CN103031568B - A kind of method of electrolytic preparation metallic lithium - Google Patents
A kind of method of electrolytic preparation metallic lithium Download PDFInfo
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- CN103031568B CN103031568B CN201110306668.5A CN201110306668A CN103031568B CN 103031568 B CN103031568 B CN 103031568B CN 201110306668 A CN201110306668 A CN 201110306668A CN 103031568 B CN103031568 B CN 103031568B
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Abstract
The method of electrolytic preparation metallic lithium: being the aqueous solution at least containing lithium ion in the anode cavities of electrolyzer, is the organic solvent with lithium ion conductive in cathode cavity; The barrier film separating anode cavities and cathode cavity is the lithium ion conductor ceramic membrane with lithium ion conductor character, or the composite membrane of lithium ion conductor and polymkeric substance; Under normal temperature and pressure, volts DS is applied in anode collector and cathode current collector, lithium ion in anode cavities in aqueous phase under voltage driven effect through the barrier film with lithium ion conductor characteristic, in the organic solvent of cathode cavity, be reduced to metallic lithium simple substance, and obtain product in the enrichment of cathode current collector surface deposition; Cathode cavity is inert atmosphere.Present invention, avoiding traditional high-temperature fusion electrolysis process and prepare severe condition required for metallic lithium, have energy consumption low, put forward lithium efficiency high, product purity is high, environmental friendliness and the feature such as raw material sources are extensive.
Description
Technical field
The present invention relates to a kind of method of lithium ion enrichment and electrochemical production metallic lithium, more specifically relate to a kind of method of electrolytic preparation metallic lithium.
Background technology
Lithium is the silvery white metal that occurring in nature is the lightest, because it has very strong chemically reactive and some other property, lithium by a large amount of for glass-ceramic industry, aerospace and energy field, be acknowledged as the energy metal of world's progress " promote ", its metal and salt are strategic materials significant in national economy and national defense construction.
Battery industry is that world's lithium resource consumes maximum market, the electronic product consumptions such as future world removable computer, mobile telephone, digital camera and mobile electric instrument can continue to increase, these electronic products need rechargeable cell, the chargeable number of times of lithium ion battery and generated energy are better than other battery, and estimated market value can more more options lithium ion battery; The exploitation of clean energy are paid attention in countries in the world, and hybrid vehicle will become the main stream traffic instrument in market, and hybrid vehicle probably selects lithium ion battery more.Glass and ceramic industry will become the second largest market of lithium product, because the constantly progress of world's glass industry technology, the various multifunctional glass such as ultra-clear glasses, energy-saving glass and environmental protection glass have huge market, lithium compound has multinomial beneficial effect to glass production, glass industry to the demand of lithium product by sustainable growth.Because the industry of metallic lithium own belongs to new forms of energy, field of new, in today of energy growing tension, sustained economic development, all thriving demand is maintained to novel material and new forms of energy in global range, thus drive the quick growth of upstream metal lithium, in whole modern industry and national defense industry industry chain (supply chain), be in critical positions, product has very strong irreplaceability.Under have Application Areas updating also in continuous expansion along with industrial technology, and may there is explosive growth in the market capacity in future due to the exploitation of product innovation, novelty teabag.According to related data prediction, by 2015, global metallic lithium demand will reach 7243 tons, and domestic needs amount also will reach 1368 tons.
Earth land lithium resource is mainly composed to be existed in salt lake brine, GEOTHERMAL WATER and granitic pegmatite-type mineral deposit, and basic unit price is 2637.75 ten thousand tons, and in above-mentioned lithium resource, bittern has accounted for more than 4/5ths of whole resource reserve.
The main method that metallic lithium is prepared in current industry the lithium salts that bittern extracts is carried out electrolysis obtain metal simple-substance.The technique that bittern extracts lithium salts mainly can be divided into the precipitator method, solvent extration, ion exchange adsorption, carborization etc., wherein precipitator method cardinal principle will concentrate containing lithium bittern evaporation in evaporatively, acidifying takes off boron again, then remaining boron and calcium, magnesium ion is separated, adding sodium carbonate etc. again makes lithium with the form Precipitation of Quilonum Retard, eventually passes dry obtained lithium carbonate product.But also there is technical process length, put forward lithium complex steps and energy consumption high shortcoming in the precipitator method.Solvent extration adopts organic solvent to be separated by the lithium salts in bittern and enters oil phase, then add hydrochloric acid to strip, be that lithium chloride enters aqueous phase and final separation obtains product, but the organic extract liquid that the method adopts is serious to equipment corrosion, and production cost is high, be difficult to realize industrialization.Lithium ion in bittern is carried out selective adsorption by adopting lithium ion polymeric adsorbent (CN1001928828A) or inorganic manganese system lamellar compound (CN101961634A) by ion exchange adsorption, carry out the operation of wash-out lithium subsequently, finally obtain lithium salts.The ion(ic)sieve granulation adopted in ion exchange adsorption is more difficult, and sorbent material loss is serious, and therefore large-scale application still exists a lot of problem.
