CN104577243A - 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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- CN104577243A CN104577243A CN201410681653.0A CN201410681653A CN104577243A CN 104577243 A CN104577243 A CN 104577243A CN 201410681653 A CN201410681653 A CN 201410681653A CN 104577243 A CN104577243 A CN 104577243A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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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 extracting lithium resource, be specially a kind of lithium ion carrier that utilizes from containing the method extracting lithium resource lithium ion solution, be suitable for any natural and containing lithium ion solution or containing lithium waste liquid, mainly comprising and concentrate containing lithium salts lake, salt pan the lithium-containing solution obtained containing the old halogen of lithium and process used Li ion cell etc. through processing.
Background technology
Lithium, as the minimum metallic element of occurring in nature atomic weight, with the chemical property that it is more active, is widely used in lithium ion battery, metal hydride and and the field such as nuclear fusion.Along with fast developments such as lithium ion batteries, facilitate increasing progressively fast of lithium resource demand, facilitate novel containing the exploitation of lithium minerals and the recovery of useless lithium resource.According to ASSOCIATE STATISTICS, mainly can be used at present exploiting the lithium resource utilized is granite peamatite mineral deposit, bittern deposit and seawater mineral deposit.Because the difficulties in exploration containing lithium deposite is comparatively large, can exploit in the world at present and utilize the country directly producing lithium carbonate containing lithium bittern and lithium ore to mainly contain China, the U.S., Chile and Argentinian.China's lithium resource is mainly distributed in the ground such as Qinghai, Tibet, Sichuan, Jiangxi, Xinjiang, the wherein Salt Lake Zabuye of Northwestern Part of Tibet and the Bange-Du Jiali lake of east, and in the salt lake such as the Cha Er Han of Chaidamu Basin, Qinghai Province, Yi Liping, West Taijinar, East Taijinaier and large Chai Dan.Present stage, how China still based on primary lithium ore deposit to the extraction of lithium resource, accelerates China and develops from lithium-containing solution and reclaim secondary lithium resource, becomes the key of the sustainable fast development of health of China's lithium salts industry.
Report that the separation of lithium salts and recovery method mainly contain at present: the precipitation method, solvent extraction, dipping calcination method and absorption method etc.The typical precipitation method such as China Patent Publication No. CN1335263 (producing the method for lithium carbonate with carbonizatin method separating magnesium lithium from salt lake brine with high magnesium-lithium ratio) utilizes carbonizatin method to produce the method for lithium carbonate from magnesium lithium solution.Usually, precipitation method process treatment process is complicated, and because magnesium carbonate can absorb lithium ion in precipitation process, therefore the method is not suitable in process stoste containing a large amount of Mg
2+and Ca
2+etc. a large amount of alkaline-earth metal containing lithium ion solution.Solvent extraction utilizes the cationic liquid containing exchangeable cations functional group to exchange the lithium ion in solution usually, be considered to one of effective ways carrying lithium from high magnesium chloride Salt-lake brine, its typical patent of invention CN87103431 (a kind of from containing the method extracting anhydrous Lithium chloride lithium bittern) reports the employing of Qinghai Salt Lake research institute of the Chinese Academy of Sciences and consists of 50%-70%TBP, 30%-50%200 solvent naphtha extracts large bavin dawn high magnesium lithium-containing ion waste liquid as solvent, it is expensive to there is extractant in this method, the water-soluble loss of regenerative process is serious, so there is no commercial Application report at present.The technological process of patent CN1724372 (producing the method for lithium carbonate, magnesium oxide and hydrochloric acid with high-Mg Li-contained bittern) is spraying dry, calcine, add water washing, evaporation and concentration, precipitation operation after obtain lithium carbonate product.The method utilizes and calcines Li-Mg contained bittern up to 1200 DEG C of high temperature, its pyrolysis is made to be magnesium oxide, reclaim lithium carbonate simultaneously, although this technique consumption of raw materials is less, but the subtractive process that Problems existing is magnesium can make flow process trend towards complexity, and gas containing hydrogen chloride is serious to equipment corrosion in production process, energy consumption is higher.Absorption method utilizes to the adsorbent of the selective absorption of lithium ion to adsorb lithium ion, and then eluted by lithium ion, reach the object that lithium ion is separated with other foreign ion, wherein typical lithium adsorbent is as MnO
2ion sieve, utilizes it to Li
+there is special Selective adsorption to realize the adsorption capacity of lithium ion.Patent CN1511963 (method of extracting lithium from salt lake brine by manganese dioxide) describes and must contain lithium concentrated brine for salt pan solar evaporation, uses MnO
2adsorbent adsorption selection Li
+after, with hydrochloric acid solution wash-out by the Li adsorbed
+, more refining through eluent, concentrated after, obtain raw material qualified needed for lithium carbonate or lithium chloride.Similar patent such as CN101654741 (a kind of method of separation and recovery lithium and cobalt from lithium ion battery) discloses the sample after a kind of lithium magnesium Mn oxide pickling processes as the acid-soluble rear lithium ion adsorbent containing lithium filtrate of used Li ion cell, and with submerged ultrafiltration combination of elements, after making to proceed to maximal absorptive capacity in Lithium-ion embeding to ion sieve interstitial void, finally with acid solution, wash-out is carried out to adsorbent, reach the object reclaiming lithium.We observe, and the method needs secondary to utilize hydrochloric acid to process before and after wash-out, not only creates serious equipment corrosion, waste acid liquor, and the chlorine that processing procedure produces also easily causes environmental pollution.
