CN106910889A - A kind of method that positive active material is regenerated from waste lithium iron phosphate battery - Google Patents

A kind of method that positive active material is regenerated from waste lithium iron phosphate battery Download PDF

Info

Publication number
CN106910889A
CN106910889A CN201710110134.2A CN201710110134A CN106910889A CN 106910889 A CN106910889 A CN 106910889A CN 201710110134 A CN201710110134 A CN 201710110134A CN 106910889 A CN106910889 A CN 106910889A
Authority
CN
China
Prior art keywords
active material
iron phosphate
step
lithium
lithium iron
Prior art date
Application number
CN201710110134.2A
Other languages
Chinese (zh)
Other versions
CN106910889B (en
Inventor
方静
杨声海
刘文文
赖延清
张治安
洪波
张凯
李劼
Original Assignee
中南大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中南大学 filed Critical 中南大学
Priority to CN201710110134.2A priority Critical patent/CN106910889B/en
Publication of CN106910889A publication Critical patent/CN106910889A/en
Application granted granted Critical
Publication of CN106910889B publication Critical patent/CN106910889B/en

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic slats or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries

Abstract

The invention discloses a kind of renovation process of lithium iron phosphate battery anode active material:1) after waste lithium iron phosphate battery is discharged through salt solution, organic solvent, core and sheathing material are disassembled out;2) after the step such as size-reduced, roasting of core, vibration screening isolates active material, Copper Foil and aluminium foil.Waste gas containing fluoride is absorbed with limewash, magnetic method separates Copper Foil and aluminium foil, and active material utilizes sulfuric acid leaching, isolated leachate and carbon slag;3) leachate is using adding the method for iron powder reducing by Cu therein2+Elemental copper is reduced into, while by Fe3+It is reduced into Fe2+, after being removed by filtration copper and unnecessary scum, alkali lye precipitation except aluminium, again toward supplementing phosphorus source in filtrate after filtering, and by plus alkali lye adjust pH value, generation raw phosphoric acid iron lithium precipitation is last sintered to obtain battery-grade iron phosphate lithium.The present invention realizes the comprehensive utilization of waste lithium iron phosphate battery and the regeneration of active material using simple and practical, economically viable method, and any secondary pollution is not produced, is adapted to industrialized production.

Description

A kind of method that positive active material is regenerated from waste lithium iron phosphate battery

Technical field

The invention belongs to lithium rechargeable battery recycling field, and in particular to one kind regenerates from waste lithium iron phosphate battery The method of positive active material.

Background technology

With the high speed development of modernization science and technology, social energy and environment ecological pollution problem becomes increasingly conspicuous, various discarded Battery is to the pollution problem of environment and ecology into the focus of social concerns.And ferric phosphate lithium cell due to its low cost, Cycle performance is good, be widely used in electrokinetic cell and energy-storage battery the features such as have a safety feature, and power and energy-storage battery pair The demand of battery material is typically larger than conventional compact battery.Therefore, in The Next 3-5 Years, there will be substantial amounts of LiFePO4 electricity Pond is scrapped, and it is carried out to reclaim has social value very high.

However, it is domestic at present still also without can simply efficiently and energy synthetical recovery waste lithium iron phosphate battery technology road Line, the ferric phosphate lithium cell also without specialty reclaims company, and major part is turned on the company for reclaiming banner, also only reclaims stock old Material rather than waste battery.Therefore, a complete process route capable of being industrialized is designed most important.Existing published recovery The patent of waste lithium iron phosphate battery all can not well take into account environment benefits and economic gains.

Presently disclosed recovery LiFePO4 old and useless battery is broadly divided into two methods:

One is directly reclaim lithium salts, without carrying out any effectively processing to phosphorus and ferro element.

For example, the Chinese patent literature of Publication No. CN103280610A discloses a kind of positive pole waste tablet from ferric phosphate lithium cell Recovery method, the method is using aluminium, iron and lithium in soda acid lixiviation process recovery LiFePO4 old and useless battery positive pole waste paper.The method is simultaneously Without reference to the treatment of Phosphorus From Wastewater element, secondary pollution is caused to environment;In addition, valuable metal ferro element does not have appropriate returning Receive, can also reduce the economic benefit of the program.

The second is being settled out ferric phosphate, lithium carbonate respectively, then synthesize new LiFePO4 through calcination process.

For example, the Chinese patent literature of Publication No. CN102664294A discloses a kind of returning for waste lithium iron phosphate battery Receiving method, the method processes refuse battery positive electrode successively using soda acid, and precipitate and separate obtains ferric phosphate and lithium carbonate, Ran Houfen Analysis obtains iron, lithium, the mol ratio of phosphorus of material, adds appropriate reactant adjustment proportioning, finally calcines in an inert atmosphere Obtain new lithium iron phosphate positive material.The technical scheme will certainly residual fraction during precipitate phosphoric acid iron, lithium carbonate In reaction solution, so as to influence the rate of recovery of valuable element;It is elongated that other precipitation respectively can directly result in recovery process so that place Uncontrollable factor increases during reason, and needs the reactant of addition to increase, so as to improve production cost.Additionally, the technology The specific capacity and coulombic efficiency of the composite positive pole of the final obtained LiFePO4/random carbon of scheme can be poor;Reason master It is:Random carbon in the composite positive pole produced will not provide any capacity, therefore the capacity of the composite is main Depending on the content of LiFePO4, that is to say, that carbon content is higher, the specific capacity of the composite is necessarily fewer;Secondly, cladding Irregular carbon material, may cause the specific surface of material to increase, and unnecessary side reaction can be produced (such as in first circle discharge process SEI films), so as to influence the coulombic efficiency of first circle.

