CN103797159A - Method for recovering lithium using an electrochemical method - Google Patents
Method for recovering lithium using an electrochemical method Download PDFInfo
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- CN103797159A CN103797159A CN201280027626.0A CN201280027626A CN103797159A CN 103797159 A CN103797159 A CN 103797159A CN 201280027626 A CN201280027626 A CN 201280027626A CN 103797159 A CN103797159 A CN 103797159A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 118
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 84
- 238000002848 electrochemical method Methods 0.000 title abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims abstract description 32
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000011889 copper foil Substances 0.000 claims abstract description 18
- 239000004020 conductor Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims description 41
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 239000005030 aluminium foil Substances 0.000 claims description 18
- 229910009343 Li1.33 Mn1.67 O4 Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract 4
- 238000013019 agitation Methods 0.000 abstract 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 more specifically Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
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- 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
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a method for recovering lithium using an electrochemical method. More particularly, the method according to the present invention comprises: putting a raw material made of lithium manganese oxide, a conductive material, and a binder into an agitator; performing agitation for the production of sludge by putting a solvent into the agitator into which the raw material is put through the inputting of the raw material; coating an aluminum foil or a copper foil with the sludge produced through the performing of the agitation; drying the sludge with which the aluminum foil or the copper foil is coated through the coating; evaluating a reaction potential using cyclic voltammetry by putting the aluminum foil or the copper foil, which is coated with the sludge dried through the drying, into an electrolyzer provided with an electrode plate and a lithium metal; maintaining the reaction potential evaluated by means of evaluating the reaction potential for the precipitation of lithium on a surface of the electrode plate; and separating the lithium precipitated on the surface of the electrode plate through the precipitating of the lithium.
Description
Technical field
Originally the present invention relates to the recovery method of the lithium that utilizes electrochemical process, more specifically, relate to one and make lithium manganese oxide realize mud, application cycle voltammetry, reclaims the recovery method of the lithium that utilizes electrochemical process of lithium from lithium manganese oxide.
Background technology
The present invention relates to the recovery method of the lithium that utilizes electrochemical process, more specifically, relate to one and make lithium manganese oxide realize mud, application cycle voltammetry, reclaims the recovery method of the lithium that utilizes electrochemical process of lithium from lithium manganese oxide.
Due to the development rapidly of mobile phone, notebook computer and ev industry, the international demand in mobile model energy supply source increases gradually.As this energy supply source, the application of lithium secondary battery just increases at explosion type, and at present, lithium secondary battery industry is just launched centered by Korea S, Japan, China, along with the sharply increase of lithium secondary battery demand, also sharply increase as the consumption of the lithium of core material.In addition, lithium for making tritium propagation, therefore, further strengthens the requirement of lithium in thermonuclear fusion (thermonuclear fusion) generating that is sent to great expectations as energy supply of new generation source.
In seawater, dissolve by inference the lithium ion of 2,500 hundred million tons of having an appointment, start the lithium source of supply that is considered to important.But its concentration is very low, be every 1 liter of seawater 0.17mg, consider the economy that lithium ion reclaims, expense reclaims the system of lithium ion cheaply selectively.
In order to reclaim lithium ion from seawater, study the method such as ion exchange adsorption, solvent-extraction process, coprecipitation method, in these are attempted, having utilized the lithium ion recovery method of the Mn oxide based inorganic material adsorbent of the ion exchange property with very high selectivity is one of most preferred method.Therefore, developed diversified Mn oxide based inorganic material adsorbent (with reference to Ind.Eng.Chem.Res., 40,2054,2001).Mn oxide is that inorganic adsorbent can be in the liquid that comprises lithium ion, by means of the ion-exchange of hydrogen ion and lithium ion,, adsorb the lithium ion of described liquid by means of phase place extraction (topotactic extraction), then, adsorb the inorganic adsorbent of lithium ion in diluted hydrochloric acid aqueous solution, by the ion-exchange of hydrogen ion and lithium ion, can reclaim lithium ion.Therefore, this Mn oxide is that inorganic adsorbent has advantages of can Reusability.
But, utilized in the past aqueous acid to tens of kilograms even the particulate form lithium manganese oxide powder of the above approximately 10 a large amount of μ m sizes of ton unit process and form the step of Mn oxide, need large-scale acid resistance tank and for make aqueous acid can with the flow-through appt of described powder effecting reaction, in addition, also append receive after requiring to process with described aqueous acid separation and the drying process of liquid.As mentioned above, lithium recovery method is in the past very complicated loaded down with trivial details, has the problem such as should be noted that in treatment step.
