdered.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The cathode product can be the vanadium metal coating or vanadium metal film being attached on the metal base surface.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The method can also include by the vanadium metal coating or vanadium metal film from the isolated metal vanadium powder of the metallic matrix
The step at end.
In an exemplary embodiment of the method that low temperature electrochemical reduction barium oxide of the invention prepares vanadium metal,
The thickness of the vanadium metal coating or vanadium metal film can be 10 μm -500 μm.
Compared with prior art, the beneficial effect comprise that method of the invention can be electrochemical at a lower temperature
It learns reduction barium oxide and vanadium metal is prepared, can significantly shorten preparation flow, reduce production cost and operation temperature, it can
Equipment corrosion is reduced, current efficiency is improved, can be realized the green production of vanadium metal.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
What the vanadic anhydride that Fig. 1 shows an illustrative embodiment of the invention restored in choline chloride-urea follows
Ring volt-ampere curve, wherein dotted line indicates that choline chloride-urea electrochemical window, solid line indicate five oxidation two on glass-carbon electrode
The cyclic voltammetry curve of vanadium；
Fig. 2 shows the cathode product figures of an illustrative embodiment of the invention, wherein (a) is the cathodic metal taken out
Matrix (b) is schemed for the SEM of product metal vanadium.
Specific embodiment
Hereinafter, low temperature electrochemical reduction vanadium oxidation according to the present invention will be described in detail in conjunction with exemplary embodiment
The method that object prepares vanadium metal.
What the vanadic anhydride that Fig. 1 shows an illustrative embodiment of the invention restored in choline chloride-urea follows
Ring volt-ampere curve, wherein dotted line indicates that choline chloride-urea electrochemical window, solid line indicate five oxidation two on glass-carbon electrode
The cyclic voltammetry curve of vanadium.Fig. 2 shows the cathode product figures of an illustrative embodiment of the invention, wherein (a) is to take out
Cathode (b) is schemed for the SEM of vanadium metal.
The present invention provides the methods that a kind of low temperature electrochemical reduction barium oxide prepares vanadium metal.In low temperature of the invention
Electrochemical reduction barium oxide is prepared in an exemplary embodiment of the method for vanadium metal, and the method may include following steps
It is rapid:
Using barium oxide as raw material, it is added in il electrolyte, using metallic matrix as cathode, inactive, conductive material is
Anode applies the tank voltage of 2.0V~4.5V, carries out electro-deposition under the conditions of 60 DEG C~100 DEG C of temperature.After deposition, take
Cathode product out obtains vanadium metal simple substance.
In the present embodiment, the barium oxide can be vanadic anhydride, vanadium trioxide, vanadium dioxide and an oxygen
Change one or more of vanadium mixture.The barium oxide can be powder or bulk.Preferably, the barium oxide is
It is powdered.Powdered barium oxide is conducive to dissolve in the electrolytic solution, can shorten the preparation time of vanadium metal.Further
, the granularity of the barium oxide can be 100 μm hereinafter, certainly, the granularity of barium oxide is the smaller the better.
In the present embodiment, the electrolyte is il electrolyte.Ionic liquid is the abbreviation of ionic liquid at room temperature,
Be be made of certain cationic and anion in room temperature or be bordering on the molten salt system being in a liquid state at room temperature.With other solvent phases
Than, ionic liquid have volatility is small, thermal stability is high, liquid state range is big, electrochemical window mouth width, can dissolve many organic matters and
The excellent physicochemical properties such as inorganic matter.Ionic liquid can dissolve barium oxide as solvent, and be capable of providing one kind
The entirely different reaction environment with conventional solvent obtain the chemical reaction wherein occurred may with traditional chemical fully reacting not
Same result.In terms of barium oxide electroreduction, ionic liquid has wider electrochemical window, can be obtained at room temperature
Obtained vanadium metal and alloy could be electrolysed in high-temperature molten salt, without strong corrosive as high-temperature molten salt；Simultaneously as
Ionic liquid has good electric conductivity and relatively negative reduction potential, can be electrolysed to obtain vanadium metal and alloy and nothing at room temperature
Side reaction.