In view of this, for current a large amount of former lithium mineral products or the lithium-containing solution reclaiming the generation of lithium battery process, invent a kind of recovery lithium resource technique of clean and effective, and at utmost reduce in lithium resource removal process, the discharge of related chemistry raw material or auxiliary material, makes the recovery of lithium resource meet atom economy method extremely urgent.
Summary of the invention
The object of the invention is the problem overcoming prior art, provide a kind of novel green method to reclaim lithium ion, namely providing a kind of lithium ion carrier that utilizes from containing the method extracting lithium resource lithium ion solution.
For achieving the above object, the present invention adopts following technical scheme.
Utilize lithium ion carrier from containing the method extracting lithium resource lithium ion solution, comprise the steps:
(1) lithium ion in the lithium ion solution that under the reducing conditions, the lithium ion carrier absorption of poor lithium state is to be recycled obtains the lithium ion carrier of rich lithium state;
(2) under oxidative conditions, make the lithium ion carrier of the rich lithium state of step (1) discharge lithium ion, and bear the lithium ion carrier of poor lithium state again.
(3) by iterative cycles step (1) and (2), lithium ion carrier is made constantly from lithium ion solution, to reclaim lithium resource.
The present invention is by changing the state-of-charge of lithium ion carrier, make it realize the lithium resource recovery method added without chemical raw material in the process of carrying out reversible deintercalate lithium ions containing lithium ion solution, thus make the removal process of lithium resource meet the requirement of atomic economy reaction.Show through theory calculate and experiment, the lithium ion carrier of described poor lithium state, can be one or more in Mn oxide, barium oxide, or discharge lithium ion from the lithium ion carrier of rich lithium state and become poor lithium state by after its de-lithium, can adopt the method for any method of the prior art or above-mentioned steps of the present invention (2), wherein the lithium ion carrier of rich lithium state is as follows: LiCoO
2, LiMn
2o
4, LiNiO
2, LiFePO
4, LiMnO
2, LiV
3o
8, LiVO
2, LiV
2o
4, Li
6v
5o
15, Li
4ti
5o
12, LiCo
0.2ni
0.8o
2, LiCo
0.5ni
0.5, LiNi
xco
1-2xmn
xo
2, LiNi
1-x-yco
xmn
yo
2, LiNi
xco
1-x-ymn
yo
2, LiNi
xco
ymn
1-x-yo
2wherein x (0<x<0.5) and y (0<y<1) is atom number ratio, is existing doping techniques.
The pending lithium ion solution that contains of the present invention can be the aqueous solution containing lithium ion or organic solution, such as concentrate containing lithium salts lake, salt pan the organic electrolyte containing lithium ion that the lithium-containing solution after containing the old halogen of lithium, used Li ion cell process and all kinds of lithium battery crack generation, described lithium ion solution is for containing LiNO
3, LiCl, Li
2sO
4, LiOH, LiClO
4, LiAsF
6, LiPF
6, Li
2cO
3, LiI, LiBr, Li
2s, Li
2sO
3, LiIO
3, one or more mixtures in LiAc lithium salts solution, its lithium concentration is 0.01-11000mmol/L.Material containing lithium ion can be LiNO
3, LiCl, Li
2sO
4, LiOH, LiClO
4, LiAsF
6, LiPF
6, Li
2cO
3, LiI, LiBr, Li
2s, Li
2sO
3, LiIO
3, one or more mixed solutions in LiAc.