To sum up analyze, prior art has that complex process, purpose element recovery rate be low, high cost outer, prepared mostly LiFePO4 product dephasign it is many, the problems such as thing phase homogeneity is poor, chemical property is poor.

The content of the invention

For the LiFePO 4 material dephasign for solving existing recovery is more, thing phase homogeneity is poor, recovery process is complicated, purpose The low problem of product recoveries, the present invention provides a kind of renovation process of lithium iron phosphate battery anode active material, it is intended to a step Realize the regeneration of battery-grade iron phosphate lithium.

A kind of method that positive active material is regenerated from waste lithium iron phosphate battery, comprises the following steps:

Step (1):After waste lithium iron phosphate battery is substantially discharged, disassemble to obtain core;

Step (2):It is calcined under air atmosphere after described core is broken;The product screening of roasting is obtained into copper, aluminium foil And active material;

Step (3):The active material that step (2) is obtained is immersed in acid solution, the pH of the acid solution is less than or equal to 2; After impregnation process leachate is obtained through separation of solid and liquid;Li is included in described leachate+、Fe3+、Al3+、Cu2+、PO4 3-

Step (4):Iron is added in leachate to step (3), with Fe3+And Cu2+Reduction reaction is carried out, through solid after reaction Liquid separates to obtain copper removal liquid;Described iron adds mole more than or equal to making Fe3+And Cu2+The theoretical molar amount of reduction;

Step (5):Copper removal liquid pH is to 3~5 for adjustment, and subsequent separation of solid and liquid must include Li+、Fe2+、PO4 3-Presoma it is molten Liquid;

Step (6):Lithium, iron, the mol ratio of phosphorus are 1~1.2: 1: 1 in adjustment precursor solution, then under pH=5~7 Separate out precipitation, separation of solid and liquid and obtain ferric lithium phosphate precursor;Described ferric lithium phosphate precursor is calcined under protective atmosphere again LiFePO4.

In the present invention, processed by roasting under air atmosphere, the acidleach under the pH, using iron to the treatment of leachate, Lithium, iron, the regulation and control of the mol ratio of phosphorus, ferric lithium phosphate precursor are separated out in regulation and control, the precursor solution of copper removal liquid pH scopes Each parameter such as pH and the collaboration of operation, are capable of achieving ferric lithium phosphate precursor and are generated in same solution system, can effectively ensure that again The quality of raw LiFePO4, for example, reduce the dephasign of product, improve product thing phase homogeneity;And then it is obviously improved obtained phosphorus The electric property of sour iron lithium.

In the present invention, in step (1), the waste lithium iron phosphate battery is substantially discharged through salt solution, described fully puts Electricity refers to:Waste lithium iron phosphate battery is discharged to final voltage less than 1V through salt solution.

Preferably, described salt solution is the sodium-chloride water solution of 10~30g/L.

Waste lithium iron phosphate battery after being substantially discharged mechanically or manually is disassembled, obtain organic solvent, core and Sheathing material.

Preferably, the size controlling of product is in 2.5mm~10mm after broken.In the preferred particle size range, more Beneficial to follow-up recovery.Active material can be caused to be difficult to separate with pole piece if particle diameter is too small, if particle diameter crosses conference causes bonding agent Incomplete combustion, reduces the rate of recovery of active material.

In the present invention, broken material is calcined under air atmosphere.

Preferably, in step (2), the temperature of roasting is 400~600 DEG C.

Preferably, in step (2), roasting time is 1~10h.The roasting time being more highly preferred to is 5~8h.

In step (2), the product vibration screening of roasting is obtained particle and the copper/aluminium foil (copper/aluminium mixing of active material Thing);Described copper, aluminium foil is separated by magnetic separation mode again.

In step (2), it is calcined the flue gas (waste gas) for producing and is processed through limewash (calcium hydroxide aqueous solution) absorption.

Contain HF in the flue gas that roasting is produced, the present invention absorbs torrefaction waste gas using limewash, fixes HF, and had The calcirm-fluoride of value.

Preferably, the concentration of described limewash is not less than 40mg/L.

In step (3), described acid solution is hydrochloric acid or sulfuric acid solution.

Further preferably, described acid solution is sulfuric acid solution.

Still more preferably, the concentration of described sulfuric acid solution is 0.1~5mol/L (with H2SO4Meter).

The inventors discovered that, in acid solution leaching process, control the pH of Leaching Systems in described scope, prevent Fe3+It is heavy Shallow lake causes iron loss.

Still more preferably, in step (3), in acid solution leaching process, pH <=1 is controlled.

In step (3), the solid-liquid system of acidleach is carried out into separation of solid and liquid, obtain leached mud and leachate.Described leaching Slag is mainly the charcoal in active component.Described leachate includes Li+、Fe3+、Al3+、Cu2+、PO4 3-Plasma.