The lithium resource limited relative to land, contain in seawater and have a large amount of lithium resources, according to surveying and determination, often liter of seawater is about containing lithium 0.17 milligram, estimate according to thalassographer, lithium estimation of reserves in ocean has 2,400 hundred million tons, and the Extracting Lithium from Seawater technology of research and development novel efficient, less energy-consumption, to grasping following strategic resource, is of great immediate significance.Ou Deng state of current Japan and Korea S has all started and extracted elemental lithium experiment from seawater, the human hairs such as T.Ishimori (US4243641) understand that a kind of separating for several times seawater obtains the technique (US4243641) of high density lithium salts, seawater pumps in the adsorption column of manganese and oxygen compound filling by Japan, make lithium ion selective adsorption in packed column, then desorption concentrating and separating obtains Quilonum Retard, and in seawater, the lithium rate of recovery is about is 27%.
Adopt the patent of electrochemical method extraction metallic lithium less, the people such as H.Kanoh take lithium manganese oxide as working electrode, purified from lithium salt electrolyte lithium compound, M.Itoh reports and applies current potential in lithium ion conductor both sides and concentrate the patent (US591843) that reduction obtains lithium salts.
Summary of the invention
The object of the present invention is to provide a kind of have energy consumption low, carry that lithium efficiency is high, product purity is high, the method for the electrolytic preparation metallic lithium of environmental friendliness and the feature such as raw material sources are extensive.
For achieving the above object, the method for electrolytic preparation metallic lithium provided by the invention, to the effect that: being the aqueous solution at least containing lithium ion in the anode cavities of electrolyzer, is the organic solvent with lithium ion conductive in cathode cavity; The barrier film separating anode cavities and cathode cavity is the lithium ion conductor ceramic membrane with lithium ion conductor character, or the composite membrane of lithium ion conductor and polymkeric substance;
Under normal temperature and pressure, volts DS is applied in anode collector and cathode current collector, lithium ion in anode cavities in aqueous phase under voltage driven effect through the barrier film with lithium ion conductor characteristic, in the organic solvent of cathode cavity, be reduced to metallic lithium simple substance, and obtain product in the enrichment of cathode current collector surface deposition; Cathode cavity is inert atmosphere.
The method of described electrolytic preparation metallic lithium, have organic electrolyte or the ionic liquid of lithium ion conductive in organic solvent wherein in cathode cavity, wherein organic electrolyte is one or more mixing of lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, LiBF4, hexafluoroarsenate lithium; Organic solvent is the mixing of one or more of acetonitrile, propylene carbonate, diethyl carbonate, methylcarbonate, NSC 11801; Ionic liquid is the mixing of one or more of 1-butyl-3-methyl-imidazoles phosphofluoric acid, 1-butyl-3-methyl-imidazoles Tetrafluoroboric acid, 1,2-dimethyl-4-fluorine pyrazoles a tetrafluoro borate.
The method of described electrolytic preparation metallic lithium, containing the aqueous solution of lithium ion in wherein in anode cavities, comprises the aqueous solution of lithium salts and the positively charged ion mixing solutions containing lithium ion.
The method of described electrolytic preparation metallic lithium, wherein comprises lithium chloride, Lithium Sulphate, lithium hydroxide, bittern, natural sea-water concentrated solution, the mixed solution of one or more containing lithium minerals solution containing the aqueous solution of lithium ion.
The method of described electrolytic preparation metallic lithium, wherein anode collector and cathode cavity collector select metal electrode, carbon or carbon composite electrode, metal oxide electrode or ceramic electrode.
The method of described electrolytic preparation metallic lithium, the lithium ion conductor ceramic membrane with lithium ion conductor character wherein separating anode cavities and cathode cavity is LISICON structure or LiLaTiO
3the ceramic membrane of perovskite structure; The composite membrane of lithium ion conductor and polymkeric substance is the lithium ion conductor of amorphous glass and the composite membrane of polymkeric substance, and polymkeric substance is fluoropolymer.