More than, the electrolyte can be eutectic solvent, glyoxaline ion liquid or pyridine ionic liquid.For
Traditional fused salt electrolysis process prepare vanadium metal be using the fused salts such as calcium chloride be electrolyte.The fusing point of the fused salts such as calcium chloride is higher,
Need it is external apply very high temperature, it is huge to will cause energy consumption, equipment seriously corroded.The present invention using eutectic solvent,
Glyoxaline ion liquid or pyridine ionic liquid plasma liquid are electrolyte, can electrochemistry is also at a lower temperature
Original obtains vanadium metal, can save energy consumption.For eutectic solvent, eutectic solvent it is cheap, to water and air
Stablize, the requirement to equipment is very low, has good solvability to barium oxide.For glyoxaline ion liquid or pyridines
For ionic liquid, the electrochemical window oral sex of glyoxaline ion liquid or pyridine ionic liquid is wide, can be in electrolytic process
It is middle to apply biggish tank voltage, the reduction rate of barium oxide can be accelerated.
In the present embodiment, the electrolyte can be the electrolyte that can dissolve barium oxide.For vanadium can be dissolved
For the electrolyte of oxide, by apply current potential can on cathode precipitating metal vanadium.It is described to dissolve barium oxide electricity
The solubility for solving liquid need to be greater than 10mmol/L, for example, solubility can be greater than 25mmol/L, for another example can be 100mmol/L
Or 56mmol/L.Electrolyte that is smaller for solubility or cannot dissolving barium oxide, vanadium metal are difficult to be deposited on cathode
On, or even cannot be deposited on cathode, and be likely to result in the barium oxide in product containing low price, cause product impure.
The solubility of electrolyte is bigger, and the concentration of vanadium ion is bigger in solution, and in electrodeposition process, the vanadium ion of cathode surface is dense
Degree is bigger, the deposition potential of vanadium metal can be made to shuffle, and accelerate deposition velocity.Inventor the study found that barium oxide from
It, can be preferably to barium oxide by the temperature and voltage of above-mentioned setting when solubility in sub- liquid is greater than 30mmol/L
It is restored, and detects less barium oxide impurity in the product.The electrolyte can for choline chloride-urea or
Person's choline chloride-malonic acid etc..For example, being wider than five oxidations two as shown in Figure 1, choline chloride-urea electrochemical window is wider
The reduction potential of vanadium.Reduction peak C1, the reduction that C2 may infer that as vanadic anhydride, vanadium in vanadic anhydride is from 5 valences to 3
Valence, then to 0 valence, obtain vanadium metal.In figure, A1 indicates oxidation peak, and ordinate indicates that electric current, abscissa indicate current potential, relative to
Reference electrode silver, unit is volt.
In the present embodiment, the electrolyte can also be the ionic liquid of big long-chain.The ionic liquid of big long-chain more holds
Soluble barium oxide.
In the present embodiment, the electrolysis temperature can be 60 DEG C~100 DEG C.Above-mentioned electrolysis temperature, which is arranged, can ensure vanadium
Oxide can restore in electrolyte of the invention.60 DEG C of the temperature low temperature of setting, reduction efficiency is low, and barium oxide restores not
Thoroughly, it is mingled with low oxide in product；The temperature of setting is higher than 100 DEG C, will cause electrolyte decomposition, and increase the energy
Consumption.Further, the electrolysis temperature can be 65 DEG C~95 DEG C, can be 72 DEG C~90 DEG C further, example
It such as, can be 80 DEG C.
In the present embodiment, in order to further increase the solubility of electrolyte, increase electrolytic efficiency and production efficiency, it can
Additive to be added in the electrolytic solution.The additive can be malonic acid, ascorbic acid or salicylic acid etc., to improve vanadium oxygen
Solubility and electrolytic efficiency of the compound in eutectic solvent.Certainly, additive of the invention is without being limited thereto, can be improved vanadium oxygen
The additive of compound electrolytic efficiency.
In the present embodiment, the tank voltage of the electrolysis can be 2.0V~4.5V.Above-mentioned voltage is set, is on the one hand needed
Consider the reduction potential of vanadium ion, on the other hand also needs to consider the decomposition voltage of electrolyte.In practical electrodeposition process, institute
The tank voltage of application has to be larger than vanadium ion and is reduced to voltage required for vanadium metal, and is necessarily less than the electricity of electrolyte decomposition
Pressure.Above-mentioned tank voltage can also be adjusted according to used raw material and electrolyte.For example, for being with vanadic anhydride
Raw material, using the wider ionic liquid of electrochemical window as electrolyte, so that it may suitably use biggish tank voltage.