The present inventor is originally processed leachate using iron, can unexpectedly be reduced obtained in a final step The dephasign of LiFePO4, improves the electric property of product.

The addition of iron has influence to reducing the dephasign of obtained LiFePO4, improving electric property, preferably, institute The mole that adds of the iron stated is to make Fe3+And Cu2+It is reduced into Fe2+With 1~1.2 times of the theoretical molar amount of Cu.

The dosage of iron is controlled, can on the one hand by the Fe in leachate3+It is reduced to Fe2+, on the other hand can also be by putting Change reaction and remove the Cu being mixed with solution2+, purified solution.On the other hand, ferrous iron in material waste and solution system can be avoided Ion imbalance.

Plus after iron reaction, separation of solid and liquid being carried out, the solid portion for obtaining is the impurity such as the copper of generation;The liquid portion for obtaining It is copper removal liquid, wherein, mainly contain Li+、Fe2+、Al3+、PO4 3-Plasma.

In step (5), the pH of copper removal liquid is adjusted to 3~5, make the Al in copper removal liquid3+With Al (OH)3Form separate out, Subsequent separation of solid and liquid is that can obtain Li+、Fe2+、PO4 3-Precursor solution in same solution system.

In the present invention, Al that can with high selectivity in precipitation system under the conditions of the described pH3+, can be further ensured that follow-up The performance of LiFePO4 product.Higher than the described pH upper limits, ferric lithium phosphate precursor co-precipitation, influence is easily set to reclaim effect Rate;Less than the pH lower limits, the dephasign of obtained product is more.

Preferably, in step (5), the pH for regulating and controlling copper removal liquid is 3.5~4.5.

In step (6), to the mol ratio that the described lithium of phosphorus source regulation and control, iron, phosphorus are filled into precursor solution;Described phosphorus source It is water-soluble phosphate.

Preferably, described phosphorus source be sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, At least one in DAP, potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.

In step (6), lithium, iron, the pH of the solution system of the mol ratio of phosphorus will be adjusted and adjusted to 5~7, in described pH bodies In system, separate out ferric lithium phosphate precursor combined in-situ in same solution system, the homogeneity of material is good, and purity is high, recovery Rate is high;Contribute to subsequent calcination that the LiFePO4 of excellent electric property is obtained.

The pH of ferric lithium phosphate precursor original position crystallization has influence to the quality of product, higher than the pH upper limits, easily to Dephasign is introduced in product, while can also increase cost.

Preferably, step (6):PH value is 5.5~6.5.

Preferably, in step (6), the temperature of calcining is 600~900 DEG C.

In step (6), described protective atmosphere is nitrogen and/or inert gas.

Described inert gas is, for example, helium, argon gas etc..

Under described calcining heat, preferred calcination time is 12~24h.

In the present invention, the obtained LiFePO4 of regeneration is LITHIUM BATTERY.

Battery-grade iron phosphate lithium obtained in renovation process of the present invention is used for the positive-active material of ferric phosphate lithium cell Material.

Separation of solid and liquid of the present invention can select existing conventional method, for example filter, be centrifuged etc..

The alkali lye that adjustment system pH of the present invention is used is, for example, at least one in NaOH, potassium hydroxide, ammoniacal liquor The aqueous solution.

A kind of preferred renovation process of the present invention, specifically includes following steps:

Step a) ferric phosphate lithium cells split:

After the waste lithium iron phosphate battery is substantially discharged through salt solution, organic solvent, core are mechanically or manually disassembled out And sheathing material;Described salt solution is the sodium chloride solution of 10~30g/L;Described being substantially discharged refers to low final discharging voltage In 1V;

Step b) active materials are separated:

The core that step a) is obtained is broken using mechanical force, is calcined 1~10h, vibration at 400~600 DEG C in atmosphere Filter out active material and copper, aluminium foil;

Torrefaction waste gas being absorbed with limewash and obtaining calcirm-fluoride, described lime water concentration is not less than 40mg/L;

Copper, aluminium foil use the isolated Copper Foil of magnetic method and aluminium foil;

Active material utilizes sulfuric acid leaching, is separated by filtration and obtains carbon slag and containing Li+、Fe3+、Al3+、Cu2+、PO4 3-Plasma Acid leaching solution;The pH controls of leaching process are 2 and less;The concentration of described sulfuric acid is 0.1~5mol/L (with H2SO4 Meter);

It is prepared by step c) lithium iron phosphate precursor solutions:

The leachate obtained to step b) adds iron powder, and the mole that adds of described iron is to make Fe3+And Cu2+It is reduced into Fe2+With 1~1.2 times of the theoretical molar amount of Cu;Described iron is respectively by Fe3+And Cu2+It is reduced into Fe2+And copper simple substance, after reaction Filtering, isolated filtrate (copper removal liquid);Alkali lye is added in filtrate again and adjusts pH to 3~5, make Al3+With Al (OH)3Form Separate out, filtering must contain Li+、Fe2+、PO4 3-Lithium iron phosphate precursor solution;

Step d) battery-grade iron phosphates lithium regenerates:

To supplementing phosphorus source in the precursor solution described in step c) so that lithium, iron, the mol ratio of phosphorus are adjusted to 1~1.2: 1 : 1, recycle alkali lye to adjust pH to 5~7, raw phosphoric acid iron lithium precipitation is filtrated to get, under an inert atmosphere, in 600~900 finally DEG C calcining 12~24h obtain battery-grade iron phosphate lithium.