The present invention is in the process extracting lithium resource, and reduction described above and oxidation can adopt electrochemical reduction and oxidation.Be that the lithium ion carrier of poor lithium state is placed in lithium ion solution to be recycled under reducing condition described in step (1), and carry out with the cathode contacts of electrolysis tank the lithium ion carrier that reduction process obtains rich lithium state.The oxidizing condition of step (2) is placed in by the lithium ion carrier of rich lithium state to wait to collect the solution of lithium ion, and carry out the lithium ion carrier of the poor lithium state of lithium ion solution that oxidation reaction is recycled and regeneration with the positive contact of electrolysis tank.
Lithium ion carrier directly can be positioned in electrolysis tank and react with electrode contact, or lithium ion carrier is suspended in solution to be recycled or to be collected, make it to be in suspended state by stirring solution constantly or flowing, thus ensure the effective contact between lithium ion carrier and electrode, inert anode carrier can be adopted or/and inert cathode carrier.
Further in order to increase the electronic conduction ability of lithium ion carrier, and accelerate lithium ion carrier receiving and losing electrons process fast in a cell, the present invention also carries out by electrode lithium ion carrier can be made into containing lithium ion carrier, detailed process is that lithium ion carrier, electric conducting material, carrier and adhesive are made electrode slice, and the weight percent content of four components of composition electrode slice is as follows:
Lithium ion carrier: 20-99.5%;
Electric conducting material: 0.2-40%;
Carrier material: 0.2-20%;
Adhesive: 0.1-20%.
Wherein electric conducting material is one or several any composite materials in expanded graphite, acetylene black, active carbon, electric capacity carbon, carbon nano-tube; Carrier material is any one material in nickel foam, stainless (steel) wire, carbon cloth, titanium plate, graphite cake; Adhesive is one in polytetrafluoroethylene (PTFE), Kynoar (PVDF), PVP (PVP) or multiple mixed materials arbitrarily.
Method of the present invention relies on electrolysis tank and carries out.This electrolysis tank adopts external direct current power supply, and electrolysis tank centre barrier film separates, and forms anode chamber and cathode chamber.The solution treating collection of ions is filled by its anode chamber, and cathode chamber fills lithium ion solution to be recycled.
The condition of the present invention to electrolysis does not specially require, as long as lithium ion is adsorbed in energy cathodic reduction, lithium ion is deviate from anodic oxidation.Preferred each cyclic process can adopt constant-current electrolysis, and its current density makes every gram of lithium ion carrier corresponding current 1-5000mA (be called current density, be designated as 1-5000mA/g, be as follows).In order to optimize electrolytic process, the present invention preferably adopts electrolysis stage by stage further, the initial rank of each circulation of cathodic reduction absorption lithium ion adopt constant-current electrolysis pattern, current density is 1-5000mA/g, constant-potential electrolysis pattern is converted to when the lithium ion carrier of poor lithium state completes theoretical adsorbance 50-95%, until lithium ion carrier adsorption lithium ion is saturated, cathodic reduction control of Electric potentials is at-1.5--0.1V (being equivalent to saturated calomel electrode), wherein theoretical adsorbance is the amount of lithium ions that the lithium ion carrier of poor lithium state needs absorption when becoming the lithium ion carrier of rich lithium state completely, the initial rank of each circulation of anodic oxidation lithium ionic insertion/deinsertion adopt constant-current electrolysis pattern, current density 1-5000mA/g, constant-potential electrolysis pattern is converted to when the lithium ion carrier of rich lithium state completes theoretical de-lithium amount 50-90%, anodization potentials controls in 0.3-2.5V (relative to saturated calomel electrode), and wherein theoretical de-lithium amount is the amount of lithium ions that the lithium ion carrier of rich lithium state needs desorption when becoming the lithium ion carrier of poor lithium state completely.
The present invention can in same electrolysis tank in order to simplify the reason such as step and economic problems further, and the lithium ion carrier of the lithium ion carrier absorption lithium ion of the poor lithium state of negative electrode and the rich lithium state of anode discharges lithium ion to carry out simultaneously.
The solution waiting to collect lithium ion of the present invention is the electrolyte solution of conduction, and the general solution selected containing lithium ion, can facilitate separation and recovery.
