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 PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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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
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.
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