After waste lithium iron phosphate battery electric discharge is disassembled leaching by the present invention, cheap and the Fe powder with reproducibility, one are added Aspect can be by Fe3+It is reduced to Fe2+, on the other hand can also remove the Cu being mixed with solution by replacing reaction2+, purify molten Liquid (copper removal liquid).Alkali lye regulation pH to 3~5 is added to remove Al after filtering thereto3+, the preparations of pH to 5~7 are adjusted after filtering and impurity removing again Ferric lithium phosphate precursor;Described ferric lithium phosphate precursor calcines to obtain LiFePO4 under protective atmosphere again.The program is not only P elements effective recovery is obtained into, it is to avoid it causes the secondary pollution of environment, and also improves other valuable metals The rate of recovery.The heavy LiFePO4 of one-step method that the program is used, greatly reduces production cost, and shorten production procedure.Separately Outward, before the heavy LiFePO4 of one-step method, the impurity in solution is first got rid of, so that the LiFePO4 product for preparing Thing is mutually uniform, and crystal property more preferably, and then obtains more useful chemical property.

The inventive method specifically has the advantages that:

In the present invention, by calcination atmosphere, acidleach pH, iron treatment and dosage, copper removal liquid pH, lithium, iron, phosphorus mole Than, the in situ coordinated regulation for separating out each parameters such as pH and operation, ferric lithium phosphate precursor group in same solution system is capable of achieving Symphysis into, and can effectively ensure that the quality of the LiFePO4 of regeneration, reduce the dephasign of product, improve product thing phase homogeneity;Enter And it is obviously improved the electric property of obtained LiFePO4.

The present invention is separated active material with other materials using simple chemical method one by one, so that efficiently and inexpensive The each several part valuable material of ground synthetical recovery waste lithium iron phosphate a, while step realizes the regeneration of battery-grade iron phosphate lithium, flow Simply, the rate of recovery is high.

The present invention realizes the simple and effective synthetical recovery of waste lithium iron phosphate battery, including housing, Copper Foil, aluminium foil, The recovery of carbon slag and LiFePO4;The secondary pollution of environment is not resulted in during recycling;Through the phosphorus obtained by regeneration Sour iron lithium material reaches LITHIUM BATTERY, can be directly used as the positive electrode of secondary cell;In addition, the inventive method takes into account environmental protection and warp Ji benefit, process is simple, low production cost, are adapted to large-scale industrial production.

Brief description of the drawings

Fig. 1 is schematic flow sheet of the invention;

Fig. 2 is the X-ray diffraction spectrogram of the battery-grade iron phosphate lithium material that embodiment 1 is obtained.

Fig. 3 is the electrochemical property test figure of the LiFePO4 that embodiment 1 is reclaimed.

Fig. 4 is the X-ray diffraction spectrogram of the product that comparative example 1 is prepared.

Specific embodiment

It is below exemplary embodiments of the invention, it should be understood that the invention is not restricted to these embodiments.

Embodiment 1

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 20g/L, is 0.5V to final discharging voltage, manually Disassemble and isolate organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 5mm to core, in atmosphere in 500 5h is calcined at DEG C, then vibrations filter out active material and copper aluminium foil, and torrefaction waste gas are absorbed with 40mg/L lime aqueous solutions, magnetic separation Isolated Copper Foil and aluminium foil, the active material sulfuric acid leaching of 2mol/L, control ph is 0.5, is separated by filtration and obtains carbon slag And leachate.Then to addition copper removal and Fe in leachate3+The iron powder that 1.1 times of theoretical amount, by Fe3+And Cu2+It is reduced into Fe2+With Copper simple substance, removes filter residue after filtering, then appropriate NaOH regulation pH is added in filtrate equal to 4, makes Al3+With Al (OH)3's Form is separated out, and is filtrated to get lithium iron phosphate precursor solution.Then to supplementing appropriate sodium phosphate in the precursor solution for obtaining, So that the mol ratio of lithium, iron, phosphorus is adjusted to 1.05: 1: 1, adds appropriate NaOH regulation pH and be equal to 6, be filtrated to get raw phosphoric acid Iron lithium is precipitated, finally in N2Under atmosphere, calcine 12h in 800 DEG C and obtain battery-grade iron phosphate lithium.According to reckoning, LiFePO4 The rate of recovery is up to 95%.

The X-ray diffraction spectrogram of the battery-grade iron phosphate lithium material that embodiment 1 is prepared is as shown in Figure 2.

The electrode of lithium iron phosphate positive material is prepared and electrochemical property test:

By lithium iron phosphate positive material, conductive carbon, binding agent (PVDF) obtained in example 1 in mass ratio for 8: 1: 1 is abundant Mixing, with METHYLPYRROLIDONE (NMP) as dispersant, hand lapping is to obtaining homogeneous slurry.The slurry that will be obtained It is coated on aluminium foil, is put into 60 DEG C of vacuum oven 12h, then breaks into the collar plate shape pole piece of a diameter of 10mm.So Afterwards with the pole piece as working electrode, metal lithium sheet is reference electrode, and Celgard 2400 is used as barrier film, the LiPF6/EC of 1mol/L + DEC+DMC is assembled into CR2025 button cells as electrolyte in the glove box full of argon gas.Under room temperature (25 DEG C), limit Voltage processed carries out constant current charge-discharge test for 2~4.3V.After through 50 circle circulations, LiFePO4 remains unchanged and maintains the ratio of 155mAh/g Capacity.