The method of described electrolytic preparation metallic lithium, wherein fluoropolymer is one or more of vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene or polyvinylidene difluoride (PVDF).
The method of described electrolytic preparation metallic lithium, wherein the composite membrane of lithium ion conductor and polymkeric substance is sandwich structure, middle layer take lithium ion conductor as matrix, respectively there is the porous membrane of one layer of polymeric the both sides of lithium ion conductor, polymkeric substance be vinylidene class, tetrafluoroethylene, polyethylene glycols one or more.
The method of described electrolytic preparation metallic lithium, wherein the composite membrane of lithium ion conductor and polymkeric substance is the nano particle of lithium ion conductor and the composite membrane of polymkeric substance, polymkeric substance be polyimide, polyethylene terephthalate one or more.
The method of described electrolytic preparation metallic lithium, its electrolyzer is room, the two poles of the earth or multipole room, and solution flows between room, each pole.
The present invention is by applying certain potentials in the barrier film both sides with lithium ion conductor character, anode side containing lithium ion in lithium aqueous phase under the effect of reduction potential, through middle barrier film, be reduced in the organic electrolyte of cathode cavity and at cathode current collector surface deposition, obtain high-purity lithium product.The present invention proposes lithium ion enrichment under a kind of mild conditions and prepare the novel method of metallic lithium, avoid traditional high-temperature fusion electrolysis process and prepare severe condition required for metallic lithium, there is energy consumption low, put forward lithium efficiency high, product purity is high, environmental friendliness and the feature such as raw material sources are extensive.
Accompanying drawing explanation
Fig. 1 is that the present invention is for lithium ion enrichment and electrochemical production metallic lithium device schematic diagram.
Fig. 2 is Li of the present invention
1.4al
0.4ti
1.6(PO
4)
3the XRD figure spectrum of lithium ion conductor ceramic membrane.
Fig. 3 is Li of the present invention
1.4al
0.4ti
1.6(PO
4)
3the stereoscan photograph of lithium ion conductor ceramic membrane.
Primary clustering nomenclature in accompanying drawing:
1 cathode cavity; 2 anode cavities; 3 organic electrolytes; 4 containing the lithium aqueous solution; 5 lithium ion conductor barrier films; 6 cathode current collectors; 7 anode collector; 8 direct supplys.
Embodiment
The present invention, by the barrier film with lithium ion conductor character, specifically comprises lithium ion conductor LiM
2-xn
x(PO
4)
3(0≤x≤0.8, M is Ti, Ge; N is the elements such as Al, Si, Ga) or LiLaTiO
3or lithium ion conductor-polymer inorganic organic composite barrier film both sides apply certain DC potential, anode side containing lithium ion in lithium aqueous phase under the effect of reduction potential, through middle barrier film, be reduced in the organic electrolyte of cathode cavity and at cathode current collector surface deposition, obtain high-purity lithium product.
In the present invention in cathode cavity for having the non-aqueous solvent of the organic electrolyte of lithium ion conductive or ionic liquid etc., wherein organic electrolyte is lithium hexafluoro phosphate (LiPF
6), trifluoromethyl sulfonic acid lithium (CF
3sO
3li), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6) etc. one or more mixing; Organic solvent is the mixing of one or more of acetonitrile (AN), propylene carbonate (PC), diethyl carbonate (DEC), methylcarbonate (DMC), NSC 11801 (EC) etc.; Ionic liquid can be but be not limited to 1-butyl-3-methyl-imidazoles phosphofluoric acid (BMIPF
6), 1-butyl-3-methyl-imidazoles Tetrafluoroboric acid (BMIBF
4), 1,2 dimethyl 4 fluorine pyrazoles a tetrafluoro borate (DMFPBF
4) etc.; Be the aqueous solution containing lithium ion in anode cavities, including, but not limited to lithium chloride (LiCl), Lithium Sulphate (Li
2sO
4), the aqueous solution of the common lithium salts such as lithium hydroxide (LiOH) and containing lithium ion positively charged ion mixing solutions (as bittern, natural sea-water concentrated solution, containing lithium minerals solution) etc.