In the present embodiment, the metallic matrix can be the metals class matrixes such as copper sheet, stainless steel, nickel sheet, titanium sheet.It is described
Inactive, conductive material can be graphite-like electrode, for example, graphite flake, graphite rod, platinized platinum etc..
In the present embodiment, the cathode product can be the vanadium metal coating or vanadium metal for being attached to metal base surface
Film.But when needing vanadium metal powder, need to separate the vanadium metal coating or vanadium metal film from metallic matrix.Example
Such as, it can directly be scraped off from metallic matrix with utensil.The thickness of the obtained vanadium metal coating or vanadium metal film can
Think 10 μm -500 μm, can be 10 μm -200 μm further.As shown in Fig. 2 (a), using metallic matrix copper as cathode, metal
Vanadium is deposited on metallic matrix copper, forms vanadium coating.2 (b) be the indicator and microscopic appearance figure of 2 (a) vanadium coating, wherein in figure
MAG indicate amplification multiple；WD represents operating distance, represents objective focal length；Det indicates detector type.
Exemplary embodiment of the present invention is described in further detail below in conjunction with specific example.
Example 1
Vanadium pentoxide powder is added in choline chloride-urea, using copper sheet as cathode, graphite rod is anode, in temperature
62 DEG C, electro-deposition is carried out under conditions of voltage 2.1V.After deposition, cathode product is taken out, vanadium metal is obtained.
Example 2
Vanadium trioxide powder is added in choline chloride-malonic acid, using nickel sheet as cathode, platinized platinum is anode, in temperature
98 DEG C, electro-deposition is carried out under conditions of voltage 4.3V.After deposition, cathode product is taken out, vanadium metal is obtained.
Example 3
Hypovanadous oxide powder is added in choline chloride, using nickel sheet as cathode, platinized platinum is anode, at 78 DEG C of temperature, voltage
Electro-deposition is carried out under conditions of 3.1V.After deposition, cathode product is taken out, vanadium metal is obtained.
In conclusion method of the invention can obtain vanadium metal, energy by electrochemical reduction barium oxide under cryogenic
Enough significant shortening preparation flows, reduce production cost and operation temperature, reduce equipment corrosion, improve current efficiency, can be realized
The green production of vanadium metal.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (9)
1. a kind of method that low temperature electrochemical reduction barium oxide prepares vanadium metal, which is characterized in that the method includes following
Step:
By barium oxide be added electrolyte in, using metallic matrix as cathode, inactive, conductive material is anode, temperature 60 C~
It 100 DEG C, carries out electro-deposition under conditions of voltage 2.0V~4.5V, after deposition, takes out cathode product, obtain vanadium metal,
In, the electrolyte is ionic liquid, and solubility of the barium oxide in ionic liquid is greater than 10mmol/L.
2. the method that low temperature electrochemical reduction barium oxide according to claim 1 prepares vanadium metal, which is characterized in that institute
Barium oxide solubility is stated greater than 30mmol/L.
3. the method that low temperature electrochemical reduction barium oxide according to claim 1 or 2 prepares vanadium metal, feature exist
In the ionic liquid is one or more of eutectic solvent, glyoxaline ion liquid and pyridine ionic liquid
Combination.
4. the method that low temperature electrochemical reduction barium oxide according to claim 1 or 2 prepares vanadium metal, feature exist
In the method also includes additive is added into the electrolyte, the additive is malonic acid, ascorbic acid or salicylic acid
One or more of combination.
5. the method that low temperature electrochemical reduction barium oxide according to claim 1 or 2 prepares vanadium metal, feature exist
In the barium oxide is one or more of vanadic anhydride, vanadium trioxide, vanadium dioxide and hypovanadous oxide group
It closes.
6. the method that low temperature electrochemical reduction barium oxide according to claim 1 or 2 prepares vanadium metal, feature exist
In the barium oxide is powdered.
7. the method that low temperature electrochemical reduction barium oxide according to claim 1 or 2 prepares vanadium metal, feature exist
In the cathode product is the vanadium metal coating or vanadium metal film being attached on the metallic matrix.
8. the method that low temperature electrochemical reduction barium oxide according to claim 7 prepares vanadium metal, which is characterized in that institute
The method of stating further includes the step by the vanadium metal coating or vanadium metal film from the isolated metal vanadium powder of the metallic matrix
Suddenly.
9. the method that low temperature electrochemical reduction barium oxide according to claim 7 prepares vanadium metal, which is characterized in that institute
State vanadium metal coating or vanadium metal film with a thickness of 10 μm -500 μm.
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