CN108190922A - A kind of recovery method of waste and old lithium titanate anode piece - Google Patents
A kind of recovery method of waste and old lithium titanate anode piece Download PDFInfo
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- CN108190922A CN108190922A CN201711339874.XA CN201711339874A CN108190922A CN 108190922 A CN108190922 A CN 108190922A CN 201711339874 A CN201711339874 A CN 201711339874A CN 108190922 A CN108190922 A CN 108190922A
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- lithium titanate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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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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- 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 discloses a kind of recovery method of waste and old lithium titanate anode piece, including：Under a shielding gas, the waste and old lithium titanate anode piece containing electrolyte is calcined to obtain lithium titanate anode piece；By lithium titanate anode piece or waste and old lithium titanate anode piece ultrasonic vibration without electrolyte, lithium titanate powder is made to come off from aluminium foil；Placement is sealed after concentrated sulfuric acid stirring is added in lithium titanate powder, adds heating stirring after water, filters to obtain leachate；The water phase that multitple extraction must be containing titanium and lithium ion is carried out after adjusting pH of leaching solution；It will be concentrated containing the water phase of titanium and lithium ion, metatitanic acid and lithium sulfate solution precipitated to obtain after hydrolysis；Lithium sulfate solution evaporative crystallization is obtained into lithium sulfate.The recovery method of waste and old lithium titanate anode piece proposed by the present invention, it can detach, purify the metals such as aluminium, titanium, lithium in waste and old lithium titanate anode piece, and flow is short, efficient, separation is excellent, easy to operate, environmentally protective, has extremely strong social value and considerable economic benefit.
Description
Technical field
The present invention relates to waste lithium cell recovery technology field more particularly to a kind of recycling sides of waste and old lithium titanate anode piece
Method.
Background technology
Lithium titanate has three-dimensional lithium ion diffusion admittance specific to spinel structure, has power characteristic excellent and height
The advantages that warm excellent performance.Lithium titanate anode lithium ion battery charging when, lithium ion is deviate from from anode, by electrolyte and every
Film is embedded into cathode；When then discharging, lithium ion is deviate from from cathode, again by electrolyte and diaphragm, then is embedded into just
In extremely.Such iterative cycles since lithium ion has the relatively-stationary space and position that can accommodate in positive and negative electrode, ensure
Battery charging and discharging reaction has good invertibity, so as to also ensure that the cycle life and safety of battery to a certain extent
Performance.Compared with common ferric phosphate lithium cell, ternary lithium battery, lithium titanate anode lithium ion battery discharges at low ambient temperatures
Efficiency decays small, fast charge efficiency strong (6 minutes can be fully charged), cycle life can be more than 30,000 times.With new-energy automobile city of China
Expansion and energy storage market gradual exploitation, lithium titanate battery with other batteries as, have a wide range of applications with rapidly
Growth, and the waste and old lithium titanate battery of the thing followed can also increase year by year.
Waste and old lithium titanate anode piece mainly by aluminium foil, lithium titanate, nonactive conductive agent (such as conductive carbon), additive (such as
The doping metals such as zirconium, strontium, silver, copper), adhesive (such as CMC, PVDF), electrolyte (such as LiPF6, EC, EMC, DMC, PC) etc.
Composition.This causes waste and old lithium titanate anode tablet raw material to can be divided mainly into two kinds：One kind is lithium battery manufacturer in generation metatitanic acid
It, can be because in slurry, coating, roll-in, cutting, winding, hot pressing, the workshop sections such as welding be closed, due to technology and operation during lithium cathode sheet
Reason, caused by unqualified or leftover pieces, the lithium titanate anode piece through disassembling.Since it is not handled by fluid injection, no
There are the influences of electrolyte, it is possible to directly lithium titanate anode tablet raw material be handled；Another kind is fluid injection, chemical conversion
It is unsatisfactory for criterion of acceptability afterwards and forces to disassemble the lithium titanate separated in lithium titanate battery scrapping or scrapping after using
Negative plate, this raw material need first to be collected electrolyte, then to lithium titanate anode tablet raw material due to impregnating in the electrolytic solution
It is recycled.
In recent years, many researchers do a large amount of work with regeneration to the recycling of waste and old lithium titanate anode material
Make.