The chemical property of the LiFePO4 that example 1 is reclaimed is as shown in Figure 3.

Embodiment 2

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 30g/L, is 0.1V to final discharging voltage, disassembled Isolate organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 6mm to core, in atmosphere at 400 DEG C Roasting 10h, then vibrations filter out active material, copper aluminium foil, and torrefaction waste gas are absorbed with 40mg/L lime aqueous solutions, and magnetic separation is separated Obtain Copper Foil and aluminium foil, the active material sulfuric acid leaching of 5mol/L, control ph is equal to 1, is separated by filtration and obtains carbon slag and leaching Go out liquid.Then amount of copper and Fe are removed to theoretical in leachate3+1 times of iron powder, removes cupric filter residue, then added in filtrate after filtering Appropriate potassium hydroxide regulation pH is equal to 4, makes Al3+With Al (OH)3Form separate out, be filtrated to get lithium iron phosphate precursor solution. Then to supplementing appropriate potassium phosphate in the precursor solution for obtaining so that lithium, iron, the mol ratio of phosphorus are adjusted to 1.2: 1: 1, add Plus appropriate potassium hydroxide regulation pH is equal to 6, raw phosphoric acid iron lithium precipitation is filtrated to get, finally in N2Under atmosphere, in 700 DEG C of calcinings 20h obtains battery-grade iron phosphate lithium.It is estimated that, the rate of recovery of LiFePO4 is up to 92%.

The electrochemical property test and example 1 of lithium iron phosphate positive material prepared by embodiment 2 are identical.Circulated through 50 circles Afterwards, the specific capacity of the ferric phosphate lithium cell is 145mAh/g.

Embodiment 3

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 20g/L, is 0.5V to final discharging voltage, disassembled Isolate organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 4mm to core, in atmosphere at 600 DEG C Roasting 8h, then vibrations filter out active material, copper aluminium foil, and torrefaction waste gas are absorbed with 60mg/L lime aqueous solutions, and magnetic separation is separated Obtain Copper Foil and aluminium foil, the active material sulfuric acid leaching of 0.1mol/L, control ph is equal to 0.8, is separated by filtration and obtains carbon slag And leachate.Then it is theoretical except amount of copper and Fe to being added in leachate3+1.05 times of iron powder, must remove cupric filter residue after filtering, Appropriate NaOH regulation pH is added in filtrate again and is equal to 4, make Al3+With Al (OH)3Form separate out, be filtrated to get ferric phosphate Lithium precursor solution.Then to supplementing appropriate sodium phosphate in the precursor solution for obtaining so that lithium, iron, the mol ratio of phosphorus are adjusted It is whole to add appropriate NaOH regulation pH and be equal to 6 to 1: 1: 1, raw phosphoric acid iron lithium precipitation is filtrated to get, under an ar atmosphere finally, 24h is calcined in 600 DEG C obtain battery-grade iron phosphate lithium.According to reckoning, the rate of recovery of LiFePO4 is up to 94%.

The electrochemical property test and example 1 of lithium iron phosphate positive material prepared by embodiment 3 are identical.Circulated through 50 circles Afterwards, the specific capacity of the ferric phosphate lithium cell is 152mAh/g.

Embodiment 4

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 10g/L, is 1V to final discharging voltage, machinery is torn open Solution isolates organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 2.5mm to core, in atmosphere in 600 1h is calcined at DEG C, then vibrations filter out active material, copper aluminium foil, and torrefaction waste gas are absorbed with 50mg/L lime aqueous solutions, magnetic separation Isolated Copper Foil and aluminium foil, the active material salt Ore Leaching of 2mol/L, control pH be separated by filtration equal to 2. obtain carbon slag with Leachate.Then to addition copper removal and Fe in leachate3+The iron powder that 1.1 times of theoretical amount, obtains cupric filter residue after filtering, then in filter Appropriate ammoniacal liquor regulation pH is added in liquid and is equal to 5, make Al3+With Al (OH)3Form separate out, be filtrated to get ferric lithium phosphate precursor molten Liquid.Then to supplementing appropriate ammonium phosphate in the precursor solution for obtaining so that lithium, iron, the mol ratio of phosphorus are adjusted to 1.1: 1: 1, add appropriate ammoniacal liquor regulation pH and be equal to 6.5, raw phosphoric acid iron lithium precipitation is filtrated to get, under an ar atmosphere, in 600 DEG C of calcinings finally 24h obtains battery-grade iron phosphate lithium.According to reckoning, the rate of recovery of LiFePO4 is 72%.

The electrochemical property test and example 1 of lithium iron phosphate positive material prepared by embodiment 4 are identical.Circulated through 50 circles Afterwards, the specific capacity of the ferric phosphate lithium cell is 145mAh/g.