Summary of the invention
(1) technical problem that will solve
The object of the present invention is to provide a kind of recovery method of the lithium that utilizes electrochemical process that demonstrates the effect that operation is simple, the lithium rate of recovery is high.
Another object of the present invention is to provide a kind of owing to using electrochemical process, thereby little for reclaiming the consumption of the chemical substance that lithium uses, demonstrate the recovery method of the lithium that utilizes electrochemical process of economic impacts.
(2) technical scheme
Object of the present invention is reached by the recovery method that a kind of lithium that utilizes electrochemical process is provided, and it is characterized in that, comprising: raw material drops into step, and the raw material being made up of lithium manganese oxide, conductor and binding agent is dropped into stirrer; Whipping step drops into solvent in the stirrer that drops into described raw material, manufactures mud; Whipping step drops into solvent in the stirrer that has dropped into raw material by described raw material input step, manufactures mud; Application step, coats aluminium foil or Copper Foil the mud of manufacturing by described whipping step; Drying step, is dried the mud of coating aluminium foil or Copper Foil by described application step; Reaction electromotive force is confirmed step, by the dry coating of described drying step aluminium foil or the Copper Foil of mud put into the electrolyzer that possesses battery lead plate and lithium metal, utilize cyclic voltammetry to confirm to react electromotive force; Lithium is separated out step, and electrolyzer is maintained at by described reaction electromotive force and confirms the reaction electromotive force that step is confirmed, lithium is separated out on the surface of battery lead plate; And lithium separating step, separate separate out the lithium that step separates out at electrode plate surface by described lithium.
According to preferred feature of the present invention, described raw material is made up of lithium manganese oxide 100 weight parts, conductor 25 to 35 weight parts and binding agent 10 to 20 weight parts.
According to more preferably feature of the present invention, described lithium manganese oxide has can use general formula LixMyMnzO
4the spinel structure of representative, described x is 1.33 to 2, and described M is made up of the one of selecting from the group forming with Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Si, Mg and Zn, and described y is 0 to 0.5, and described z is 1 to 1.67.
According to more preferably feature of the present invention, described lithium manganese oxide is by the Li from share limit with 4 valency mn ions
1.6mn
1.6o
4, Li
1.33mn
1.67o
4and Li
2mnO
3the one of selecting in the group forming forms.
According to more preferably feature of the present invention, described conductor is carbon black.
According to more preferably feature of the present invention, described binding agent is polyvinylidene difluoride (PVDF) or Walocel MT 20.000PV.
According to more preferably feature of the present invention, described solvent is made up of N-first-2-Pyrrolidone or water.
According to more preferably feature of the present invention, described whipping step utilizes stirrer to carry out 3 hours.
According to more preferably feature of the present invention, described drying step utilizes a conventional oven, carries out after 30 minutes at 60 ℃, in vacuum drying oven, carries out 12 to 20 hours with the temperature of 80 ℃.
According to more preferably feature of the present invention, described reaction electromotive force confirms that step, described lithium separate out step and described lithium separating step and carry out having filled in the glove box of argon gas or kiln.
According to more preferably feature of the present invention, described electrolyzer has contained to dissolve the non-aqueous electrolyte of lithium salts.
According to more preferably feature of the present invention, described battery lead plate forms with lithium plate or copper coin, with net morphosis.
The recovery method of the lithium that utilizes electrochemical process of the present invention, operation is simple, and demonstrates the remarkable lithium rate of recovery.
In addition, Applied Electrochemistry method, few for reclaiming the consumption of the chemical substance that uses of lithium, thereby demonstrate remarkable economy.
(3) beneficial effect
The recovery method of the lithium that utilizes electrochemical process of the present invention, operation is simple, and demonstrates the remarkable lithium rate of recovery.
In addition, Applied Electrochemistry method, few for reclaiming the consumption of the chemical substance that uses of lithium, thereby demonstrate remarkable economy.
Accompanying drawing explanation
Fig. 1 is the schema that shows the recovery method of the lithium that utilizes electrochemical process of the present invention.
Fig. 2 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.33mn
1.67o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (50 times) show that lithium is separated out situation on copper grid.