The present invention illustrates recovery principle of the present invention by some typical removal process.The cathode carrier of electrolysis tank is placed the electrode slice of the lithium ion carrier containing poor lithium state, and cathode chamber passes into quantitative lithium ion solution to be recycled simultaneously.The anode carrier of electrolysis tank is placed the lithium ion carrier of rich lithium state, and passes into rarer lithium ion solution in anode chamber.In electrolytic process, the lithium ion carrier of poor lithium state constantly reduces under cathode current, and the lithium ion absorbed in lithium ion solution to be recycled is transformed into the lithium ion carrier of rich lithium state; The lithium ion carrier of the rich lithium state of anode chamber is under oxidation current simultaneously, is constantly oxidized, discharges lithium ion simultaneously, make lithium ion carrier be poor lithium state by rich lithium condition conversion gradually.The lithium ion carrier of this poor lithium state can be positioned on the next electric tank cathode carrier circulated for absorbing the lithium resource in lithium ion solution to be recycled.The oxidation-reduction process that the present invention is consumed without chemical raw material by one, lithium ion constantly in lithium-containing solution is constantly transferred in anolyte liquid, thus achieving the lasting enrichment solution of lithium ion, the lithium ion solution that final enrichment obtains high concentration achieves the clean recovery of lithium resource.The high concentration lithium ion solution that these enrichments obtain also can obtain lithium salts by evaporating liquid Crystallization Separation.
Compared to the prior art the present invention has the following advantages:
(1) removal process of the present 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, thus significantly can reduce cost recovery, can reclaim lithium resource efficiently simultaneously.
(2) present invention process is simple, and carries out extraction lithium under containing the pH condition of lithium ion waste liquid itself, does not need to consume alkali adjust ph.
(3) the present invention has higher lithium ion selectivity, especially China's high Mg/Li ratio area, and the method effectively can extract lithium resource wherein.The cycle life of the lithium ion carrier material in addition in the present invention can reach more than 500-1000 time, and its longer life-span reduce further the cost recovery of lithium resource.
Accompanying drawing explanation
Fig. 1 is the method schematic diagram reclaiming lithium in the present invention;
1. the lithium ion solution that electrolysis tank 2. negative electrode 3. anode 4. barrier film 5. circulating pump 6. is to be recycled
7. wait to collect lithium ion solution 8. liquid outlet.
Embodiment
Below in conjunction with embodiment, more specific description content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.Fig. 1 is shown in by the schematic diagram of equipment therefor and method.
Embodiment 1
With 100 grams of LiCoO
2as the lithium ion carrier of rich lithium state, 316L stainless steel is made cylinder type (diameter 8cm, height 6cm), as anode, lithium ion carrier is placed in straight tube, makes in the container bottom magnetic agitation of reaction thus ensure LiCoO
2with the effective contact between electrode is in circular base ground inner suspension state, negative electrode is the cylindric negative electrode of nickel foam (diameter 5cm, height 6cm) that diaphragm paper separates.Anode electrolytic cell and cathode solution are all filled to identical 0.5mol/L LiCl solution external direct current power supply, carry out electrolysis 16 hours, make LiCoO with constant current 1A (current density: 10mA/g)
2change the lithium ion carrier of poor lithium state into.
The carrier that the lithium ion lithium ion carrier obtaining poor lithium state being above used for class salt lake bittern solution absorbs.Now with above-mentioned 316L stainless steel for negative electrode, nickel foam is anode, cathode chamber fill electrolyte be class salt lake bittern, concrete composition is as shown in table 1.The current density controlling electrolytic process makes 10mA/g (the lithium ion carrier relative to suspending in solution), make the lithium ion carrier of poor lithium state continuous electron reduction under cathode current condition, lithium ion simultaneously in own absorption class salt lake bittern solution, is transformed into the lithium ion carrier of rich lithium state; Continuous constant-current electrolysis 16 hours, until electrolysis terminates.Catholyte chamber's electrolyte is class salt lake bittern solution (seeing the following form).
The lithium ion carrier of rich lithium state puts into anode chamber again, be oxidized under anode constant current, release lithium ion, be transformed into the lithium ion carrier of poor lithium state, put into next circulation, repetitive operation 30 times, finally by crystallisation by cooling after the evaporation of the LiCl solution of enrichment, obtain LiCl solid, its content is 99.9%, and in whole process, the rate of recovery of Li is 92.1%.