Embodiment 5

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 30g/L, is 0.1V to final discharging voltage, disassembled Isolate organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 10mm to core, in atmosphere at 400 DEG C Roasting 10h, then vibrations filter out active material, copper aluminium foil, and torrefaction waste gas are absorbed with 40mg/L lime aqueous solutions, and magnetic separation is separated Copper Foil and aluminium foil are obtained, the active material sulfuric acid leaching of 5mol/L controls pH to be equal to 0.5, is separated by filtration and obtains carbon slag and leaching Go out liquid.Then to being added to copper removal and Fe in leachate3+The iron powder that 1.1 times of theoretical amount, removal cupric filter residue after filtering, then Appropriate potassium hydroxide regulation pH is added in filtrate and is equal to 3.5, make Al3+With Al (OH)3Form separate out, be filtrated to get LiFePO4 Precursor solution.Then to supplementing appropriate potassium phosphate in the precursor solution for obtaining so that lithium, iron, the mol ratio adjustment of phosphorus To 1.2: 1: 1, add appropriate potassium hydroxide regulation pH and be equal to 7, raw phosphoric acid iron lithium precipitation is filtrated to get, finally in N2Under atmosphere, 20h is calcined in 700 DEG C obtain battery-grade iron phosphate lithium.According to reckoning, the rate of recovery of LiFePO4 is 92%.

The electrochemical property test and example 1 of lithium iron phosphate positive material prepared by embodiment 5 are identical.Circulated through 50 circles Afterwards, the specific capacity of the ferric phosphate lithium cell is 120mAh/g.

Comparative example 1

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 20g/L, is 0.5V to final discharging voltage, manually Disassemble and isolate organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 5mm to core, in atmosphere in 500 5h is calcined at DEG C, then vibrations filter out active material and copper aluminium foil, and torrefaction waste gas are absorbed with 40mg/L lime aqueous solutions, magnetic separation Isolated Copper Foil and aluminium foil, the active material sulfuric acid leaching of 2mol/L, control ph is 0.5, is separated by filtration and obtains carbon slag And leachate.Processed without any removal of impurities, directly to supplementing appropriate sodium phosphate in the leachate for obtaining so that lithium, iron, phosphorus Mol ratio is adjusted to 1.05: 1: 1, adds appropriate NaOH regulation pH and is equal to 6, mixture precipitation is filtrated to get, finally in N2 Under atmosphere, calcine 12h in 800 DEG C and obtain product.

The X-ray diffraction spectrogram of the product that comparative example 1 is prepared is as shown in Figure 4.

The electrochemical property test and example 1 of lithium iron phosphate positive material prepared by comparative example 1 are identical.Circulated through 50 circles Afterwards, the specific capacity of the ferric phosphate lithium cell is 52mAh/g.

Comparative example 2

Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 20g/L, is 0.1V to final discharging voltage, disassembled Isolate organic solvent, core and housing.Through Mechanical Crushing, the particle diameter after crushing is 8mm to core, in atmosphere at 300 DEG C Roasting 10h, then vibrations filter out active material, copper aluminium foil, and torrefaction waste gas are absorbed with 40mg/L lime aqueous solutions, and magnetic separation is separated Copper Foil and aluminium foil are obtained, the active material sulfuric acid leaching of 3mol/L controls pH to be equal to 0.5, is separated by filtration and obtains carbon slag and leaching Go out liquid.Then to the iron powder that 1.3 times of copper removal theoretical amount is added in leachate, cupric filter residue is removed after filtering, then in filtrate The middle appropriate potassium hydroxide regulation pH of addition is equal to 4, makes Al3+With Al (OH)3Form separate out, be filtrated to get ferric lithium phosphate precursor Solution.Then to supplementing appropriate potassium phosphate in the precursor solution for obtaining so that lithium, iron, the mol ratio of phosphorus are adjusted to 1.2: 1 : 1, add appropriate potassium hydroxide regulation pH and be equal to 6, raw phosphoric acid iron lithium precipitation is filtrated to get, finally in N2Under atmosphere, in 700 DEG C Calcining 20h obtains battery-grade iron phosphate lithium.According to reckoning, the rate of recovery of LiFePO4 is 62%.

The electrochemical property test and example 1 of lithium iron phosphate positive material prepared by comparative example 2 are identical.Circulated through 50 circles Afterwards, the specific capacity of the ferric phosphate lithium cell is 102mAh/g.

Claims (10)