Fig. 3 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.33mn
1.67o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (200 times) show that lithium is separated out situation on copper grid.
Fig. 4 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.33mn
1.67o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (500 times) show that lithium is separated out situation on copper grid.
Fig. 5 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.33mn
1.67o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (1000 times) show that lithium is separated out situation on copper grid.
Fig. 6 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.33mn
1.67o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (1500 times) show that lithium is separated out situation on copper grid.
Fig. 7 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.6mn
1.6o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (50 times) show that lithium is separated out situation on copper grid.
Fig. 8 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.6mn
1.6o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (200 times) show that lithium is separated out situation on copper grid.
Fig. 9 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.6mn
1.6o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (500 times) show that lithium is separated out situation on copper grid.
Figure 10 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.6mn
1.6o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (1000 times) show that lithium is separated out situation on copper grid.
Figure 11 is in the recovery method of the lithium that utilizes electrochemical process of the present invention, uses Li
1.6mn
1.6o
4as lithium manganese oxide, separate out while using copper grid as battery lead plate in step at lithium, utilize flying-spot microscope (FE-SEM, Hitachi S-4800) to take the photo that (1500 times) show that lithium is separated out situation on copper grid.
Reference numeral
S101: raw material drops into step S103: whipping step
S105: application step S107: drying step
S109: reaction electromotive force is confirmed step S111: lithium is separated out step
S113: lithium separating step
Embodiment
Describe the physical property of the preferred embodiments of the present invention and each composition below in detail, but this is for describing in detail, so that those skilled in the art can easily carry out an invention, therefore, and does not mean that restriction technological thought of the present invention and category.
The recovery method of the lithium that utilizes electrochemical process of the present invention comprises: raw material drops into step (S101), and the raw material being made up of lithium manganese oxide, conductor and binding agent is dropped into stirrer; Whipping step (S103) drops into solvent in the stirrer that drops into described raw material, manufactures mud; Application step (S105), coats aluminium foil or Copper Foil the mud of manufacturing by described whipping step; Drying step (S107), is dried the mud of coating aluminium foil or Copper Foil by described application step; Reaction electromotive force is confirmed step (S109), by the dry coating of described drying step aluminium foil or the Copper Foil of mud put into the electrolyzer that possesses battery lead plate and lithium metal, utilize cyclic voltammetry to confirm to react electromotive force; Lithium is separated out step (S111), and electrolyzer is maintained at by described reaction electromotive force and confirms the reaction electromotive force that step is confirmed, lithium is separated out on the surface of battery lead plate; And lithium separating step (S113), separate separate out the lithium that step separates out at electrode plate surface by described lithium.
Described raw material drops into step (S101) as the step that the raw material being made up of lithium manganese oxide, conductor and binding agent is dropped into stirrer, preferred described raw material is made up of lithium manganese oxide 100 weight parts, conductor 25 to 35 weight parts and binding agent 10 to 20 weight parts, and described lithium manganese oxide has can use general formula LixMyMnzO
4the spinel structure of representative, described x is 1.33 to 2, and described M is made up of the one of selecting from the group forming with Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Si, Mg and Zn, and described y is 0 to 0.5, and described z is 1 to 1.67.
More preferably, in order to separate out in step (S111) and to demonstrate outstanding reactivity at described lithium, described lithium manganese oxide is by the Li from share limit with 4 valency mn ions
1.6mn
1.6o
4, Li
1.33mn
1.67o
4and Li
2mnO
3in the group forming, the one selected forms, described by from Li
1.6mn
1.6o
4, Li
1.33mn
1.67o
4and Li
2mnO
3a kind of lithium manganese oxide of selecting in the group forming, by γ-MnOOH or Mn
2o
3with the manufacture of reacting of LiOH, more specifically, γ-MnOOH or Mn
2o
3with the microwave (Microwave) of LiOH in aqueous solvent internal radiation 915 to 2450Hz, be heated to the temperature range of 100 to 140 ℃, reaction 30 to 120 minutes, manufacture after lithium manganese composite oxide thermal treatment manufacture under oxygen atmosphere.
In addition, preferred described conductor is made up of the outstanding carbon black of electroconductibility, described binding agent is made up of the polyvinylidene difluoride (PVDF) that can make described lithium manganese oxide be combined physically with described conductor (PVDF, Polyvinylidene fluoride) or Walocel MT 20.000PV.