Table 1 embodiment class salt lake bittern solution composition (unit g/L)
| Ion | Li + | Mg 2+ | K + | SO 4 2- | Cl - |
| Concentration | 5 | 98 | 0.93 | 12.4 | 302 |
Embodiment 2
The spinelle LiMn after lithium is taken off with pre-acidified
2o
4as the lithium ion carrier of poor lithium state, wherein pre-acidified refers to 10 grams of LiMn
2o
4constantly stir in the HCl solution of 2 liters of 0.2mol/L, make it abundant contact, react after 12 hours, filter, washing, drying obtain the lithium ion carrier of poor lithium state.(for prior art) is made electrode, and the weight percent content of electrode four components is as follows:
Lithium ion carrier is the spinelle LiMn after pre-acidified takes off lithium
2o
4: 51.3%;
Electric conducting material is expanded graphite: 8.8%;
Carrier material nickel foam: 37.8%;
Adhesive PTFE:2.1%.
Be that electric capacity carbon is blended in PTFE and makes auxiliary electrode to electrode.The cathode carrier of electrolysis tank is placed the electrode slice of the carrier of the above-mentioned lithium ion containing poor lithium state, and cathode chamber passes into 0.1mol/L Li simultaneously
2sO
4with 2mol/L MgSO
4mixed solution, 0.5mol/L LiNO places in anode chamber
3solution carries out electrolysis, and the lithium ion of the lithium ion carrier absorption cathode chamber of this process poor lithium state is transformed into the carrier of the lithium ion of rich lithium state.The carrier of the lithium ion of this rich lithium state and electric capacity carbon are exchanged, as the anode of electrolysis tank.Electrolysis tank centre barrier film separates, external direct current power supply, and with constant-current electrolysis, corresponding current density is 12mA/g lithium ion carrier, continuous electrolysis 12h.Wherein the carrier electrode of the lithium ion of rich lithium state is namely containing LiMn
2o
4electrode be oxidized under anode current, release lithium ion, be transformed into the lithium ion carrier of poor lithium state, carry out next one circulate.Above-mentioned oxidative reduction step circulates 10 times, recording lithium concentration in last 5 secondary cathode room electrolyte mixed liquors (being equivalent to waste liquid) respectively with ICP is: 0.107mol/L, 0.082mol/L, 0.043mol/L, 0.011mol/L, 0.005mol/L, so the rate of recovery of Li is 99% in whole process, magnesium ion concentration is constant.
Embodiment 3
With commercially available LiCoO
2for the carrier of the lithium ion of rich lithium state, made electrode and carry out, the weight percent content of electrode four components is as follows:
Lithium ion carrier is LiCoO
2: 49.4%;
Electric conducting material is expanded graphite: 9.6%;
Carrier material nickel foam: 38.8%;
Adhesive PTFE:2.2%.
The removal process of lithium ion is as follows:
(1) by 100 grams of LiCoO
2the lithium ion carrier electrode made according to aforementioned proportion is as anode, and be that electric capacity carbon is blended in PTFE and makes auxiliary electrode to electrode, reference electrode is SCE electrode.Cathode chamber passes into 0.5 liter of 0.5mol/L MgSO to be recycled
4with 0.5mol/L Li
2sO
4mixed solution be catholyte.Anode chamber passes into 1 liter of 1mol/L Na
2sO
4be anolyte with 0.005mol/L LiOH solution.
Relative to LiCoO
2theoretical can 85% stage of deintercalate lithium ions total amount, 10A constant current (current density is 100mA/g) is adopted to carry out electrolysis 1.3 hours, controlling anode potential is subsequently 1.9V (relative to saturated calomel electrode), continues electrolysis 3 hours, until Li residual in lithium ion carrier
+enter anolyte, now obtain the lithium ion carrier electrode of poor lithium state.
(2) the lithium ion carrier electrode of the poor lithium state obtained with (1) process is for negative electrode, and be that electric capacity carbon is blended in PTFE and makes auxiliary electrode to electrode, reference electrode is SCE electrode.Cathode chamber still passes into 0.5 liter of 0.5mol/L MgSO to be recycled
4with 0.5mol/L Li
2sO
4mixed solution be catholyte.Anode chamber passes into 1 liter of 1mol/L Na
2sO
4be anolyte with 0.005mol/L LiOH solution.
Before electrode completes 70% stage of Absorbable rod lithium ion total amount in relative to cathode chamber, 10A (being equivalent to current density is 100mA/g) constant current is adopted to carry out electrolysis 1 hour, controlling anodization potentials is subsequently that 2.0V (relative to saturated calomel electrode) carries out constant-potential electrolysis, continue electrolysis 4 hours, until the lithium ion carrier in catholyte becomes rich lithium state completely, now obtain the lithium ion carrier electrode of rich lithium state.