Chinese Patent Application No.：201610665778.3 disclose a kind of method for recycling lithium titanate electrode plate, packet
Negative electrode active material and aluminium foil pole piece will be contained by, which including, carries out high-temperature roasting separation, and negative electrode active material is through crushing, being burnt into, sieving
To lithium titanate anode material.Chinese Patent Application No.：201710226858.3 it discloses one kind to return from waste and old lithium titanate battery
The method that receipts prepare lithium titanate anode material, including by the way that waste and old lithium titanate battery to be discharged to, torn open shell, sub-argument goes out pole piece, and adds
Hot submersion, the lithium titanate battery material paste sintering isolated remove conductive carbon materials, then by itself and conductive covering, doping
Agent and lithium salt material mixing, calcining, prepare lithium titanate anode material.This two patents are preparing lithium titanate anode material process
In, necessary removal of impurities processing is not carried out to raw material, during entire technological operation and carrying out, is inevitably introduced newly
Impurity can all produce bigger effect every electrical property of final products-lithium titanate anode material.
Chinese Patent Application No.：201611245696.X a kind of recoverying and utilizing method of waste and old lithium titanate is disclosed, including
Binding agent and conductive agent in pole piece is removed by calcining, alkali leaches to obtain lithium titanate leachate, through precipitant mix, ageing,
Filtering finally obtains lithium carbonate, titanium dioxide.The leaching of the peroxide root complexometry that this patent uses under alkaline condition, to technique
More demanding, leaching rate fluctuation is larger, while also has larger impact to the processing of follow-up titanium, lithium separation, realizes that industrialization is more difficult.
Invention content
Technical problems based on background technology, the present invention propose a kind of recycling side of waste and old lithium titanate anode piece
Method can detach, purify the metals such as aluminium, titanium, lithium in waste and old lithium titanate anode piece, and flow is short, efficient, separation is excellent, behaviour
Make it is simple, environmentally protective, have extremely strong social value and considerable economic benefit.
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, calcining：Under a shielding gas, the waste and old lithium titanate anode piece containing electrolyte is calcined into 2- at 350-550 DEG C
4h obtains lithium titanate anode piece and tail gas；
S2, ultrasonic Separation：Lithium titanate anode piece in S1 or the waste and old lithium titanate anode piece without electrolyte are placed in super
0.5-2h is shaken in acoustic wave oscillator, lithium titanate powder is made to come off from aluminium foil, realizes the two separation, wherein, concussion frequency is
30-40KHz；
S3, sulfuric acid dump leaching：The concentrated sulfuric acid being added in S2 in gained lithium titanate powder to stir evenly, 12-48h is placed in sealing,
1-2h is stirred at 60-80 DEG C after adding water, filters to obtain leachate and leached mud；
S4, abstraction impurity removal：The pH value of leachate is adjusted as 2.5-4, obtained after being extracted using extractant containing titanium and lithium from
The water phase of son；
S5, the heavy titanium of hydrolysis：It will be concentrated obtained by S4 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and sulphur after hydrolysis
Sour lithium solution；
S6, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S5 is obtained into lithium sulfate.
Preferably, in S1, the protective gas is the mixture of one or more of nitrogen, helium, argon gas.
Preferably, in S1, the waste and old lithium titanate anode piece containing electrolyte is from the intercell scrapped or waste and old
The waste and old lithium titanate anode piece directly dismantled on battery.
Preferably, in S1, direct emission or collection recycling after the condensed liquefaction recycling organic matter of tail gas.
Preferably, in S2, the waste and old lithium titanate anode piece without electrolyte is the waste and old metatitanic acid without fluid injection
Lithium cathode sheet.
Preferably, in S3, the mass ratio of lithium titanate powder and the concentrated sulfuric acid is 1：1-3.
Preferably, in S3, the mass ratio of lithium titanate powder and water is 1：3-5.
Preferably, in S4, the pH value of leachate is adjusted with ammonium hydroxide.
Preferably, in S4, the extractant is P204, N263, one or more mixing in TBP, sulfonated kerosene
Object.
Preferably, in S4, in extraction process, saponification rate 20-50%, O/A=1：3-4；The extraction is multistage
Counter-current extraction.
Compared with prior art, beneficial effects of the present invention：The present invention is according to two distinct types of lithium titanate anode piece
Using different pre-treatment schemes, electrolyte is avoided to the influence of subsequent technique and its constantly volatilization to the shadow of working environment
It rings；By the way of sulfuric acid dump leaching, on the one hand, the concentrated sulfuric acid can be made directly to destroy lithium titanate lattice and improve follow-up leaching rate, it is another
Aspect, due to having destroyed lithium titanate lattice so that sour amount, temperature, time all decrease needed for follow-up leaching；Using extraction
Removal of impurities, can effectively reduce the foreign metal in leachate, possibility is provided to obtain pure metatitanic acid and lithium sulfate.The present invention
Middle lithium, titanium are efficiently separated, and good separating effect, purity are high, have preferable productivity effect.
