CN104577243B - Method for recovering lithium resource from lithium-ion-containing solution by using lithium ion carrier - Google Patents
Method for recovering lithium resource from lithium-ion-containing solution by using lithium ion carrier Download PDFInfo
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- CN104577243B CN104577243B CN201410681653.0A CN201410681653A CN104577243B CN 104577243 B CN104577243 B CN 104577243B CN 201410681653 A CN201410681653 A CN 201410681653A CN 104577243 B CN104577243 B CN 104577243B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a method for recovering a lithium resource from a lithium-ion-containing solution by using a lithium ion carrier and belongs to the technical field of extraction of lithium sources. The method comprises the following steps: under a reducing condition, absorbing lithium ions from a lithium ion solution to be recovered by a lithium ion carrier in a poor lithium state to obtain the lithium ion carrier in a rich lithium state; and under an oxidizing condition, releasing lithium ions from the lithium ion carrier in the rich lithium state and regenerating the lithium ion carrier in the poor lithium state. Through repeated recycling, the lithium source is continuously recovered by the lithium ion carrier from the lithium ion source. In a lithium ion recovery process, consumption of chemical raw materials is avoided, so that the method meets the requirement of atomic economic reaction and has the advantages of cleanness, efficiency and no discharge of waste liquid. The lithium ion carrier provided by the invention theoretically has an infinite cycle index and the actual cycle life reaches 500-1000 times.
Description
Technical field
The invention belongs to the technical field of lithium resource is extracted, it is specially a kind of to utilize lithium ion carrier from solution containing lithium ion
The middle method for extracting lithium resource, is suitable for any natural and through processing solution containing lithium ion or waste liquid containing lithium, main to wrap
Lake containing lithium salts, salt pan concentration are included containing the old halogen of lithium and the lithium-containing solution that used Li ion cell etc. is obtained is processed.
Background technology
Lithium, is widely used in its more active chemical property as the minimum metallic element of atomic weight in nature
Lithium ion battery, metal hydride and and the field such as nuclear fusion.With fast developments such as lithium ion batteries, lithium resource is promoted
The quick of demand is incremented by, and promotes the new exploitation containing lithium minerals and the recovery of useless lithium resource.It is according to ASSOCIATE STATISTICS, main at present
Can be used to exploit the lithium resource for utilizing is granite peamatite mineral deposit, bittern deposit and sea water mineral deposit.Due to surveying containing lithium deposite
Visit that difficulty is larger, can be exploited in the world during the country for lithium carbonate being directly produced using salt containing lithium and lithium ore mainly has at present
State, the U.S., Chile and Argentina.China's lithium resource is mainly distributed on the ground such as Qinghai, Tibet, Sichuan, Jiangxi, Xinjiang, its Chinese and Western
Hide the Salt Lake Zabuye of the northwestward and the Bange-Du Jiali lakes of east, and the Cha Er Han of Chaidamu Basin, Qinghai Province, Yi Liping,
In the salt lakes such as West Taijinar, East Taijinaier and big Chai Dan.At this stage, extraction of the China to lithium resource with primary lithium ore deposit be still
It is main, how to accelerate China and secondary lithium resource is developed and reclaimed from lithium-containing solution, the health for becoming China's lithium salts industry can be held
Continue fast-developing key.