1. it is a kind of from waste lithium iron phosphate battery regenerate positive active material method, it is characterised in that comprise the following steps:
Step (1):After waste lithium iron phosphate battery is substantially discharged, disassemble to obtain core;
Step (2):It is calcined under air atmosphere after described core is broken;The product screening of roasting is obtained into copper, aluminium foil and work Property material;
Step (3):The active material that step (2) is obtained is immersed in acid solution, the pH of the acid solution is less than or equal to 2;Dipping After treatment leachate is obtained through separation of solid and liquid;Li is included in described leachate+、Fe3+、Al3+、Cu2+、PO4 3-
Step (4):Iron is added in leachate to step (3), with Fe3+And Cu2+Reduction reaction is carried out, through separation of solid and liquid after reaction Obtain copper removal liquid;Described iron adds mole more than or equal to making Fe3+And Cu2+The theoretical molar amount of reduction;
Step (5):Copper removal liquid pH is to 3~5 for adjustment, and subsequent separation of solid and liquid must include Li+、Fe2+、PO43-Precursor solution;
Step (6):Lithium, iron, the mol ratio of phosphorus are 1~1.2: 1: 1 in adjustment precursor solution, then in the lower precipitation in pH=5~7 Precipitation, separation of solid and liquid obtain ferric lithium phosphate precursor;Described ferric lithium phosphate precursor calcines to obtain phosphoric acid under protective atmosphere again Iron lithium.
2. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 1, it is characterised in that In step (2), the temperature of roasting is 400~600 DEG C;Roasting time is 1~10h.
3. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 1, it is characterised in that The mole that adds of described iron is to make Fe3+And Cu2+It is reduced into Fe2+With 1~1.2 times of the theoretical molar amount of Cu.
4. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 3, it is characterised in that In step (3), in acid solution leaching process, pH <=1 is controlled.
5. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 4, it is characterised in that In step (5), the pH for regulating and controlling copper removal liquid is 3.5~4.5.
6. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 5, it is characterised in that In step (6), pH value is 5.5~6.5.
7. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 1, it is characterised in that In step (6), to the mol ratio that the described lithium of phosphorus source regulation and control, iron, phosphorus are filled into precursor solution;Described phosphorus source is water solubility Phosphate.
8. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 1, it is characterised in that Described protective atmosphere is nitrogen and/or inert gas;The temperature of calcining is 600~900 DEG C.
9. the method for regenerating positive active material from waste lithium iron phosphate battery as claimed in claim 1, it is characterised in that In step (1), the size controlling of product is in 2.5mm~10mm after crushing;Described is substantially discharged finger:By waste lithium iron phosphate electricity Pond is discharged to final voltage less than 1V through salt solution;Described salt solution is the sodium-chloride water solution of 10~30g/L.
10. as described in any one of claim 1~9 from waste lithium iron phosphate battery regenerate positive active material method, Characterized in that, the obtained LiFePO4 of regeneration is LITHIUM BATTERY.
CN201710110134.2A 2017-02-27 2017-02-27 A method of regenerating positive active material from waste lithium iron phosphate battery CN106910889B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710110134.2A CN106910889B (en) 2017-02-27 2017-02-27 A method of regenerating positive active material from waste lithium iron phosphate battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710110134.2A CN106910889B (en) 2017-02-27 2017-02-27 A method of regenerating positive active material from waste lithium iron phosphate battery

Publications (2)

Publication Number Publication Date
CN106910889A true CN106910889A (en) 2017-06-30
CN106910889B CN106910889B (en) 2019-07-23

Family

ID=59208066

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710110134.2A CN106910889B (en) 2017-02-27 2017-02-27 A method of regenerating positive active material from waste lithium iron phosphate battery

Country Status (1)

Country Link
CN (1) CN106910889B (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107819121A (en) * 2017-10-27 2018-03-20 重庆特瑞新能源材料有限公司 A kind of LiFePO 4 activity regenerating method
CN107946572A (en) * 2017-11-20 2018-04-20 广西师范大学 A kind of novel metal elemental copper/lithium iron phosphate/carbon composite material and its preparation method and application
CN107955879A (en) * 2017-12-05 2018-04-24 广东省稀有金属研究所 A kind of method of valuable element in recycling waste lithium ion battery electrode material
CN108110357A (en) * 2017-12-14 2018-06-01 眉山顺应动力电池材料有限公司 A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate
CN108298514A (en) * 2017-12-11 2018-07-20 中国科学院过程工程研究所 A kind of method of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode
CN108400403A (en) * 2018-03-14 2018-08-14 中国科学院过程工程研究所 A method of preparing lithium carbonate with waste material containing lithium electrode
CN108486378A (en) * 2018-03-14 2018-09-04 中国科学院过程工程研究所 A kind of processing method of the leachate of waste material containing lithium electrode
CN109193059A (en) * 2018-09-26 2019-01-11 王书珍 A kind of regeneration treating method of LiFePO4 waste material
CN109573974A (en) * 2018-10-22 2019-04-05 天齐锂业(江苏)有限公司 Aluminum removing method based on acid leaching solution in waste lithium iron phosphate battery recycling
CN109652654A (en) * 2018-12-30 2019-04-19 沈阳化工研究院有限公司 A kind of method of waste and old ternary dynamic lithium battery resource utilization metallic element
CN110112481A (en) * 2019-04-23 2019-08-09 北京科技大学 Waste lithium iron phosphate battery recycles the method for preparing lithium iron phosphate positive material
CN110643814A (en) * 2018-06-26 2020-01-03 中南大学 Method for removing aluminum and recycling waste lithium iron phosphate batteries

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102403554A (en) * 2011-11-10 2012-04-04 大连交通大学 Method for recycling waste lithium iron phosphate ion battery anode material
CN102956936A (en) * 2011-08-25 2013-03-06 深圳市格林美高新技术股份有限公司 Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile
CN104953200A (en) * 2015-06-30 2015-09-30 哈尔滨工业大学 Method for recycling battery-grade iron phosphate in lithium iron phosphate battery and preparing lithium iron phosphate positive material by utilizing waste lithium ion phosphate battery
CN105977569A (en) * 2016-07-24 2016-09-28 合肥国轩高科动力能源有限公司 Method for preparing lithium iron ii phosphate from lithium iron ii phosphate waste