Description of the drawings
Fig. 1 is the flow chart of the recovery method of waste and old lithium titanate anode piece proposed by the present invention.
Specific embodiment
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
Fig. 1 is the flow chart of the recovery method of waste and old lithium titanate anode piece proposed by the present invention；With reference to Fig. 1, the present invention carries
The recovery method of a kind of waste and old lithium titanate anode piece gone out, includes the following steps：
S1, calcining：The waste and old lithium titanate anode piece (containing electrolyte) directly dismantled from the intercell scrapped is taken,
Under nitrogen protection, it is put into tube furnace, 4h is calcined at 350 DEG C and obtains lithium titanate anode piece and tail gas, the condensed liquid of tail gas
Change recycling organic matter, gas is mainly be passed through protective gas nitrogen after purification, collects and recycles；
S2, ultrasonic Separation：The lithium titanate anode piece obtained after being calcined in S1, which is placed in ultrasonic oscillator, shakes separation,
Frequency 40KHz is shaken, 0.5h is shaken, lithium titanate powder is made to come off from aluminium foil and is detached；
S3, sulfuric acid dump leaching：In the lithium titanate powder obtained in S2 according to solid-liquid mass ratio be 1:3 add in the concentrated sulfuric acid, stir
It mixes uniformly, and seals and place 12h, water is added in after the concentrated sulfuric acid destroys lithium titanate lattice completely, wherein, lithium titanate powder and water
Weight ratio is 1:5,2h is stirred at 60 DEG C, filters to obtain leached mud and the leachate containing lithium, titanium；
S4, abstraction impurity removal：The pH=4 of leachate is adjusted with ammonium hydroxide, filtering is configured to extract with P204, TBP, sulfonated kerosene
Agent is taken to carry out Pyatyi counter-current extraction, wherein, saponification rate 50%, O/A=1:4, P204, TBP, sulfonated kerosene weight ratio be
25:10:65, by extraction, foreign metal ion enters organic phase, lithium, titanium ion stay in water phase obtain containing titanium and lithium from
The water phase of son；
S5, the heavy titanium of hydrolysis：By in S4 gained containing the water phase of titanium and lithium ion concentrate, hydrolysis, be settled out metatitanic acid and obtain
To lithium sulfate solution；
S6, evaporative crystallization：By the lithium sulfate solution evaporative crystallization of gained in S5, lithium sulfate is obtained.
Embodiment 2
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, calcining：The waste and old lithium titanate anode piece (containing electrolyte) directly dismantled from the intercell scrapped is taken,
It under helium protection, is put into tube furnace, calcining 2h at 550 DEG C obtains lithium titanate anode piece and tail gas, the condensed liquefaction of tail gas
Organic matter is recycled, predominantly the be passed through protective gas helium of gas, direct emission after purification；
S2, ultrasonic Separation：The lithium titanate anode piece obtained after being calcined in S1, which is placed in ultrasonic oscillator, shakes separation,
Frequency 30KHz is shaken, 2h is shaken, lithium titanate powder is made to come off from aluminium foil and is detached；
S3, sulfuric acid dump leaching：In the lithium titanate powder obtained in S2 according to solid-liquid mass ratio be 1:1 adds in the concentrated sulfuric acid, stirs
It mixes uniformly, and seals and place 48h, water is added in after the concentrated sulfuric acid destroys lithium titanate lattice completely, wherein, lithium titanate powder and water
Weight ratio is 1:3,1h is stirred at 80 DEG C, filters to obtain leached mud and the leachate containing lithium, titanium；
S4, abstraction impurity removal：The pH=2.5 of leachate is adjusted with ammonium hydroxide, filtering is configured to extract with N263 and sulfonated kerosene
Agent carries out seven stage countercurrent extractions, wherein, saponification rate 20%, O/A=1:3, N263 and sulfonated kerosene weight ratio be 20:80,
By extraction, foreign metal ion enters organic phase, and lithium, titanium ion stay in water phase the water phase obtained containing titanium and lithium ion；
S5, the heavy titanium of hydrolysis：By in S4 gained containing the water phase of titanium and lithium ion concentrate, hydrolysis, be settled out metatitanic acid and obtain
To lithium sulfate solution；
S6, evaporative crystallization：By the lithium sulfate solution evaporative crystallization of gained in S5, lithium sulfate is obtained.