At present it has been reported that the separation of lithium salts is mainly had with recovery method：The sedimentation method, solvent extraction, dipping calcination method and
Absorption method etc..The typical sedimentation method such as China Patent Publication No. CN1335263 (is divided from salt lake brine with high magnesium-lithium ratio with carbonizatin method
From the method that magnesium lithium produces lithium carbonate) using carbonizatin method from magnesium lithium solution produce lithium carbonate method.Generally, at sedimentation method technique
Reason process is complicated, as magnesium carbonate can absorb lithium ion in precipitation process, therefore contains during the method is not suitable for processing stock solution
A large amount of Mg2+And Ca2+Etc. the solution containing lithium ion of a large amount of alkaline-earth metal.Solvent extraction is generally utilized and contains exchangeable cations
The cationic liquid of functional group is exchanging the lithium ion in solution, it is considered to be from high magnesium chloride Salt-lake brine carry lithium
One of effective ways, a kind of its typical patent of invention CN87103431 (method that anhydrous Lithium chloride is extracted from salt containing lithium)
Report the Chinese Academy of Sciences's Qinghai Salt Lake institute employing 50%-70%TBP, 30%-50%200 solvent naphtha is consisted of as solvent
To extract big bavin denier high magnesium lithium-containing ion waste liquid, the method has that extractant is expensive, and the loss of regenerative process water solublity is serious, institute
There is no commercial Application to report at present.Patent CN1724372 (produces lithium carbonate, magnesium oxide and hydrochloric acid with high-Mg Li-contained bittern
Method) technological process to be spray-dried, calcine, the washing that adds water, evaporation and concentration, precipitate operation after obtain lithium carbonate product.Should
Method calcines Li-Mg contained salt using up to 1200 DEG C high temperature so as to which pyrolytic is magnesium oxide, while lithium carbonate is reclaimed, should
Although technique consumption of raw materials is less, the problem for existing is that the subtractive process of magnesium can make flow process be intended to complexity, and production process
Middle gas containing hydrogen chloride is serious to equipment corrosion, and energy consumption is higher.Absorption method is using the absorption to the selective absorption of lithium ion
Then lithium ion is eluted, reaches lithium ion purpose detached with other foreign ions, wherein allusion quotation adsorbing lithium ion by agent
The lithium adsorbent of type such as MnO2Ion sieve, using which to Li+There is special Selective adsorption to realize the absorbability of lithium ion.Specially
Sharp CN1511963 (method of extracting lithium from salt lake brine by manganese dioxide) describes and must contain lithium concentration for salt pan solar evaporation
Salt, uses MnO2Adsorbent selects absorption Li+Afterwards, the Li being adsorbed with hydrochloric acid solution eluting+, then refine, concentrate through eluent
Afterwards, obtain raw material qualified needed for lithium carbonate or lithium chloride.(one kind is from lithium ion battery for similar patent such as CN101654741
The method of middle separation and recovery lithium and cobalt) sample after a kind of use lithium magnesium Mn oxide pickling processes is disclosed as used Li ion electricity
Lithium ion adsorbent containing lithium filtrate after pond acid is molten, and combined with submerged ultrafiltration element, Lithium-ion embeding is made to ion sieve
After proceeding to maximal absorptive capacity in interstitial void, eluting is carried out to adsorbent with acid solution finally, reach the purpose for reclaiming lithium.I
Observe, the method needs secondary utilization hydrochloric acid to be processed before and after eluting, not only creates serious equipment corrosion, give up
Acid solution, and the chlorine that processing procedure is produced also easily causes environmental pollution.
In view of this, the lithium-containing solution for producing for current a large amount of original lithium mineral products or recovery lithium battery process, invention one
The recovery lithium resource technique of clean and effective is planted, and is at utmost reduced in lithium resource removal process, related chemistry raw material or auxiliary
The discharge of material, makes the recovery of lithium resource meet atom economy method extremely urgent.
The content of the invention
The purpose of the present invention is to overcome problem of the prior art, there is provided a kind of novel green method reclaims lithium ion, that is, carry
A kind of method for extracting lithium resource for utilization lithium ion carrier from solution containing lithium ion.
For achieving the above object, the present invention is adopted the following technical scheme that.
A kind of method that utilization lithium ion carrier extracts lithium resource from solution containing lithium ion, comprises the steps：
(1) under the reducing conditions, the lithium ion in the lithium ion carrier absorption of lean lithium state lithium ion solution to be recycled
Obtain the lithium ion carrier of rich lithium state；
(2) under oxidative conditions, make the lithium ion carrier of step (1) richness lithium state discharge lithium ion, and regenerate lean
The lithium ion carrier of lithium state.
(3) by iterative cycles step (1) and (2), make lithium ion carrier constantly lithium be reclaimed from lithium ion solution and provide
Source.
The present invention by change lithium ion carrier state-of-charge so as to solution containing lithium ion carry out reversible removal lithium embedded from
Son process come realize without chemical raw material addition lithium resource recovery method so that the removal process of lithium resource meets atom Jing
The requirement of Ji reaction.Show through Theoretical Calculation and experiment, the lithium ion carrier of described lean lithium state, can be manganese oxidation
One or more in thing, barium oxide, or lithium ion is discharged by the lithium ion carrier of rich lithium state will be after its de- lithium
It is changed into lean lithium state, the method that any method of the prior art or above-mentioned steps of the present invention (2) can be adopted, wherein rich lithium state
Lithium ion carrier it is as follows：LiCoO2、LiMn2O4、LiNiO2、LiFePO4、LiMnO2、LiV3O8、LiVO2、LiV2O4、
Li6V5O15、Li4Ti5O12、LiCo0.2Ni0.8O2、LiCo0.5Ni0.5、LiNixCo1-2xMnxO2、LiNi1-x-yCoxMnyO2、
LiNixCo1-x-yMnyO2、LiNixCoyMn1-x-yO2Wherein x (0<x<0.5) with y (0<y<1) it is atom number ratio, is existing doping
Technology.