(3) by the lithium ion carrier electrode of rich lithium state, it puts into anode chamber, repeats the process of (1), makes it be oxidized under anode current, and release lithium ion, is transformed into the lithium ion carrier of poor lithium state, and the negative electrode putting into next circulation utilizes.
Lasting use continues circulation step (2) and (3) 20 all after date Na under the anolyte of one circulation and the condition of catholyte
2sO
4in solution, lithium concentration constantly increases, by the Na containing lithium ion
2sO
4solution carries out heating and concentrates, and adds Na after cooling
2cO
3solid, obtains a certain amount of Li after filtration
2cO
3precipitation, in whole process, the rate of recovery of Li is 85.2%.
Embodiment 4
As the carrier of the lithium ion of poor lithium state after heating 3 hours with commodity electrolytic manganese dioxide (EMD) at 310 DEG C, made electrode and carry out, the weight percent content of electrode four components is as follows:
Manganese dioxide: 53.2%;
Electric conducting material is expanded graphite: 7.8%;
Carrier material nickel foam: 36.8%;
Adhesive PTFE:2.2%.
Above-mentioned manganese dioxide electrode is graphite rod as cathodic counter electrode, is assembled into electrolysis tank.Electrolysis tank centre barrier film separates, and wherein anode chamber's electrolyte is 1 liter of 1mol/L LiNO
3solution, cathode chamber electrolyte is the LiNO of 2 liters of 0.5mol/L
3with the Mg (NO of 0.5mol/L
3)
2mixed solution (a kind of containing lithium ion solution).
(1) before completing 90% stage relative to initial cathode chamber li-ion electrode absorption lithium amount total amount, carry out constant-current electrolysis reduction, current density is 120mA/g (relative to manganese dioxide).
(2) 10% stage residual relative to initial cathode chamber li-ion electrode absorption lithium amount total amount is completed, control cathode reduction potential is-0.7 (relative to saturated calomel electrode) V constant-potential electrolysis 5h, until manganese dioxide electrode constantly adsorbs the Li in this lithium ion solution under cathodic reduction electric current
+, be transformed into the lithium ion carrier of rich lithium state.
(3) by the lithium ion carrier of rich lithium state, it puts into anode chamber, is oxidized under anode current, and release lithium ion, is transformed into the lithium ion carrier of poor lithium state, and the negative electrode putting into next circulation utilizes.
By the anode chamber LiNO of continuous enriching lithium ion after accumulative circulation 50 times
3solution evaporative crystallization, obtains LiNO
3solid, its content is 99.9%, and in whole process, the rate of recovery of Li is 82.9%.
Embodiment 5
With spinelle LiMn
2o
4as the carrier of the lithium ion of rich lithium state, made electrode and carry out, the weight percent content of electrode four components is as follows:
Lithium ion carrier is spinelle LiMn
2o
4: 51.4%;
Electric conducting material is expanded graphite: 8.6%;
Carrier material nickel foam: 37.9%;
Adhesive PTFE:2.1%.
Same auxiliary electrode is VO
2, it, as the carrier of the lithium ion of poor lithium state, makes electrode slice, and as auxiliary electrode, the weight percent content of electrode four components is as follows:
Lithium ion carrier is VO
2: 56.8%;
Electric conducting material is expanded graphite: 6.3%;
Carrier material nickel foam: 33.7%;
Adhesive PTFE:3.2%.
The cathode carrier of electrolysis tank is placed the VO containing poor lithium state
2electrode slice, cathode chamber passes into the class salt lake bittern solution of embodiment 1 simultaneously, places the LiMn of rich lithium state on the anode carrier of electrolysis tank simultaneously
2o
4electrode slice, anode chamber passes into 1mol/L LiNO
3solution.Electrolysis tank centre barrier film separates, external direct current power supply, electrolysis is carried out to 50% degree of depth with constant current 240mA/g, enter the constant-potential electrolysis stage of second stage subsequently, arranging cathodic reduction current potential is-0.80V (relative to saturated calomel electrode), continue electrolysis 4 hours, wherein the lithium ion carrier electrode of poor lithium state is namely containing VO
2electrode, constantly reduce in cathode current, the lithium ion in absorption salt lake old halogen, is transformed into rich lithium state; The lithium ion carrier of rich lithium state is namely containing LiMn simultaneously
2o
4electrode in anode chamber, be oxidized under anode current, release lithium ion, be transformed into poor lithium state.After exceeding decomposition voltage scope, exchange two electrode slice positions, namely containing LiMn
2o
4the lithium ion carrier of poor lithium state that has been transformed into of electrode put into cathode chamber, cathodic reduction, the lithium ion in the old halogen in absorption salt lake, and then be transformed into the lithium ion carrier of rich lithium state; Containing VO
2electrode be transformed into the lithium ion carrier of rich lithium state at said process after, put into anodic oxidation, in anolyte, discharge lithium ion, be transformed into the lithium ion carrier of poor lithium state.Be more than a circulation, operate 30 times according to above-mentioned steps, in the process, LiNO in anode chamber
3in solution, lithium concentration constantly increases, finally by LiNO
3solution evaporative crystallization, obtains LiNO
3solid, its content is 99.8%, in whole process, the rate of recovery of Li is 91.1%.