Embodiment 3
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
The waste and old lithium titanate anode piece without fluid injection is taken to be placed in ultrasonic oscillator and shakes separation, shakes frequency
40KHz shakes 1h, lithium titanate powder is made to come off from aluminium foil and is detached；By lithium titanate powder according to solid-liquid mass ratio be 1:2
The concentrated sulfuric acid is added in, is stirred evenly, and seals placement for 24 hours, water is added in after the concentrated sulfuric acid destroys lithium titanate lattice completely, wherein, titanium
The weight ratio of sour lithium powder and water is 1:5,2h is stirred at 70 DEG C, filters to obtain leached mud and the leachate containing lithium, titanium；Use ammonia
Water adjusts the pH=3.5 of leachate, and filtering is configured to extractant with P204 and sulfonated kerosene and carries out Pyatyi counter-current extraction, wherein,
Saponification rate is 30%, O/A=1:4, P204 and sulfonated kerosene weight ratio be 25:75, by extraction, foreign metal ion enters
Organic phase, lithium, titanium ion stay in water phase the water phase obtained containing titanium and lithium ion；By the water containing titanium and lithium ion of gained
It mutually concentrates, hydrolysis is settled out metatitanic acid and obtains lithium sulfate solution；By the lithium sulfate solution evaporative crystallization of gained, lithium sulfate is obtained.
Embodiment 4
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, calcining：Under a shielding gas, the waste and old lithium titanate anode piece containing electrolyte is calcined 4h to obtain at 350 DEG C
Lithium titanate anode piece and tail gas；
S2, ultrasonic Separation：Lithium titanate anode piece in S1 is placed in ultrasonic oscillator and shakes 0.5h, makes lithium titanate powder
Material comes off from aluminium foil, realizes the two separation, wherein, concussion frequency is 40KHz；
S3, sulfuric acid dump leaching：The concentrated sulfuric acid is added in S2 in gained lithium titanate powder to stir evenly, 48h is placed in sealing, adds water
2h is stirred at 60 DEG C afterwards, filters to obtain leachate and leached mud；
S4, abstraction impurity removal：The pH value of leachate is adjusted as 4, is obtained after being extracted using extractant containing titanium and lithium ion
Water phase；
S5, the heavy titanium of hydrolysis：It will be concentrated obtained by S4 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and sulphur after hydrolysis
Sour lithium solution；
S6, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S5 is obtained into lithium sulfate.
Embodiment 5
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, calcining：Under a shielding gas, the waste and old lithium titanate anode piece containing electrolyte is calcined 2h to obtain at 550 DEG C
Lithium titanate anode piece and tail gas；
S2, ultrasonic Separation：Waste and old lithium titanate anode piece without electrolyte is placed in ultrasonic oscillator and shakes 2h, is made
Lithium titanate powder comes off from aluminium foil, realizes the two separation, wherein, concussion frequency is 30KHz；
S3, sulfuric acid dump leaching：The concentrated sulfuric acid is added in S2 in gained lithium titanate powder to stir evenly, 12h is placed in sealing, adds water
1h is stirred at 80 DEG C afterwards, filters to obtain leachate and leached mud；
S4, abstraction impurity removal：The pH value for adjusting leachate is 2.5, is obtained after being extracted using extractant containing titanium and lithium ion
Water phase；
S5, the heavy titanium of hydrolysis：It will be concentrated obtained by S4 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and sulphur after hydrolysis
Sour lithium solution；
S6, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S5 is obtained into lithium sulfate.