The pending solution containing lithium ion of the present invention can be the aqueous solution containing lithium ion or organic solution, for example
Lake containing lithium salts, salt pan concentration crack generation containing the lithium-containing solution and all kinds of lithium batteries after the old halogen of lithium, used Li ion cell process
The organic electrolyte containing lithium ion, described lithium ion solution is containing LiNO3、LiCl、Li2SO4、LiOH、LiClO4、
LiAsF6、LiPF6、Li2CO3、LiI、LiBr、Li2S、Li2SO3、LiIO3, one or more mixture in LiAc lithium salts it is molten
Liquid, its lithium concentration are 0.01-11000mmol/L.Material containing lithium ion can be LiNO3、LiCl、Li2SO4、
LiOH、LiClO4、LiAsF6、LiPF6、Li2CO3、LiI、LiBr、Li2S、Li2SO3、LiIO3, one or more in LiAc mix
Close solution.
, during lithium resource is extracted, reduction described above and oxidation can be using the reduction of electrochemistry and oxygen for the present invention
Change.It is that the lithium ion carrier of lean lithium state is placed in lithium ion solution to be recycled under reducing condition described in step (1), and
The lithium ion carrier that reduction process obtains rich lithium state is carried out with the cathode contacts of electrolysis bath.The oxidizing condition of step (2) be by
The lithium ion carrier of rich lithium state is placed in the solution of lithium ion to be collected, and carries out oxidation reaction with the positive contact of electrolysis bath
The lithium ion solution being recycled and the lithium ion carrier of the lean lithium state of regeneration.
Lithium ion carrier is reacted with electrode contact in being placed directly in electrolysis bath, or lithium ion carrier is hanged
Float in solution to be recycled or to be collected, be allowed in suspension by being constantly stirred to solution or flowing
State, so as to ensure the effective contact between lithium ion carrier and electrode, can adopt inert anode carrier or/and inert cathode to carry
Body.
Further for the electronic conduction ability for increasing lithium ion carrier, and accelerate lithium ion carrier fast in a cell
The receiving and losing electrons process of speed, lithium ion carrier can also be fabricated to the electrode containing lithium ion carrier by the present invention to be carried out, specifically
Process is that lithium ion carrier, conductive material, carrier and binding agent are made electrode slice, constitutes the weight of four components of electrode slice
Degree is as follows：
Lithium ion carrier：20-99.5%；
Conductive material：0.2-40%；
Carrier material：0.2-20%；
Binding agent：0.1-20%.
Wherein conductive material is expanded graphite, acetylene black, activated carbon, electric capacity carbon, one or several in CNT
Any mixing material；Carrier material is nickel foam, stainless (steel) wire, carbon cloth, titanium plate, any one material in graphite cake；Binding agent
For one kind or any multiple mixed materials in politef (PTFE), Kynoar (PVDF), polyvidone (PVP).
Method of the present invention relies on electrolysis bath and carries out.The electrolysis bath adopts external direct current power supply, in the middle of electrolysis bath
Separated with barrier film, form anode chamber and cathode chamber.The solution of collection of ions is treated in its anode chamber's filling, and cathode chamber filling is to be recycled
Lithium ion solution.