Embodiment 6
With spinelle LiMn
2o
4as the lithium ion carrier of rich lithium state, made electrode and carry out, the weight percent content of electrode four components is as follows:
Lithium ion carrier is spinelle LiMn
2o
4: 51.4%;
Electric conducting material is expanded graphite: 8.7%;
Carrier material nickel foam: 37.8%;
Adhesive PTFE:2.1%.
By 20 grams of LiMn
2o
4the lithium ion carrier electrode made according to aforementioned proportion, be that auxiliary electrode made by nickel plate to electrode, reference electrode is SCE electrode, and electrolysis tank centre barrier film separates.The anode carrier of electrolysis tank is placed the lithium ion carrier containing rich lithium state and LiMn
2o
4electrode slice, anode chamber passes into and sets to 0 .5mol/LLiNO
3solution, cathode chamber passes into above-mentioned class salt lake bittern solution simultaneously.Relative to LiMn
2o
4theoretical can 85% stage of deintercalate lithium ions total amount, 1A constant current (current density is 50mA/g) is adopted to carry out electrolysis 1.5 hours, controlling anode potential is subsequently 2.2V (relative to saturated calomel electrode), continues electrolysis 1 hour, until Li residual in lithium ion carrier
+enter anolyte, this process LiMn
2o
4release lithium ion, becomes the lithium ion carrier electrode of poor lithium state.
The lithium ion carrier of the poor lithium state of above-mentioned anodized gained is placed on the negative electrode of electrolysis tank, external direct current power supply, electrolysis is carried out to 90% degree of depth with constant current 120mAh/g, residual 10% enters the constant-potential electrolysis stage subsequently, now to arrange anodization potentials be voltage is 2.2V (relative to saturated calomel electrode), continues electrolysis 5 hours.Wherein lithium ion carrier electrode is namely containing LiMn
2o
4electrode, constantly reduce in cathode current, the lithium ion in absorption class salt lake bittern solution, is transformed into the lithium ion carrier of rich lithium state; By the lithium ion carrier of rich lithium state, it puts into anode chamber, is oxidized under anode current, and release lithium ion, is transformed into the lithium ion carrier of poor lithium state, and the negative electrode putting into next circulation utilizes.Above-mentioned oxidative reduction step circulates 20 times, in the process, and LiNO in anode chamber
3in solution, lithium concentration constantly increases, finally by LiNO
3solution evaporative crystallization, obtains LiNO
3solid, its content is 98.7%, and in whole process, the rate of recovery of Li is 96.5%.
Claims (10)
1. utilize lithium ion carrier from containing the method extracting lithium resource lithium ion solution, it is characterized in that, comprise the steps:
(1) lithium ion in the lithium ion solution that under the reducing conditions, the lithium ion carrier absorption of poor lithium state is to be recycled obtains the lithium ion carrier of rich lithium state;
(2) under oxidative conditions, make the lithium ion carrier of the rich lithium state of step (1) discharge lithium ion, and bear the lithium ion carrier of poor lithium state again.
(3) by iterative cycles step (1) and (2), lithium ion carrier is made constantly from lithium ion solution, to reclaim lithium resource.
2. according to the method described in claims 1, the lithium ion carrier of the poor lithium state described in its step (1) is one or more in Mn oxide, barium oxide, or taken off by the lithium ion carrier of rich lithium state that lithium obtains, wherein the lithium ion carrier of rich lithium state is LiCoO
2, LiMn
2o
4, LiNiO
2, LiFePO
4, LiMnO
2, LiV
3o
8, LiVO
2, LiV
2o
4, Li
6v
5o
15, Li
4ti
5o
12, LiCo
0.2ni
0.8o
2, LiCo
0.5ni
0.5, LiNi
xco
1-2xmn
xo
2, LiNi
1-x-yco
xmn
yo
2, LiNi
xco
1-x-ymn
yo
2, LiNi
xco
ymn
1-x-yo
2one or several mixtures in material, wherein 0<x<0.5 and 0<y<1.