For separating the barrier film with lithium ion conductor character in anode and cathode chamber in the present invention, comprise LiM including, but not limited to inorganic lithium ionophore
2-xn
x(PO
4)
3lISICON structure, the LiLaTiO of (0≤x≤0.8, M is Ti, Ge, and N is the elements such as Al, Si, Ga)
3the pottery of perovskite structure, the lithium ion conductor of amorphous glass and lithium ion conductor and organic polymer Inorganic whisker every closing film, its thickness is more than or equal to 0.01 millimeter.
In the present invention, the enrichment of lithium ion and the preparation condition of metallic lithium are normal temperature and pressure; certain volts DS is applied between negative electrode and anode; it negative electrode is negative potential; realize lithium ion and the organic electrolyte in cathodic area, be reduced to lithium simple substance from positive column through barrier film; and at cathode current collector surface deposition; wherein cathodic area reaction is carried out under protection of inert gas atmosphere, enters to prevent air and water.
Be the aqueous solution containing lithium ion in Anodic chamber of the present invention, including, but not limited to lithium chloride (LiCl), Lithium Sulphate (Li
2sO
4), the aqueous solution of the common lithium salts such as lithium hydroxide (LiOH) and containing lithium ion positively charged ion mixing solutions (as bittern, natural sea-water concentrated solution, containing lithium minerals solution) etc.
Middle-jiao yang, function of the spleen and stomach cathode cavity collector of the present invention, can select metal electrode (as stainless steel, nickel, copper etc.), carbon dioxide process carbon electrode, metal oxide electrode or ceramic electrode etc. as required.
In the present invention, electrochemistry carries the energy source of lithium is thermoelectricity, solar electrical energy generation, wind power generation, ocean power generation etc.
The key step of a kind of lithium ion enrichment provided by the invention and electrochemical production metallic lithium is:
1) cathode current collector is fixed in cathode cavity, and injects organic electrolyte, by lithium ion conductor barrier film, cathode cavity is sealed;
2) the rich lithium aqueous solution is injected anode cavities;
3) by deposition apparatus put in circuit, and between anode cavities and cathode cavity, apply the current potential being greater than 3V, carry out the metallic lithium deposition of 1-24 hour;
4) by step 3 deposition obtain metallic lithium together with cathode current collector be transferred under an argon atmosphere the glove box being full of argon gas carry out processing preservation;
5) organic electrolyte in cathode cavity reclaimed and be placed in glove box preservation, can recycle.
It is high that the method extracting metallic lithium based on lithium ion conductor from seawater/bittern provided in the present invention has the lithium purity obtained, the features such as energy consumption is low, environmental friendliness.
The present invention adopts and applies current potential in lithium ion conductor barrier film both sides, from containing enriching lithium ion in the lithium aqueous solution or prepare metallic lithium, is further illustrated the embodiment of technical solution of the present invention by following embodiment.
Embodiment 1
Two pieces of thickness as shown in Figure 1, are 5mm by device of the present invention, and area is 100cm
2copper sheet is individually fixed in positive cathode cavity both end sides as collector, gets 500ml lithium hexafluoro phosphate (LiPF
6) organic electrolyte injection cathode cavity also complete covering copper collector, be 1mm by area x thickness, area is 120cm
2lithium ion conductor pottery LiTi
2(PO
4)
3be fixed between cathode cavity and anode cavities, keep the excellent sealing of cathode cavity, get 500ml concentrated seawater and inject anode cavities, by positive cathode wire put in circuit, regulating voltage was 3.2V, through 24 hours depositions, anode cavities maritime interior waters is discharged, organic electrolyte in cathode cavity is reclaimed in the glove box being full of argon gas, obtains the collector copper sheet depositing metallic lithium, test result show gained to metallic lithium purity reach more than 99.8%.The lithium ion conductor pottery LiTi wherein adopted
2(PO
4)
3the X ray diffracting spectrum of barrier film is shown in Fig. 2.Fig. 3 is shown in by the surface topography electron micrograph of this ceramic membrane.
Embodiment 2
Be 4mm by two pieces of thickness, area is 100cm
2nickel sheet is individually fixed in positive cathode cavity both end sides as collector, and get 500ml carbon propylene carbonate (PC) organic electrolyte and inject cathode cavity and cover nickel collector completely, be 1mm by area x thickness, area is 120cm
2lithium ion conductor pottery Li
0.5la
0.5tiO
3be fixed between cathode cavity and anode cavities, keep the excellent sealing of cathode cavity, get 500ml concentrated brine and inject anode cavities, by positive cathode wire put in circuit, regulating voltage is 3.1V, through 24 hours depositions, is discharged by bittern in anode cavities, organic electrolyte in cathode cavity is reclaimed in the glove box being full of argon gas, obtains the collector nickel sheet depositing metallic lithium.