The present invention is not specially required to the condition being electrolysed, as long as can cathodic reduction absorption lithium ion, anodic oxidation abjection
Lithium ion.It is preferred that each cyclic process can adopt constant-current electrolysis, its electric current density to cause every gram of lithium ion carrier pair
Induced current 1-5000mA (referred to as electric current density, is designated as 1-5000mA/g, as follows).In order to optimize electrolytic process, the present invention enters
Preferably using being electrolysed stage by stage, initial rank of cathodic reduction absorption lithium ion each circulation adopts constant-current electrolysis pattern to one step,
Electric current density is 1-5000mA/g, is converted to when the lithium ion carrier of lean lithium state completes theoretical adsorbance 50-95%
Constant-potential electrolysis pattern, up to lithium ion carrier adsorption lithium ion saturation, cathodic reduction control of Electric potentials is (suitable in -1.5--0.1V
In saturated calomel electrode), wherein the lithium ion carrier that theoretical adsorbance is lean lithium state becomes the lithium ion of rich lithium state completely
The amount of lithium ions of absorption is needed during carrier；Anodic oxidation lithium ionic insertion/deinsertion each circulation initial rank adopt constant-current electrolysis pattern,
Electric current density 1-5000mA/g, is converted to perseverance when the lithium ion carrier of rich lithium state completes theoretical de- lithium amount 50-90%
Potential electrolysis pattern, anodization potentials are controlled in 0.3-2.5V (relative to saturated calomel electrode), wherein theoretical de- lithium amount is
The lithium ion carrier of rich lithium state becomes the amount of lithium ions that desorption is needed during the lithium ion carrier of lean lithium state completely.
The present invention can be in same electrolysis bath in order to further simplify the reason such as step and economic problems, the lean lithium state of negative electrode
Lithium ion carrier absorption lithium ion and the lithium ion carrier of anode richness lithium state discharge lithium ion while carrying out.
The solution of the lithium ion to be collected of the present invention is conductive electrolyte solution, is typically chosen containing lithium ion
Solution, conveniently can separate and recover.
The present invention illustrates the recovery principle of the present invention by some typical removal process.Carry in the negative electrode of electrolysis bath
The electrode slice of the lithium ion carrier containing lean lithium state is placed on body, at the same cathode chamber to be passed through quantitative lithium ion to be recycled molten
Liquid.The lithium ion carrier of rich lithium state is placed on the anode carrier of electrolysis bath, and it is molten diluter lithium ion to be passed through in anode chamber
Liquid.In electrolytic process, the lithium ion carrier of lean lithium state is constantly reduced under cathode current, and absorbs lithium ion to be recycled
Lithium ion in solution is transformed into the lithium ion carrier of rich lithium state；The lithium ion carrier of the rich lithium state of anode chamber is in sun simultaneously
Under the oxidation current of pole, constantly aoxidize, while discharging lithium ion, gradually make lithium ion carrier be lean lithium shape by rich lithium condition conversion
State.The lithium ion carrier of this lean lithium state can be positioned on the electric tank cathode carrier of next circulation for absorbing lithium to be recycled
Lithium resource in solion.The present invention passes through an oxidation-reduction process consumed without chemical raw material, constantly lithium-containing solution
In lithium ion be constantly transferred in anolyte liquid, it is achieved thereby that the lasting enrichment solution of lithium ion, is finally enriched with
Lithium ion solution to high concentration realizes the cleaning recovery of lithium resource.The high concentration lithium ion solution that these enrichments are obtained also may be used
To obtain lithium salts by evaporating solution Crystallization Separation.
Compared to the prior art the present invention has the following advantages：
(1) removal process of the invention does not have the consumption of additional chemical raw material, meets the requirement of atomic economy reaction, has
Clean and effective and the advantage without discharging of waste liquid, such that it is able to cost recovery is greatly lowered, while lithium money efficiently can be reclaimed
Source.
(2) present invention process is simple, and extraction lithium is carried out under the conditions of the pH of waste liquid containing lithium ion itself, it is not necessary to disappear
Consumption alkali adjusts pH value.
(3) present invention has higher lithium ion selectivity, especially China's high Mg/Li ratio area, and the method can be effective
Extract lithium resource therein.In addition the cycle life of the lithium ion carrier material in the present invention is up to more than 500-1000 time, its
The longer life-span reduce further the cost recovery of lithium resource.
Description of the drawings
Fig. 1 is the method schematic diagram of recovery lithium in the present invention；
1. 2. negative electrode of electrolysis bath, 3. anode, 4. barrier film, 5. circulating pumps 6. lithium ion solution to be recycled
7. 8. liquid outlet of lithium ion solution to be collected.
Specific embodiment
With reference to embodiment, more specific description present disclosure.It should be appreciated that the enforcement of the present invention is not limited to
In the following examples, any pro forma flexible and/or change made to the present invention falls within the scope of the present invention.
The schematic diagram of equipment therefor and method is shown in Fig. 1.