Described whipping step (S103) is as drop into solvent in the stirrer that drops into described raw material, manufacture the step of mud, having dropped in the stirrer of raw material, drop into N-first-2-Pyrrolidone (N-methyl-2-Pyrrolidone) or water as solvent, make raw material realize mud.
Utilize described solvent to make described raw material realize the reason of mud, for ease of described raw material composition is fixed on to described aluminium foil, described solvent slowly drops into, until there is the viscosity of the degree that the blade of the stirrer using in whipping step (S103) can rotate smoothly, preferably carry out 3 hours.
Described application step (S105) is as the step of the mud of manufacturing by described whipping step (S103) being coated to aluminium foil (Aluminum Foil) or Copper Foil (Cupper Foil), be the mud of manufacturing by described whipping step (S103), utilize coating machine (Doctor Blade) to coat the step of aluminium foil.
Described drying step (S107) is as the mud of coating aluminium foil or Copper Foil by described application step (S105) is carried out to dry step, the lithium manganese oxide reactive significantly decline in described electrolyzer due to mud state, and the step of the dry impurity of removing such as the solvent etc. containing in mud.
Now, described drying step (S107) utilizes a conventional oven, at 60 ℃, carry out after 30 minutes, in vacuum drying oven, carry out 12 to 20 hours with the temperature of 80 ℃, drying step (S107) is divided into as mentioned above to the reason of carrying out for twice, because utilize a conventional oven to carry out for the first time after drying step, remove to a certain extent the liquid composition containing in mud, in the time dropping into described vacuum drying oven, prevent from aluminium foil or Copper Foil landing, therefore, in a conventional oven, carried out dry for the first time mud complete drying in vacuum drying oven.
Described reaction electromotive force confirm step (S109) as by the dry coating of described drying step (S107) aluminium foil or the Copper Foil of mud put into the electrolyzer that possesses battery lead plate and lithium metal, with cyclic voltammetry (CV, Cyclic Voltammetry) confirm the step of reaction electromotive force, preferably under having contained to dissolve the state of non-aqueous electrolyte of 1 mole of lithium salts, described electrolyzer carries out.
Possess after electrolyzer as above, to the aluminium foil of described mud or Copper Foil be coated with as working electrode, using described battery lead plate as comparative electrode, using described lithium metal as standard electrode, implement cyclic voltammetry, as mentioned above, possessing in the electrolyzer of the three-electrode battery being formed by the aluminium foil that has been coated with mud, battery lead plate and lithium metal, apply the electromotive force of 0.2 to 4.3 volt of (V) scope, carry out cyclic voltammetry with the sweep velocity of 1mVs-1, confirm reaction electromotive force.
Now, preferred described battery lead plate forms with nickel plate or copper coin, with net (copper grid) morphosis.
Described lithium is separated out step (S111) and is confirmed as the electromotive force of electrolyzer being maintained at by described reaction electromotive force the reaction electromotive force that step (S109) is confirmed, the step that lithium is separated out on the surface of battery lead plate, confirming that at described reaction electromotive force the reaction electromotive force of confirming in step (S109) puts on after described electrolyzer, through given time, the lithium composition containing in the drying sewage sludge being coated with on described aluminium foil or Copper Foil is realized ionization, move to behind the surface of battery lead plate, precipitate into the surface of battery lead plate.
Described lithium separating step (S113) is as the step separating separate out lithium that step (S111) separates out at electrode plate surface by described lithium, lithium is separated out after set degree on the surface of described battery lead plate, battery lead plate, from electrolyzer separates, is scraped to the lithium that electrode plate surface separates out and separates.
Now, preferred described reaction electromotive force confirms that step (S109), described lithium separate out step (S111) and described lithium separating step (S113) and carry out filling in the glove box (Grove Box) of argon gas or kiln, carry out, after described step, can obtaining highly purified lithium filling in the glove box of argon gas or kiln.
Therefore, the recovery method of the lithium that utilizes electrochemical process of the present invention is as shown in following Fig. 2 to Figure 11, and operation is simple, and demonstrates the remarkable lithium rate of recovery.
In addition, Applied Electrochemistry method, few for reclaiming the consumption of the chemical substance that uses of lithium, thereby demonstrate remarkable economy.