Embodiment 3
Be 4mm by two pieces of thickness, area is 100cm
2stainless steel substrates is individually fixed in positive cathode cavity both end sides as collector, and get 500ml methylcarbonate (DMC) organic electrolyte and inject cathode cavity and cover stainless steel collector completely, be 1mm by area x thickness, area is 120cm
2liTi
2(PO
4)
3-PVDF-HFP organo-mineral complexing barrier film is fixed between cathode cavity and anode cavities, keep the excellent sealing of cathode cavity, get 500ml concentrated brine and inject anode cavities, by positive cathode wire put in circuit, regulating voltage is 3.4V, through 24 hours depositions, is discharged by bittern in anode cavities, organic electrolyte in cathode cavity is reclaimed in the glove box being full of argon gas, obtains the collector stainless steel substrates depositing metallic lithium.
Claims (7)
1. the method for an electrolytic preparation metallic lithium, it is characterized in that: be the aqueous solution at least containing lithium ion in the anode cavities of electrolyzer, it is the organic solvent with lithium ion conductive in cathode cavity, have organic electrolyte or the ionic liquid of lithium ion conductive in organic solvent in cathode cavity, wherein organic electrolyte is the mixing of one or more in lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, LiBF4, hexafluoroarsenate lithium; Organic solvent is the mixing of one or more in acetonitrile, propylene carbonate, diethyl carbonate, methylcarbonate, NSC 11801; Ionic liquid is the mixing of one or more in 1-butyl-3-methyl-imidazoles phosphofluoric acid, 1-butyl-3-methyl-imidazoles Tetrafluoroboric acid, 1,2-dimethyl-4-fluorine pyrazoles a tetrafluoro borate;
The barrier film separating anode cavities and cathode cavity is the lithium ion conductor ceramic membrane with lithium ion conductor character, or
The composite membrane of lithium ion conductor and polymkeric substance;
The lithium ion conductor ceramic membrane with lithium ion conductor character separating anode cavities and cathode cavity is LISICON structure or LiLaTiO
3the ceramic membrane of perovskite structure;
The composite membrane of lithium ion conductor and polymkeric substance is the nano particle of the lithium ion conductor of amorphous glass and the composite membrane of polymkeric substance, and wherein polymkeric substance is one or more in vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene or polyvinylidene difluoride (PVDF);
Under normal temperature and pressure, volts DS is applied in anode collector and cathode current collector, lithium ion in anode cavities in aqueous phase under voltage driven effect through the barrier film with lithium ion conductor characteristic, in the organic solvent of cathode cavity, be reduced to metallic lithium simple substance, and obtain product in the enrichment of cathode current collector surface deposition;
Cathode cavity is inert atmosphere.
2. the method for electrolytic preparation metallic lithium according to claim 1, is characterized in that: anode cavities includes the aqueous solution of lithium ion, comprises the aqueous solution of lithium salts and the positively charged ion mixing solutions containing lithium ion.
3. the method for electrolytic preparation metallic lithium according to claim 1 and 2, is characterized in that: the aqueous solution containing lithium ion comprises lithium chloride, Lithium Sulphate, lithium hydroxide, bittern, natural sea-water concentrated solution, mixed solution containing one or more in lithium minerals solution.
4. the method for electrolytic preparation metallic lithium as claimed in claim 1, is characterized in that: anode collector and cathode current collector select metal electrode, carbon or carbon composite electrode, metal oxide electrode or ceramic electrode.
5. the method for electrolytic preparation metallic lithium according to claim 1, it is characterized in that: the composite membrane of lithium ion conductor and polymkeric substance is sandwich structure, middle layer take lithium ion conductor as matrix, respectively there is the porous membrane of one layer of polymeric the both sides of lithium ion conductor, and polymkeric substance is one or more in vinylidene class, tetrafluoroethylene, polyethylene glycols.
6. the method for electrolytic preparation metallic lithium according to claim 1, it is characterized in that: the composite membrane of lithium ion conductor and polymkeric substance is the nano particle of lithium ion conductor and the composite membrane of polymkeric substance, and polymkeric substance is one or more in polyimide, polyethylene terephthalate.
7. the method for electrolytic preparation metallic lithium according to claim 1, is characterized in that: electrolyzer is multipole room, and solution flows between room, each pole.
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