Embodiment 1
With 100 grams of LiCoO2As the lithium ion carrier of rich lithium state, by 316L rustless steels make cylinder type (diameter 8cm,
Height 6cm), as anode, lithium ion carrier is placed in straight tube, is made so as to ensure in the container bottom magnetic agitation of reaction
LiCoO2Effective contact and electrode between is in suspended state in annular base, the nickel foam cylinder that negative electrode separates for diaphragm paper
Shape negative electrode (diameter 5cm, height 6cm).Anode electrolytic cell and cathode solution are all filled to outside identical 0.5mol/L LiCl solution
DC source is connect, with constant current 1A (electric current densities：Electrolysis 16 hours 10mA/g) is carried out, LiCoO is made2It is changed into the lithium of lean lithium state
Ionophore.
The carrier that the lithium ion that the lithium ion carrier for being previously obtained lean lithium state is used for class salt lake bittern solution is absorbed.This
When with above-mentioned 316L rustless steels as negative electrode, nickel foam is anode, and the electrolyte of cathode chamber filling is class salt lake bittern, concrete composition
As shown in table 1.The electric current density of control electrolytic process causes 10mA/g (the lithium ion carrier relative to suspending in solution), makes lean
The lithium ion carrier of lithium state is continuous under the conditions of cathode current to obtain electron reduction, while in own absorption class salt lake bittern solution
Lithium ion, be transformed into the lithium ion carrier of rich lithium state；Continuous constant-current electrolysis 16 hours, until electrolysis terminates.Negative electrode electricity
Solution room electrolyte is class salt lake bittern solution (see the table below).
The lithium ion carrier of rich lithium state is placed again into anode chamber, and oxidation occurs under anode constant current, lithium ion is discharged,
It is transformed into the lithium ion carrier of lean lithium state, is put into next circulation, the LiCl solution of enrichment is finally steamed by repetitive operation 30 times
Crystallisation by cooling after sending out, obtains LiCl solids, and its content is 99.9%, and in whole process, the response rate of Li is 92.1%.
1 embodiment class salt lake bittern solution composition (unit g/L) of table
| Ion | Li+ | Mg2+ | K+ | SO4 2- | Cl- |
| Concentration | 5 | 98 | 0.93 | 12.4 | 302 |
Embodiment 2
With the spinelle LiMn after the de- lithium of pre-acidified2O4As the lithium ion carrier of lean lithium state, wherein pre-acidified refer to by
10 grams of LiMn2O4Constantly stir in the HCl solution of 2 liters of 0.2mol/L, be allowed to be fully contacted, after reacting 12 hours, filter,
Washing, the lithium ion carrier for being dried to obtain lean lithium state.(being prior art) is made electrode, the weight of four components of electrode
Amount degree is as follows：
Lithium ion carrier is the spinelle LiMn after the de- lithium of pre-acidified2O4：51.3%；
Conductive material is expanded graphite：8.8%；
Carrier material nickel foam：37.8%；
Binding agent PTFE：2.1%.
Electrode is blended in PTFE for electric capacity carbon and makes auxiliary electrode.Above-mentioned containing is placed on the cathode carrier of electrolysis bath
There is the electrode slice of the carrier of the lithium ion of lean lithium state, while cathode chamber is passed through 0.1mol/L Li2SO4With 2mol/L MgSO4's
Mixed solution, anode chamber place 0.5mol/L LiNO3Solution is electrolysed, the lithium ion carrier absorption of the lean lithium state of this process
The lithium ion of cathode chamber is transformed into the carrier of the lithium ion of rich lithium state.By the carrier of the lithium ion of this rich lithium state and electric capacity carbon
Exchange, as the anode of electrolysis bath.Separated with barrier film in the middle of electrolysis bath, external direct current power supply, with constant-current electrolysis, corresponding electric current
Density be 12mA/g lithium ion carriers, continuous electrolysis 12h.The carrier electrode of the lithium ion of wherein rich lithium state contains LiMn2O4
Electrode aoxidize under anode current, discharge lithium ion, be transformed into the lithium ion carrier of lean lithium state, carry out next circulation.
Above-mentioned oxidative reduction step is circulated 10 times, is measured in last 5 secondary cathode room electrolyte mixed liquor (equivalent to waste liquid) respectively with ICP
Lithium concentration is：0.107mol/L, 0.082mol/L, 0.043mol/L, 0.011mol/L, 0.005mol/L, so entirely
During Li the response rate be 99%, magnesium ion concentration is constant.