Claims (12)
1. a recovery method that utilizes the lithium of electrochemical process, is characterized in that, comprising:
Raw material drops into step, and the raw material being made up of lithium manganese oxide, conductor and binding agent is dropped into stirrer;
Whipping step drops into solvent and stirs in the stirrer that drops into described raw material, manufactures mud;
Application step, coats aluminium foil or Copper Foil the mud of manufacturing by described whipping step;
Drying step, is dried the mud of coating aluminium foil or Copper Foil by described application step;
Reaction electromotive force is confirmed step, by the dry coating of described drying step aluminium foil or the Copper Foil of mud put into the electrolyzer that possesses battery lead plate and lithium metal, utilize cyclic voltammetry to confirm to react electromotive force;
Lithium is separated out step, and electrolyzer is maintained at by described reaction electromotive force and confirms the reaction electromotive force that step is confirmed, lithium is separated out on the surface of battery lead plate; And
Lithium separating step, separates separate out the lithium that step separates out at electrode plate surface by described lithium.
2. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described raw material is made up of lithium manganese oxide 100 weight parts, conductor 25 to 35 weight parts and binding agent 10 to 20 weight parts.
3. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described lithium manganese oxide has can use general formula LixMyMnzO
4the spinel structure of representative, described x is 1.33 to 2, and described M is made up of the one of selecting from the group forming with Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Si, Mg and Zn, and described y is 0 to 0.5, and described z is 1 to 1.67.
4. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described lithium manganese oxide is by the Li from share limit with 4 valency mn ions
1.6mn
1.6o
4, Li
1.33mn
1.67o
4and Li
2mnO
3the one of selecting in the group forming forms.
5. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described conductor is carbon black.
6. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described binding agent is polyvinylidene difluoride (PVDF) or Walocel MT 20.000PV.
7. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described solvent is made up of N-first-2-Pyrrolidone or water.
8. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described whipping step utilizes stirrer to carry out 3 hours.
9. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described drying step utilizes a conventional oven, carries out after 30 minutes at 60 ℃, in vacuum drying oven, carries out 12 to 20 hours with the temperature of 80 ℃.
10. the recovery method of the lithium that utilizes electrochemical process according to claim 1, is characterized in that,
Described reaction electromotive force confirms that step, described lithium separate out step and described lithium separating step and carry out having filled in the glove box of argon gas or kiln.
The recovery method of 11. lithiums that utilize electrochemical process according to claim 1, is characterized in that,
Described electrolyzer has contained to dissolve the non-aqueous electrolyte of lithium salts.
The recovery method of 12. lithiums that utilize electrochemical process according to claim 1, is characterized in that,
Described battery lead plate forms with lithium plate or copper coin, with net morphosis.
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| KR1020110139288A KR101345559B1 (en) | 2011-12-21 | 2011-12-21 | Recovery method of lithium using electrochemistry process |
| KR10-2011-0139288 | 2011-12-21 | ||
| PCT/KR2012/010737 WO2013094917A1 (en) | 2011-12-21 | 2012-12-11 | Method for recovering lithium using an electrochemical method |
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| CN105937038A (en) * | 2016-06-17 | 2016-09-14 | 天齐锂业股份有限公司 | Method for recycling lithium in lithium iron phosphate through electrochemical method |
| CN107541753A (en) * | 2017-08-10 | 2018-01-05 | 中国铝业股份有限公司 | A kind of removing method of the Hull cell containing lithium in lithium electrolyte |
| CN110592617A (en) * | 2019-08-29 | 2019-12-20 | 青海物产工业投资有限公司 | Secondary starting method for full-series power failure of aluminum electrolysis cell |
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| CN104112882A (en) * | 2014-07-24 | 2014-10-22 | 国家电网公司 | Method for electrochemically extracting lithium from positive electrode material of lithium ion battery |
| KR102606229B1 (en) | 2020-10-29 | 2023-11-23 | 코스모화학 주식회사 | Selective recovery of lithium from ternary cathode active material of spent lithium ion batteries |
| KR20230081900A (en) | 2021-11-30 | 2023-06-08 | 코스모화학 주식회사 | Selective recovery of valuable metal from cathode active material of spent lithium ion batteries |
| KR102631721B1 (en) | 2021-11-30 | 2024-02-01 | 코스모화학 주식회사 | Selective recovery of lithium from ternary cathode active material of spent lithium ion batteries |
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| KR101345559B1 (en) | 2014-01-02 |
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