Embodiment 6
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, calcining：Under argon gas, the waste and old lithium titanate anode piece directly dismantled from the intercell scrapped is existed
2h is calcined at 550 DEG C and obtains lithium titanate anode piece and tail gas, organic matter is recycled in the condensed liquefaction of tail gas, then direct emission；
S2, ultrasonic Separation：Lithium titanate anode piece in S1 is placed in ultrasonic oscillator and shakes 2h, makes lithium titanate powder
It comes off from aluminium foil, realizes the two separation, wherein, concussion frequency is 30KHz
S3, sulfuric acid dump leaching：The concentrated sulfuric acid is added in S2 in gained lithium titanate powder to stir evenly, lithium titanate powder and dense sulphur
The mass ratio of acid is 1：1,48h is placed in sealing, is added and is stirred 2h after water at 60 DEG C, and the mass ratio of lithium titanate powder and water is 1：3,
Filter to obtain leachate and leached mud；
S4, abstraction impurity removal：The pH value that leachate is adjusted with ammonium hydroxide is 2.5, after carrying out Pyatyi counter-current extraction using extractant
Obtain the water phase containing titanium and lithium ion；The extractant be TBP, saponification rate 20%, O/A=1：4；
S5, the heavy titanium of hydrolysis：It will be concentrated obtained by S4 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and sulphur after hydrolysis
Sour lithium solution；
S6, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S5 is obtained into lithium sulfate.
Embodiment 7
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, calcining：Under a nitrogen, by the waste and old lithium titanate anode piece directly dismantled from old and useless battery at 350 DEG C
Lower calcining 4h obtains lithium titanate anode piece and tail gas, then the condensed liquefaction recycling organic matter of tail gas is collected and recycled；
S2, ultrasonic Separation：Lithium titanate anode piece in S1 is placed in ultrasonic oscillator and shakes 0.5h, makes lithium titanate powder
Material comes off from aluminium foil, realizes the two separation, wherein, concussion frequency is 40KHz；
S3, sulfuric acid dump leaching：The concentrated sulfuric acid is added in S2 in gained lithium titanate powder to stir evenly, lithium titanate powder and dense sulphur
The mass ratio of acid is 1：3,12h is placed in sealing, is added and is stirred 1h after water at 80 DEG C, and the mass ratio of lithium titanate powder and water is 1：5,
Filter to obtain leachate and leached mud；
S4, abstraction impurity removal：The pH value that leachate is adjusted with ammonium hydroxide is 4, is obtained after carrying out four-stage counter-current extraction using extractant
To the water phase containing titanium and lithium ion；The extractant be P204, saponification rate 50%, O/A=1：3；
S5, the heavy titanium of hydrolysis：It will be concentrated obtained by S4 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and sulphur after hydrolysis
Sour lithium solution；
S6, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S5 is obtained into lithium sulfate.
Embodiment 8
A kind of recovery method of waste and old lithium titanate anode piece proposed by the present invention, includes the following steps：
S1, ultrasonic Separation：1h is shaken by being placed in ultrasonic oscillator without the waste and old lithium titanate anode piece of fluid injection, is made
Lithium titanate powder comes off from aluminium foil, realizes the two separation, wherein, concussion frequency is 35KHz；
S2, sulfuric acid dump leaching：The concentrated sulfuric acid is added in S1 in gained lithium titanate powder to stir evenly, lithium titanate powder and dense sulphur
The mass ratio of acid is 1：2,30h is placed in sealing, is added and is stirred 1.5h after water at 70 DEG C, and the mass ratio of lithium titanate powder and water is 1：
4, filter to obtain leachate and leached mud；
S3, abstraction impurity removal：The pH value that leachate is adjusted with ammonium hydroxide is 3, is obtained after carrying out seven stage countercurrent extractions using extractant
To the water phase containing titanium and lithium ion；The extractant is P204, N263, the mixture of TBP, sulfonated kerosene, and P204,
N263, TBP, sulfonated kerosene mass ratio be 2：4：5：1, saponification rate 40%, O/A=1：3；
S4, the heavy titanium of hydrolysis：It will be concentrated obtained by S3 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and sulphur after hydrolysis
Sour lithium solution；
S5, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S4 is obtained into lithium sulfate.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of recovery method of waste and old lithium titanate anode piece, which is characterized in that include the following steps：
S1, calcining：Under a shielding gas, the waste and old lithium titanate anode piece containing electrolyte is calcined 2-4h to obtain at 350-550 DEG C
To lithium titanate anode piece and tail gas；
S2, ultrasonic Separation：Lithium titanate anode piece in S1 or the waste and old lithium titanate anode piece without electrolyte are placed in ultrasonic wave
0.5-2h is shaken in oscillator, lithium titanate powder is made to come off from aluminium foil, realizes the two separation, wherein, concussion frequency is 30-
40KHz；
S3, sulfuric acid dump leaching：The concentrated sulfuric acid is added in S2 in gained lithium titanate powder to stir evenly, 12-48h is placed in sealing, adds water
1-2h is stirred at 60-80 DEG C afterwards, filters to obtain leachate and leached mud；
S4, abstraction impurity removal：The pH value of leachate is adjusted as 2.5-4, is obtained after being extracted using extractant containing titanium and lithium ion
Water phase；
S5, the heavy titanium of hydrolysis：It will be concentrated obtained by S4 containing the water phase of titanium and lithium ion, precipitation obtains metatitanic acid and lithium sulfate after hydrolysis
Solution；
S6, evaporative crystallization：Lithium sulfate solution evaporative crystallization in S5 is obtained into lithium sulfate.