Embodiment 3
With commercially available LiCoO2For the carrier of the lithium ion of rich lithium state, being made electrode is carried out, four components of electrode
Weight percent content is as follows：
Lithium ion carrier is LiCoO2：49.4%；
Conductive material is expanded graphite：9.6%；
Carrier material nickel foam：38.8%；
Binding agent PTFE：2.2%.
The removal process of lithium ion is as follows：
(1) by 100 grams of LiCoO2According to lithium ion carrier electrode made by aforementioned proportion as anode, it is electric capacity to electrode
Carbon makes auxiliary electrode in being blended in PTFE, reference electrode is SCE electrodes.Cathode chamber is passed through 0.5 liter of 0.5mol/L to be recycled
MgSO4With 0.5mol/L Li2SO4Mixed solution be catholyte.Anode chamber is passed through 1 liter of 1mol/L Na2SO4And 0.005mol/L
LiOH solution is anolyte.
Relative to LiCoO2It is theoretical can deintercalate lithium ions total amount 85% stage, adopt 10A constant currents (electric current density for
Electrolysis 1.3 hours 100mA/g) is carried out, and anode potential is subsequently controlled for 1.9V (relative to saturated calomel electrode), is continued electrolysis 3
Hour, until the Li remained in lithium ion carrier+Into anolyte, the lithium ion carrier electrode of lean lithium state is now obtained.
(2) the lithium ion carrier electrode of the lean lithium state obtained with (1) process is blended in for electric capacity carbon as negative electrode to electrode
Auxiliary electrode is made in PTFE, reference electrode is SCE electrodes.Cathode chamber is still passed through 0.5 liter of 0.5mol/L to be recycled
MgSO4With 0.5mol/L Li2SO4Mixed solution be catholyte.Anode chamber is passed through 1 liter of 1mol/L Na2SO4And 0.005mol/L
LiOH solution is anolyte.
Before in relative to cathode chamber, electrode completes 70% stage of absorbable lithium ion total amount, using 10A (equivalent to electricity
Current density is 100mA/g) constant current carries out electrolysis 1 hour, and it is 2.0V (relative to saturation calomel subsequently control anodization potentials
Electrode) constant-potential electrolysis is carried out, continue electrolysis 4 hours, until the lithium ion carrier in catholyte becomes rich lithium state completely, this
When obtain the lithium ion carrier electrode of rich lithium state.
(3) by the lithium ion carrier electrode of rich lithium state, which is put into anode chamber, repeats the process of (1) so as in anode electricity
Oxidation is flowed down, lithium ion is discharged, is transformed into the lithium ion carrier of lean lithium state, the negative electrode for being put into next circulation is utilized.
Step (2) is continued cycling through under conditions of the anolyte and catholyte of a circulation in the persistently use and (3) 20 all
Na after phase2SO4In solution, lithium concentration is continuously increased, by the Na containing lithium ion2SO4Solution carries out heating concentration, adds after cooling
Enter Na2CO3Solid, obtains a certain amount of Li after filtration2CO3Precipitation, in whole process, the response rate of Li is 85.2%.
Embodiment 4
With commodity electrolytic manganese dioxide (EMD) 310 DEG C heating 3 hours after as lean lithium state lithium ion carrier,
Being made electrode is carried out, and the weight percent content of four components of electrode is as follows：
Manganese dioxide：53.2%；
Conductive material is expanded graphite：7.8%；
Carrier material nickel foam：36.8%；
Binding agent PTFE：2.2%.
Above-mentioned manganese dioxide electrode is graphite rod as cathodic counter electrode, assembles them into electrolysis bath.Use in the middle of electrolysis bath
Barrier film separates, and wherein anode chamber's electrolyte is 1 liter of 1mol/L LiNO3Solution, cathode chamber electrolyte are 2 liters of 0.5mol/L
LiNO3With the Mg (NO of 0.5mol/L3)2Mixed solution (a kind of solution containing lithium ion).
(1) before completing to adsorb 90% stage of lithium amount total amount relative to initial cathode chamber li-ion electrode, carry out permanent electricity
Stream electroreduction, electric current density are 120mA/g (relative to manganese dioxide).
(2) complete to adsorb 10% stage of lithium amount total amount residual relative to initial cathode chamber li-ion electrode, control is cloudy
Pole reduction potential is -0.7 (relative to saturated calomel electrode) V constant-potential electrolysis 5h, until manganese dioxide electrode is in cathodic reduction
Constantly adsorb the Li in the lithium ion solution under electric current+, it is transformed into the lithium ion carrier of rich lithium state.