3. according to the method for claim 1, it is characterized in that, containing LiNO in lithium ion solution to be recycled
3, LiCl, Li
2sO
4, LiOH, LiClO
4, LiAsF
6, LiPF
6, Li
2cO
3, LiI, LiBr, Li
2s, Li
2sO
3, LiIO
3, one or more mixtures in LiAc lithium salts solution, its lithium concentration is 0.01-11000mmol/L.
4. according to the method for claim 1, it is characterized in that, described reduction and oxidation adopt electrochemical reduction and oxidation;
That the lithium ion carrier of poor lithium state is placed in lithium ion solution to be recycled by electrode slice or carrier with the form that electrode directly contacts under reducing condition described in step (1), and carry out reduction process with the cathode contacts of electrolysis tank, this process absorbs the lithium ion carrier that lithium ion obtains rich lithium state;
The oxidizing condition of step (2) is that the lithium ion carrier of rich lithium state is placed in the form that electrode directly contacts the solution waiting to collect lithium ion by electrode slice or carrier, and carries out with the positive contact of electrolysis tank the lithium ion carrier that oxidation reaction discharges the poor lithium state of lithium ion solution that lithium ion is recycled and regeneration.
5. according to the method for claim 4, it is characterized in that, the electrode be made into by lithium ion carrier containing lithium ion carrier carries out, and detailed process is that lithium ion carrier, electric conducting material, carrier and adhesive are made electrode slice, and the weight percent content of four components of composition electrode slice is as follows:
Lithium ion carrier: 20-99.5%;
Electric conducting material: 0.2-40%;
Carrier material: 0.2-20%;
Adhesive: 0.1-20%;
Electric conducting material is one or several any composite materials in expanded graphite, acetylene black, active carbon, electric capacity carbon, carbon nano-tube; Carrier material is any one material in nickel foam, stainless (steel) wire, carbon cloth, titanium plate, graphite cake; Adhesive is one in polytetrafluoroethylene (PTFE), Kynoar (PVDF), PVP (PVP) or multiple mixed materials arbitrarily.
6. according to the method for claim 4, it is characterized in that, lithium ion carrier is directly positioned in electrolysis tank and reacts with electrode contact; Or lithium ion carrier is suspended in solution to be recycled or to be collected, makes it to be in suspended state by stirring solution constantly or flowing, thus ensure the effective contact between lithium ion carrier and electrode.
7. according to arbitrary method of claim 4-6, it is characterized in that, adopt inert anode carrier or/and inert cathode carrier.
8. according to the either method of claim 4-6, it is characterized in that, in same electrolysis tank, the lithium ion carrier of the lithium ion carrier absorption lithium ion of the poor lithium state of negative electrode and the rich lithium state of anode discharges lithium ion to carry out simultaneously.
9. according to the either method of claim 4-6, it is characterized in that, each cyclic process adopts constant-current electrolysis, and its current density makes every gram of lithium ion carrier corresponding current 1-5000mA.
10. according to the either method of claim 4-6, it is characterized in that, each cyclic process adopts electrolysis stage by stage, the initial rank of each circulation of cathodic reduction absorption lithium ion adopt constant-current electrolysis pattern, current density is 1-5000mA/g, constant-potential electrolysis pattern is converted to when the lithium ion carrier of poor lithium state completes theoretical adsorbance 50-95%, until lithium ion carrier adsorption lithium ion is saturated, cathodic reduction control of Electric potentials is at-1.5--0.1V (being equivalent to saturated calomel electrode), wherein theoretical adsorbance is the amount of lithium ions that the lithium ion carrier of poor lithium state needs absorption when becoming the lithium ion carrier of rich lithium state completely, the initial rank of each circulation of anodic oxidation lithium ionic insertion/deinsertion adopt constant-current electrolysis pattern, current density 1-5000mA/g, constant-potential electrolysis pattern is converted to when the lithium ion carrier of rich lithium state completes theoretical de-lithium amount 50-90%, anodization potentials controls in 0.3-2.5V (relative to saturated calomel electrode), and wherein theoretical de-lithium amount is the amount of lithium ions that the lithium ion carrier of rich lithium state needs desorption when becoming the lithium ion carrier of poor lithium state completely.
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