2. the recovery method of waste and old lithium titanate anode piece according to claim 1, which is characterized in that in S1, the protection
Gas is the mixture of one or more of nitrogen, helium, argon gas.
3. the recovery method of waste and old lithium titanate anode piece according to claim 1 or claim 2, which is characterized in that described to contain in S1
The waste and old lithium titanate anode piece of electrolyte is the waste and old metatitanic acid directly dismantled from the intercell or old and useless battery scrapped
Lithium cathode sheet.
4. according to the recovery method of any one of the claim 1-3 waste and old lithium titanate anode pieces, which is characterized in that in S1
In, direct emission or collection recycling after the condensed liquefaction recycling organic matter of tail gas.
5. according to the recovery method of any one of the claim 1-4 waste and old lithium titanate anode pieces, which is characterized in that in S2
In, the waste and old lithium titanate anode piece without electrolyte is the waste and old lithium titanate anode piece without fluid injection.
6. according to the recovery method of any one of the claim 1-5 waste and old lithium titanate anode pieces, which is characterized in that in S3
In, the mass ratio of lithium titanate powder and the concentrated sulfuric acid is 1：1-3.
7. according to the recovery method of any one of the claim 1-6 waste and old lithium titanate anode pieces, which is characterized in that in S3
In, the mass ratio of lithium titanate powder and water is 1：3-5.
8. according to the recovery method of any one of the claim 1-7 waste and old lithium titanate anode pieces, which is characterized in that in S4
In, with the pH value of ammonium hydroxide adjusting leachate.
9. according to the recovery method of any one of the claim 1-8 waste and old lithium titanate anode pieces, which is characterized in that in S4
In, the extractant is P204, N263, one or more mixtures in TBP, sulfonated kerosene.
10. according to the recovery method of any one of the claim 1-9 waste and old lithium titanate anode pieces, which is characterized in that in S4
In, in extraction process, saponification rate 20-50%, O/A=1：3-4；The extraction is multi-stage counter current extraction.
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Cited By (5)
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| CN109216821A (en) * | 2018-09-05 | 2019-01-15 | 合肥国轩高科动力能源有限公司 | A kind of recovery method of waste and old lithium titanate battery |
| CN109524735A (en) * | 2018-10-19 | 2019-03-26 | 合肥国轩高科动力能源有限公司 | A kind of recovery method of waste lithium iron phosphate-lithium titanate battery |
| CN110735038A (en) * | 2018-07-21 | 2020-01-31 | 浙江遨优动力系统有限公司 | method for recycling electrode metal materials from waste lithium titanate batteries |
| CN111326810A (en) * | 2018-12-13 | 2020-06-23 | 多氟多化工股份有限公司 | Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece |
| CN114039118A (en) * | 2021-11-06 | 2022-02-11 | 高伟 | Electrode material recycling equipment and recycling method for waste lithium titanate battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110735038A (en) * | 2018-07-21 | 2020-01-31 | 浙江遨优动力系统有限公司 | method for recycling electrode metal materials from waste lithium titanate batteries |
| CN109216821A (en) * | 2018-09-05 | 2019-01-15 | 合肥国轩高科动力能源有限公司 | A kind of recovery method of waste and old lithium titanate battery |
| CN109524735A (en) * | 2018-10-19 | 2019-03-26 | 合肥国轩高科动力能源有限公司 | A kind of recovery method of waste lithium iron phosphate-lithium titanate battery |
| CN111326810A (en) * | 2018-12-13 | 2020-06-23 | 多氟多化工股份有限公司 | Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece |
| CN111326810B (en) * | 2018-12-13 | 2021-08-13 | 多氟多新材料股份有限公司 | Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece |
| CN114039118A (en) * | 2021-11-06 | 2022-02-11 | 高伟 | Electrode material recycling equipment and recycling method for waste lithium titanate battery |
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