(3) by the lithium ion carrier of rich lithium state, which is put into anode chamber, aoxidizes under anode current, discharges lithium ion, turns
Become the lithium ion carrier of lean lithium state, the negative electrode for being put into next circulation is utilized.
It is accumulative to circulate the anode chamber LiNO of constantly enrichment lithium ion after 50 times3Solution evaporation is crystallized, and obtains LiNO3Solid,
Its content is 99.9%, and in whole process, the response rate of Li is 82.9%.
Embodiment 5
With spinelle LiMn2O4As the carrier of the lithium ion of rich lithium state, being made electrode is carried out, four groups of electrode
The weight percent content for dividing is as follows：
Lithium ion carrier is spinelle LiMn2O4：51.4%；
Conductive material is expanded graphite：8.6%；
Carrier material nickel foam：37.9%；
Binding agent PTFE：2.1%.
Same auxiliary electrode is VO2, which makes electrode slice as the carrier of the lithium ion of lean lithium state, used as auxiliary electricity
Pole, the weight percent content of four components of electrode are as follows：
Lithium ion carrier is VO2：56.8%；
Conductive material is expanded graphite：6.3%；
Carrier material nickel foam：33.7%；
Binding agent PTFE：3.2%.
The VO containing lean lithium state is placed on the cathode carrier of electrolysis bath2Electrode slice, while cathode chamber is passed through embodiment 1
Class salt lake bittern solution, while the LiMn of rich lithium state is placed on the anode carrier of electrolysis bath2O4Electrode slice, anode chamber lead to
Enter 1mol/L LiNO3Solution.Separated with barrier film in the middle of electrolysis bath, external direct current power supply, electrolysis is carried out with constant current 240mA/g and is arrived
50% depth, subsequently enters the constant-potential electrolysis stage of second stage, and setting cathodic reduction current potential is -0.80V (relative to saturation
Calomel electrode), continue electrolysis 4 hours, wherein the lithium ion carrier electrode of lean lithium state contains VO2Electrode, negative electrode electricity
Constantly reduce in stream, adsorb the lithium ion in salt lake bittern, be transformed into rich lithium state；The lithium ion carrier of rich lithium state is simultaneously
Containing LiMn2O4Electrode in anode chamber, under anode current aoxidize, discharge lithium ion, be transformed into lean lithium state.Treat beyond electricity
After solution voltage range, two electrode slice positions are exchanged, that is, contains LiMn2O4The lithium ion of lean lithium state that has been transformed into of electrode carry
Body is put into cathode chamber, and cathodic reduction is adsorbed the lithium ion in salt lake bittern, and then is transformed into the lithium ion carrier of rich lithium state；
Containing VO2Electrode after said process is transformed into the lithium ion carrier of rich lithium state, be put into anodic oxidation, in anolyte
Middle release lithium ion, is transformed into the lithium ion carrier of lean lithium state.Circulate for one above, operate 30 times according to above-mentioned steps,
In the process, LiNO in anode chamber3In solution, lithium concentration is continuously increased, finally by LiNO3Solution evaporation is crystallized, and is obtained
LiNO3Solid, its content are 99.8%, and in whole process, the response rate of Li is 91.1%.
Embodiment 6
With spinelle LiMn2O4As the lithium ion carrier of rich lithium state, being made electrode is carried out, four components of electrode
Weight percent content it is as follows：
Lithium ion carrier is spinelle LiMn2O4：51.4%；
Conductive material is expanded graphite：8.7%；
Carrier material nickel foam：37.8%；
Binding agent PTFE：2.1%.
By 20 grams of LiMn2O4According to lithium ion carrier electrode made by aforementioned proportion, auxiliary electricity is made for nickel plate to electrode
Pole, reference electrode are SCE electrodes, are separated with barrier film in the middle of electrolysis bath.Place on the anode carrier of electrolysis bath containing rich lithium state
Lithium ion carrier be LiMn2O4Electrode slice, anode chamber is passed through and sets to 0 .5mol/LLiNO3Solution, at the same cathode chamber be passed through it is above-mentioned
Class salt lake bittern solution.Relative to LiMn2O4It is theoretical can deintercalate lithium ions total amount 85% stage, using 1A constant current (electric currents
Density is 50mA/g) electrolysis 1.5 hours is carried out, anode potential is subsequently controlled for 2.2V (relative to saturated calomel electrode), continue
Electrolysis 1 hour, until the Li remained in lithium ion carrier+Into anolyte, this process LiMn2O4Release lithium ion, becomes lean lithium
The lithium ion carrier electrode of state.
The lithium ion carrier of the lean lithium state obtained by above-mentioned anodized is placed on into the negative electrode of electrolysis bath, it is external straight
Stream power supply, is electrolysed to 90% depth with constant current 120mAh/g, and the 10% of residual enters the subsequent constant-potential electrolysis stage, this
When arrange anodization potentials be voltage be 2.2V (relative to saturated calomel electrode), continue electrolysis 5 hours.Wherein lithium ion
Carrier electrode contains LiMn2O4Electrode, constantly reduce in cathode current, adsorb class salt lake bittern solution in lithium ion,
It is transformed into the lithium ion carrier of rich lithium state；By the lithium ion carrier of rich lithium state, which is put into anode chamber, the oxygen under anode current
Change, discharge lithium ion, be transformed into the lithium ion carrier of lean lithium state, the negative electrode for being put into next circulation is utilized.Above-mentioned oxidation is also
Former step cycle 20 times, in the process, LiNO in anode chamber3In solution, lithium concentration is continuously increased, finally by LiNO3It is molten
Liquid evaporative crystallization, obtains LiNO3Solid, its content are 98.7%, and in whole process, the response rate of Li is 96.5%.
Claims (1)
1. a kind of method that utilization lithium ion carrier reclaims lithium resource from solution containing lithium ion, it is characterised in that
With spinelle LiMn2O4As the lithium ion carrier of rich lithium state, being made electrode is carried out, the weight of four components of electrode
Amount degree is as follows：
Lithium ion carrier is spinelle LiMn2O4：51.4%；
Conductive material is expanded graphite：8.7%；
Carrier material nickel foam：37.8%；
Binding agent PTFE：2.1%；
By 20 grams of LiMn2O4Lithium ion carrier electrode is made according to aforementioned proportion, auxiliary electrode, reference are made for nickel plate to electrode
Electrode is saturated calomel electrode, is separated with barrier film in the middle of electrolysis bath；The lithium of rich lithium state is placed on the anode carrier of electrolysis bath
Ionophore is LiMn2O4Electrode slice, anode chamber is passed through 0.5mol/L LiNO3Solution, while cathode chamber is passed through salt lake bittern
Solution；Relative to LiMn2O4It is theoretical can deintercalate lithium ions total amount 85% stage, electrolysis 1.5 is carried out using 1A constant currents little
When, it is 2.2V subsequently to control anode potential relative to saturated calomel electrode, continues electrolysis 1 hour, until residual in lithium ion carrier
The Li for staying+Into anolyte, this process LiMn2O4Release lithium ion, becomes the lithium ion carrier electrode of lean lithium state；
The lithium ion carrier of the lean lithium state obtained by above-mentioned anodized is placed on into the negative electrode of electrolysis bath, external unidirectional current
Source, is electrolysed relative to LiMn with constant current 120mAh/g2O490% depth of theoretical adsorbable lithium ion total amount, residual
10% enters the subsequent constant-potential electrolysis stage, and it is 2.2V now to arrange anodization potentials relative to saturated calomel electrode, after
Continuous electrolysis 5 hours；Wherein lithium ion carrier electrode contains LiMn2O4Electrode, constantly reduce in cathode current, adsorb salt
Lithium ion in lake bittern water solution, is transformed into the lithium ion carrier of rich lithium state；The lithium ion carrier of rich lithium state is put into into sun
Pole room, aoxidizes under anode current, discharges lithium ion, is transformed into the lithium ion carrier of lean lithium state, is put into next circulation
Negative electrode is utilized；Above-mentioned oxidative reduction step circulates 20 times, in the process, LiNO in anode chamber3In solution, lithium concentration is not
It is disconnected to increase, finally by LiNO3Solution evaporation is crystallized, and obtains LiNO3Solid, its content are 98.7%, the recovery of Li in whole process
Rate is 96.5%；
Wherein salt lake bittern solution composition：Li+5g/L, Mg2+98g/L, K+0.93g/L, SO4 2-12.4g/L, Cl-302g/L。
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