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102956936A (en) * 2011-08-25 2013-03-06 深圳市格林美高新技术股份有限公司 Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile
CN102403554A (en) * 2011-11-10 2012-04-04 大连交通大学 Method for recycling waste lithium iron phosphate ion battery anode material
CN104953200A (en) * 2015-06-30 2015-09-30 哈尔滨工业大学 Method for recycling battery-grade iron phosphate in lithium iron phosphate battery and preparing lithium iron phosphate positive material by utilizing waste lithium ion phosphate battery
CN105977569A (en) * 2016-07-24 2016-09-28 合肥国轩高科动力能源有限公司 Method for preparing lithium iron ii phosphate from lithium iron ii phosphate waste

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107819121A (en) * 2017-10-27 2018-03-20 重庆特瑞新能源材料有限公司 A kind of LiFePO 4 activity regenerating method
CN107946572A (en) * 2017-11-20 2018-04-20 广西师范大学 A kind of novel metal elemental copper/lithium iron phosphate/carbon composite material and its preparation method and application
CN107946572B (en) * 2017-11-20 2020-05-15 广西师范大学 Metal elemental copper/lithium iron phosphate/carbon composite material and preparation method and application thereof
CN107955879B (en) * 2017-12-05 2019-08-30 广东省稀有金属研究所 A kind of method of valuable element in recycling waste lithium ion battery electrode material
CN107955879A (en) * 2017-12-05 2018-04-24 广东省稀有金属研究所 A kind of method of valuable element in recycling waste lithium ion battery electrode material
CN108298514A (en) * 2017-12-11 2018-07-20 中国科学院过程工程研究所 A kind of method of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode
CN108456788A (en) * 2017-12-11 2018-08-28 中国科学院过程工程研究所 A kind of method of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode
CN108110357A (en) * 2017-12-14 2018-06-01 眉山顺应动力电池材料有限公司 A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate
CN108400403A (en) * 2018-03-14 2018-08-14 中国科学院过程工程研究所 A method of preparing lithium carbonate with waste material containing lithium electrode
CN108486378A (en) * 2018-03-14 2018-09-04 中国科学院过程工程研究所 A kind of processing method of the leachate of waste material containing lithium electrode
CN110643814A (en) * 2018-06-26 2020-01-03 中南大学 Method for removing aluminum and recycling waste lithium iron phosphate batteries
CN109193059A (en) * 2018-09-26 2019-01-11 王书珍 A kind of regeneration treating method of LiFePO4 waste material
CN109573974A (en) * 2018-10-22 2019-04-05 天齐锂业(江苏)有限公司 Aluminum removing method based on acid leaching solution in waste lithium iron phosphate battery recycling
CN109652654A (en) * 2018-12-30 2019-04-19 沈阳化工研究院有限公司 A kind of method of waste and old ternary dynamic lithium battery resource utilization metallic element
CN110112481A (en) * 2019-04-23 2019-08-09 北京科技大学 Waste lithium iron phosphate battery recycles the method for preparing lithium iron phosphate positive material

Also Published As

Publication number Publication date
CN106910889B (en) 2019-07-23

Similar Documents

Publication Publication Date Title
Huang et al. Recycling of lithium-ion batteries: Recent advances and perspectives
CN105206889B (en) A kind of processing method of waste and old nickle cobalt lithium manganate ternary cell positive material
Choubey et al. Advance review on the exploitation of the prominent energy-storage element Lithium. Part II: From sea water and spent lithium ion batteries (LIBs)
KR101682217B1 (en) A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery
Chen et al. Process for the recovery of cobalt oxalate from spent lithium-ion batteries
CN105428745B (en) A kind of innoxious comprehensive reutilization method of applying waste lithium ionic power battery
Weng et al. Synthesis and performance of Li [(Ni1/3Co1/3Mn1/3) 1− xMgx] O2 prepared from spent lithium ion batteries
Bian et al. A novel process to recycle spent LiFePO4 for synthesizing LiFePO4/C hierarchical microflowers
CN104868190B (en) The leaching of metal and recovery method in a kind of lithium ion cell anode waste
Xu et al. A review of processes and technologies for the recycling of lithium-ion secondary batteries
CN102751549B (en) Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries
Wang et al. An overview of recycling and treatment of spent LiFePO4 batteries in China
CN103326088B (en) A kind of comprehensive recovering process of waste and old lithium ion battery
US9257731B2 (en) Method for implementing full cycle regeneration of waste lead acid batteries
CN101831548B (en) Method for recovering valuable metals from waste lithium manganese oxide battery
CN102676827B (en) Method for recovering valuable metal from nickel cobalt lithium manganate batteries and positive pole materials
CN102496752B (en) Method for recycling electrolyte of waste lithium ion battery
CN107196004B (en) A method of recycling valuable metal from applying waste lithium ionic power battery
Shuva et al. Hydrometallurgical recovery of value metals from spent lithium ion batteries
CN104105803B (en) The recovery method of lithium
CN102560535B (en) Method for recovering lead in waste lead-acid storage battery filler by using wet process
CN104466292B (en) The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material
WO2014154152A1 (en) Method for recycling nickel-cobalt-manganese ternary anode material
EP2754201B1 (en) Method for recycling lithium batteries and/or electrodes of such batteries
CN101818251B (en) Method for recovering cobalt and lithium from waste lithium ion batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant