CN106910889B - A method of regenerating positive active material from waste lithium iron phosphate battery - Google Patents
A method of regenerating positive active material 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
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- 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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a kind of regeneration methods of lithium iron phosphate battery anode active material: 1) by waste lithium iron phosphate battery after salt water discharges, disassembling out organic solvent, core and sheathing material；2) core crushed, roast and etc. after, 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 uses the method for addition iron powder reducing by Cu therein2+It is reduced into elemental copper, while by Fe3+It is reduced into Fe2+, after being removed by filtration copper and extra scum, lye precipitating supplementing phosphorus source after filtering except aluminium into filtrate again, and by adding lye to adjust pH value, generating raw phosphoric acid iron lithium precipitating, most obtain battery-grade iron phosphate lithium through sintering afterwards.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, does not generate any secondary pollution, is suitble to industrialized production.
Description
Technical field
The invention belongs to lithium ion secondary battery recycling fields, and in particular to one kind is regenerated from waste lithium iron phosphate battery
The method of positive active material.
Background technique
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 at the focus of social concerns.And ferric phosphate lithium cell due to its is at low cost,
Cycle performance is good, the features such as having a safety feature is widely used in power battery and energy-storage battery, 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 a large amount of LiFePO4 electricity
Pond is scrapped, and recycling is carried out to it has very high social value.
However, it is domestic at present still there are no can be simple and efficient and can synthetical recovery waste lithium iron phosphate battery technology road
Line, also professional ferric phosphate lithium cell does not recycle company, is largely turned on the company of recycling banner, and also only recycling inventory is old
Material rather than waste battery.Therefore, it is most important to design a complete process route capable of being industrialized.Existing published recycling
The patent of waste lithium iron phosphate battery cannot all take into account environment benefits and economic gains well.
Presently disclosed recycling LiFePO4 old and useless battery is broadly divided into two methods:
One is directly recycle lithium salts, without any effectively handle 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, this method utilize aluminium, iron and lithium in soda acid lixiviation process recycling LiFePO4 old and useless battery anode waste paper.This method is simultaneously
Without reference to the processing of Phosphorus From Wastewater element, secondary pollution is caused to environment；It is returned in addition, valuable metal ferro element is not appropriate
It receives, can also reduce the economic benefit of the program.
The second is being settled out ferric phosphate, lithium carbonate respectively, then new LiFePO4 is synthesized 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, this method successively handle refuse battery positive electrode using soda acid, and precipitation and separation obtains ferric phosphate and lithium carbonate, then divides
Analysis obtains the molar ratio of the iron of material, lithium, phosphorus, adds reactant adjustment proportion appropriate, finally calcines in an inert atmosphere
Obtain new lithium iron phosphate positive material.The technical solution will certainly residual fraction during precipitate phosphoric acid iron, lithium carbonate
In reaction solution, to influence the rate of recovery of valuable element；In addition to directly result in recovery process elongated for precipitating respectively, so that place
Uncontrollable factor increases during reason, and reactant to be added is needed to increase, to improve production cost.In addition, the technology
Finally the specific capacity of the composite positive pole of LiFePO4/random carbon obtained and coulombic efficiency can be poor for scheme；Reason master
It wants are as follows: the random carbon in the composite positive pole produced will not provide any capacity, therefore the capacity of the composite material is main
Content depending on LiFePO4, that is to say, that carbon content is higher, and the specific capacity of the composite material is necessarily fewer；Secondly, cladding
Irregular carbon material, the specific surface that may cause material increase, and can generate extra side reaction (such as in first circle discharge process
SEI film), to influence the coulombic efficiency of first circle.
It to sum up analyzes, it is low, at high cost outer, obtained that prior art has complex process, purpose element recovery rate mostly
LiFePO4 product miscellaneous phase it is more, the problems such as object phase homogeneity is poor, chemical property is poor.
Summary of the invention
LiFePO 4 material miscellaneous phase to solve existing recycling is more, object phase homogeneity is poor, recovery process complexity, purpose
The problems such as product recoveries are low, the present invention provide a kind of regeneration method of lithium iron phosphate battery anode active material, it is intended to a step
Realize the regeneration of battery-grade iron phosphate lithium.
A method of regenerating positive active material from waste lithium iron phosphate battery, comprising the following steps:
Step (1): waste lithium iron phosphate battery be substantially discharged after, disassemble to obtain core；
Step (2): it is roasted under air atmosphere after the core is broken；The product of roasting is screened to obtain copper, aluminium foil
And active material；
Step (3): the active material that step (2) obtains is immersed in acid solution, and the pH of the acid solution is less than or equal to 2；
Leachate is separated by solid-liquid separation to obtain after impregnation；It include Li in the leachate+、Fe3+、Al3+、Cu2+、PO4 3-；
Step (4): being added iron into the leachate of step (3), with Fe3+And Cu2+Reduction reaction is carried out, through solid after reaction
Liquid separates except copper liquid；The iron add mole be greater than or equal to make Fe3+And Cu2+The theoretical molar amount of reduction；
Step (5): adjustment removes copper liquid pH to 3~5, is then separated by solid-liquid separation comprising Li+、Fe2+、PO4 3-Presoma it is molten
Liquid；
Step (6): adjustment precursor solution in lithium, iron, phosphorus molar ratio be 1~1.2: 1: 1, then under pH=5~7
Precipitating is precipitated, is separated by solid-liquid separation to obtain ferric lithium phosphate precursor；The ferric lithium phosphate precursor is calcined under protective atmosphere again
LiFePO4.
In the present invention, acidleach processing by being roasted under air atmosphere, under the pH, using iron to the processing of leachate,
Except lithium, iron, the regulation of the molar ratio of phosphorus, ferric lithium phosphate precursor are precipitated in the regulation of copper liquid pH range, the precursor solution
The collaboration of each parameter such as pH and operation can effectively ensure that again, it can be achieved that ferric lithium phosphate precursor generates in same solution system
The quality of raw LiFePO4, such as reduce the miscellaneous phase of product, improve product object phase homogeneity；And then it is obviously improved phosphorus obtained
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 water, described sufficiently puts
Electricity refers to: waste lithium iron phosphate battery is discharged to final voltage lower than 1V through salt water.
Preferably, the salt water 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
Conducive to subsequent recycling.It will lead to active material if partial size is too small and be difficult to separate with pole piece, if partial size is excessive to will lead to bonding agent
Incomplete combustion reduces the rate of recovery of active material.
In the present invention, broken material is roasted under air atmosphere.
Preferably, the temperature of roasting is 400~600 DEG C in step (2).
Preferably, calcining time is 1~10h in step (2).More preferably calcining time is 5~8h.
In step (2), (copper/aluminium is mixed for particle and copper/aluminium foil that the product vibration screening of roasting is obtained active material
Object)；The copper, aluminium foil are separated by magnetic separation mode again.
In step (2), the flue gas (exhaust gas) for roasting generation is handled through limewash (calcium hydroxide aqueous solution) absorption.
It roasts and contains HF in the flue gas generated, the present invention absorbs torrefaction waste gas, fixed HF using limewash, and is had
The calcirm-fluoride of utility value.
Preferably, the concentration of the limewash is not less than 40mg/L.
In step (3), the acid solution is hydrochloric acid or sulfuric acid solution.
Further preferably, the acid solution is sulfuric acid solution.
Still more preferably, the concentration of the sulfuric acid solution is 0.1~5mol/L (with H2SO4Meter).
The inventors discovered that controlling the pH of Leaching Systems in acid solution leaching process in the range, preventing Fe3+It is heavy
Shallow lake leads to iron loss.
Still more preferably, in step (3), in acid solution leaching process, <=1 pH is controlled.
In step (3), the solid-liquid system of acidleach is separated by solid-liquid separation, leached mud and leachate are obtained.The leaching
Slag is mainly the charcoal in active constituent.The leachate includes Li+、Fe3+、Al3+、Cu2+、PO4 3-Plasma.
The present inventor originally uses iron to handle leachate, can unexpectedly reduce made from a final step
The miscellaneous phase of LiFePO4 improves the electric property of product.
The additional amount of iron has influence to the miscellaneous phase of reduction LiFePO4 obtained, raising electric property, preferably, institute
The mole that adds for 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, it can be on the one hand by the Fe in leachate3+It is reduced to Fe2+, on the other hand can also be by setting
It changes reaction and removes the Cu being mixed in solution2+, purified solution.On the other hand, it can avoid ferrous in material waste and solution system
Ion imbalance.
It after adding iron to react, is separated by solid-liquid separation, obtained solid portion is the impurity such as the copper generated；Obtained liquid portion
For except copper liquid, wherein mainly contain Li+、Fe2+、Al3+、PO4 3-Plasma.
In step (5), it will adjust except the pH of copper liquid to 3~5, make except the Al in copper liquid3+With Al (OH)3Form be precipitated,
Then being separated by solid-liquid separation can be obtained 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 pH3+, can be further ensured that subsequent
The performance of LiFePO4 product.It higher than the pH upper limit, is easy to make ferric lithium phosphate precursor co-precipitation, influences recycling effect
Rate；Lower than the pH lower limit, the miscellaneous phase of product obtained is more.
Preferably, regulation is 3.5~4.5 except the pH of copper liquid in step (5).
In step (6), the molar ratio of the phosphorus source regulation lithium, iron, phosphorus is filled into precursor solution；The phosphorus source
For water-soluble phosphate.
Preferably, the phosphorus source be sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate,
At least one of dihydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
In step (6), the pH for the solution system for adjusting the molar ratio of lithium, iron, phosphorus is adjusted to 5~7, in the pH body
In system, ferric lithium phosphate precursor combined in-situ in same solution system is precipitated, the homogeneity of material is good, purity is high, recycling
Rate is high；Facilitate the LiFePO4 that excellent electric property is made in subsequent calcination.
The pH of ferric lithium phosphate precursor original position crystallization on the quality of product have influence, be higher than the pH upper limit, be easy to
Miscellaneous phase is introduced in product, while also will increase cost.
Preferably, step (6): pH value is 5.5~6.5.
Preferably, the temperature of calcining is 600~900 DEG C in step (6).
In step (6), the protective atmosphere is nitrogen and/or inert gas.
The inert gas is, for example, helium, argon gas etc..
Under the calcination temperature, preferred calcination time be 12~for 24 hours.
In the present invention, regenerating LiFePO4 obtained is LITHIUM BATTERY.
Battery-grade iron phosphate lithium made from regeneration method of the present invention is used for the positive-active material of ferric phosphate lithium cell
Material.
Existing conventional method, such as filtering, centrifugation etc. can be selected in separation of solid and liquid of the present invention.
It is, for example, at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide that the present invention, which adjusts lye used by system pH,
Aqueous solution.
A kind of preferred regeneration method of the present invention, specifically comprises the following steps:
Step a) ferric phosphate lithium cell is split:
By the waste lithium iron phosphate battery after salt water is substantially discharged, organic solvent, core are mechanically or manually disassembled out
And sheathing material；The salt water is the sodium chloride solution of 10~30g/L；Described being substantially discharged refers to that final discharging voltage is low
In 1V；
The separation of step b) active material:
The core that step a) is obtained is broken using mechanical force, roasts 1~10h, vibration at 400~600 DEG C in air
Filter out active material and copper, aluminium foil；
Torrefaction waste gas is absorbed with limewash and obtains calcirm-fluoride, and the 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 to obtain carbon slag and containing Li+、Fe3+、Al3+、Cu2+、PO4 3-Plasma
Acid leaching solution；The pH control of leaching process is 2 and less；The concentration of the sulfuric acid is 0.1~5mol/L (with H2SO4
Meter)；
The preparation of step c) lithium iron phosphate precursor solution:
Iron powder is added in the leachate obtained to step b), and the mole that adds of the iron is to make Fe3+And Cu2+It is reduced into
Fe2+With 1~1.2 times of the theoretical molar amount of Cu；The iron is respectively by Fe3+And Cu2+It is reduced into Fe2+And copper simple substance, after reaction
Filtering, isolated filtrate (removing copper liquid)；Lye is added in filtrate again and adjusts pH to 3~5, makes Al3+With Al (OH)3Form
It is precipitated, filters containing Li+、Fe2+、PO4 3-Lithium iron phosphate precursor solution；
The regeneration of step d) battery-grade iron phosphate lithium:
Phosphorus source is supplemented into precursor solution described in step c), so that the molar ratio of lithium, iron, phosphorus is adjusted to 1~1.2: 1
: 1, it recycles lye to adjust pH to 5~7, raw phosphoric acid iron lithium precipitating is obtained by filtration, finally under an inert atmosphere, in 600~900
DEG C calcining 12~obtain battery-grade iron phosphate lithium for 24 hours.
After the present invention leaches waste lithium iron phosphate battery electric discharge dismantling, addition is cheap and has the Fe powder of reproducibility, and one
Aspect can be by Fe3+It is reduced to Fe2+, on the other hand the Cu for removing and being mixed in solution can also be reacted by displacement2+, purify molten
Liquid (removes copper liquid).Add lye to adjust pH to 3~5 after filtering thereto and removes Al3+, the preparation of pH to 5~7 is adjusted after filtering and impurity removing again
Ferric lithium phosphate precursor；The ferric lithium phosphate precursor calcines to obtain LiFePO4 under protective atmosphere again.The program is not only
P elements have been obtained into effective recycling, have avoided it from causing the secondary pollution of environment, and also improve other valuable metals
The rate of recovery.The heavy LiFePO4 of the one-step method that the program uses, greatly reduces production cost, and shorten production procedure.Separately
Outside, before one-step method sinks LiFePO4, the impurity in solution is first got rid of, so that the LiFePO4 product prepared
Object is mutually uniform, and crystal property is more preferable, and then obtains more useful chemical property.
The method of the present invention specifically has the advantages that
In the present invention, by calcination atmosphere, acidleach pH, iron processing and dosage, except copper liquid pH, lithium, iron, phosphorus mole
Than, the in situ coordinated regulation that each parameters such as pH and operation is precipitated, it can be achieved that ferric lithium phosphate precursor group in same solution system
Symphysis is at and can effectively ensure that the quality of regenerated LiFePO4, reduce the miscellaneous phase of product, improve product object phase homogeneity；Into
And it is obviously improved the electric property of LiFePO4 obtained.
The present invention is separated active material with other materials using simple chemical method one by one, thus efficiently and inexpensive
Each section valuable material of ground synthetical recovery waste lithium iron phosphate, while a step realizes the regeneration of battery-grade iron phosphate lithium, process
Simply, the rate of recovery is high.
The present invention realizes the simple and effective synthetical recovery of waste lithium iron phosphate battery, including shell, copper foil, aluminium foil,
The recycling of carbon slag and LiFePO4；The secondary pollution of environment is not will cause during recovery processing；Through regenerating resulting phosphorus
Sour iron lithium material reaches LITHIUM BATTERY, can be directly used as the positive electrode of secondary cell；In addition, the method for the present invention takes into account environmental protection and warp
Ji benefit, simple process, production cost are low, are suitble to large-scale industrial production.
Detailed description of the invention
Fig. 1 is flow diagram of the invention；
Fig. 2 is the X-ray diffraction spectrogram for the battery-grade iron phosphate lithium material that embodiment 1 obtains.
Fig. 3 is the electrochemical property test figure for the LiFePO4 that embodiment 1 recycles.
Fig. 4 is the X-ray diffraction spectrogram for the product that comparative example 1 is prepared.
Specific embodiment
The following are exemplary embodiments of the invention, and however, it is to be understood that the present invention is not limited to these embodiments.
Embodiment 1
Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 20g/L, until final discharging voltage is 0.5V, manually
Organic solvent, core and shell are isolated in dismantling.Core is through Mechanical Crushing, and broken partial size is 5mm, in air in 500
5h is roasted at DEG C, then vibration filters out active material and copper aluminium foil, and torrefaction waste gas is absorbed with 40mg/L lime aqueous solution, magnetic separation
Isolated copper foil and aluminium foil, the sulfuric acid leaching of active material 2mol/L, control pH value are 0.5, are separated by filtration to obtain carbon slag
And leachate.Then copper removal and Fe are added into 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 adds appropriate sodium hydroxide in filtrate and adjust pH equal to 4, makes Al3+With Al (OH)3's
Form is precipitated, and lithium iron phosphate precursor solution is obtained by filtration.Then suitable sodium phosphate is supplemented into obtained precursor solution,
So that the molar ratio of lithium, iron, phosphorus is adjusted to 1.05: 1: 1, adds appropriate sodium hydroxide and adjust pH equal to 6, raw phosphoric acid is obtained by filtration
Iron lithium precipitating, finally in N2Under atmosphere, battery-grade iron phosphate lithium is obtained in 800 DEG C of calcining 12h.According to reckoning, LiFePO4
The rate of recovery is up to 95%.
The X-ray diffraction spectrogram for 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 prepares and electrochemical property test:
Lithium iron phosphate positive material made from example 1, conductive carbon, binder (PVDF) is abundant for 8: 1: 1 in mass ratio
Mixing uses n-methyl-2-pyrrolidone (NMP) as dispersing agent, and hand lapping is to obtaining uniform slurry.The slurry that will be obtained
Coated in the vacuum oven 12h on aluminium foil, being put into 60 DEG C, the collar plate shape pole piece that diameter is 10mm is then broken into.So
Afterwards using the pole piece as working electrode, metal lithium sheet is reference electrode, and Celgard 2400 is used as diaphragm, the LiPF6/EC of 1mol/L
+ DEC+DMC is used as electrolyte, is assembled into CR2025 button cell in the glove box full of argon gas.Under room temperature (25 DEG C), limit
Voltage processed is that 2~4.3V carries out constant current charge-discharge test.After 50 circle circulations, LiFePO4, which remains unchanged, maintains the ratio of 155mAh/g
Capacity.
The chemical property for the LiFePO4 that example 1 recycles is as shown in Figure 3.
Embodiment 2
Waste lithium iron phosphate battery is immersed in the sodium chloride solution of 30g/L, until final discharging voltage is 0.1V, dismantling
Isolate organic solvent, core and shell.Core is through Mechanical Crushing, and broken partial size is 6mm, in air at 400 DEG C
10h is roasted, then vibration filters out active material, copper aluminium foil, and torrefaction waste gas is absorbed with 40mg/L lime aqueous solution, magnetic separation separation
Copper foil and aluminium foil, the sulfuric acid leaching of active material 5mol/L are obtained, control pH value is equal to 1, is separated by filtration to obtain carbon slag and leaching
Liquid out.Then theoretical into leachate to remove amount of copper and Fe3+1 times of iron powder removes cupric filter residue, then adds in filtrate after filtering
Appropriate potassium hydroxide adjusts pH and is equal to 4, makes Al3+With Al (OH)3Form be precipitated, lithium iron phosphate precursor solution is obtained by filtration.
Then suitable potassium phosphate is supplemented into obtained precursor solution, so that the molar ratio of lithium, iron, phosphorus is adjusted to 1.2: 1: 1, is added
Add appropriate potassium hydroxide to adjust pH and be equal to 6, raw phosphoric acid iron lithium precipitating is obtained by filtration, finally in N2Under atmosphere, calcined in 700 DEG C
20h obtains battery-grade iron phosphate lithium.According to reckoning, 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.Through 50 circle circulations
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, until final discharging voltage is 0.5V, dismantling
Isolate organic solvent, core and shell.Core is through Mechanical Crushing, and broken partial size is 4mm, in air at 600 DEG C
8h is roasted, then vibration filters out active material, copper aluminium foil, and torrefaction waste gas is absorbed with 60mg/L lime aqueous solution, magnetic separation separation
Copper foil and aluminium foil, the sulfuric acid leaching of active material 0.1mol/L are obtained, control pH value is equal to 0.8, is separated by filtration to obtain carbon slag
And leachate.Then it is added into leachate theoretical except amount of copper and Fe3+1.05 times of iron powder must remove cupric filter residue after filtering,
Appropriate sodium hydroxide is added in filtrate again and adjusts pH equal to 4, makes Al3+With Al (OH)3Form be precipitated, ferric phosphate is obtained by filtration
Lithium precursor solution.Then suitable sodium phosphate is supplemented into obtained precursor solution, so that the molar ratio tune of lithium, iron, phosphorus
It is whole to add appropriate sodium hydroxide to 1: 1: 1 and adjust pH equal to 6, raw phosphoric acid iron lithium precipitating is obtained by filtration, finally under an ar atmosphere,
Battery-grade iron phosphate lithium is obtained for 24 hours in 600 DEG C of calcinings.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.Through 50 circle circulations
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, until final discharging voltage is 1V, machinery is torn open
Solution isolates organic solvent, core and shell.Core is through Mechanical Crushing, and broken partial size is 2.5mm, in air in 600
1h is roasted at DEG C, then vibration filters out active material, copper aluminium foil, and torrefaction waste gas is absorbed with 50mg/L lime aqueous solution, magnetic separation
Isolated copper foil and aluminium foil, the salt Ore Leaching of active material 2mol/L, control pH be equal to 2. be separated by filtration to obtain carbon slag and
Leachate.Then copper removal and Fe are added into leachate3+The iron powder that 1.1 times of theoretical amount obtains cupric filter residue, then is filtering after filtering
Appropriate ammonium hydroxide is added in liquid and adjusts pH equal to 5, makes Al3+With Al (OH)3Form be precipitated, it is molten that ferric lithium phosphate precursor is obtained by filtration
Liquid.Then suitable ammonium phosphate is supplemented into obtained precursor solution, so that the molar ratio of lithium, iron, phosphorus is adjusted to 1.1: 1:
1, it adds appropriate ammonium hydroxide and adjusts pH equal to 6.5, raw phosphoric acid iron lithium precipitating is obtained by filtration, finally under an ar atmosphere, calcined in 600 DEG C
Battery-grade iron phosphate lithium is obtained for 24 hours.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.Through 50 circle circulations
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, until final discharging voltage is 0.1V, dismantling
Isolate organic solvent, core and shell.Core is through Mechanical Crushing, and broken partial size is 10mm, in air at 400 DEG C
10h is roasted, then vibration filters out active material, copper aluminium foil, and torrefaction waste gas is absorbed with 40mg/L lime aqueous solution, magnetic separation separation
Copper foil and aluminium foil, the sulfuric acid leaching of active material 5mol/L are obtained, control pH is equal to 0.5, is separated by filtration to obtain carbon slag and leaching
Liquid out.Then copper removal and Fe are added into leachate3+The iron powder that 1.1 times of theoretical amount, removal cupric filter residue after filtering, then
Appropriate potassium hydroxide is added in filtrate and adjusts pH equal to 3.5, makes Al3+With Al (OH)3Form be precipitated, LiFePO4 is obtained by filtration
Precursor solution.Then suitable potassium phosphate is supplemented into obtained precursor solution, so that the molar ratio of lithium, iron, phosphorus adjusts
To 1.2: 1: 1, adds appropriate potassium hydroxide and adjust pH equal to 7, raw phosphoric acid iron lithium precipitating is obtained by filtration, finally in N2Under atmosphere,
Battery-grade iron phosphate lithium is obtained in 700 DEG C of calcining 20h.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.Through 50 circle circulations
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, until final discharging voltage is 0.5V, manually
Organic solvent, core and shell are isolated in dismantling.Core is through Mechanical Crushing, and broken partial size is 5mm, in air in 500
5h is roasted at DEG C, then vibration filters out active material and copper aluminium foil, and torrefaction waste gas is absorbed with 40mg/L lime aqueous solution, magnetic separation
Isolated copper foil and aluminium foil, the sulfuric acid leaching of active material 2mol/L, control pH value are 0.5, are separated by filtration to obtain carbon slag
And leachate.It is handled without any removal of impurities, suitable sodium phosphate is directly supplemented into obtained leachate, so that lithium, iron, phosphorus
Molar ratio is adjusted to 1.05: 1: 1, adds appropriate sodium hydroxide and adjusts pH equal to 6, mixture precipitation is obtained by filtration, finally in N2
Under atmosphere, product is obtained in 800 DEG C of calcining 12h.
The X-ray diffraction spectrogram for 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.Through 50 circle circulations
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, until final discharging voltage is 0.1V, dismantling
Isolate organic solvent, core and shell.Core is through Mechanical Crushing, and broken partial size is 8mm, in air at 300 DEG C
10h is roasted, then vibration filters out active material, copper aluminium foil, and torrefaction waste gas is absorbed with 40mg/L lime aqueous solution, magnetic separation separation
Copper foil and aluminium foil, the sulfuric acid leaching of active material 3mol/L are obtained, control pH is equal to 0.5, is separated by filtration to obtain carbon slag and leaching
Liquid out.Then it is added to 1.3 times of copper removal theoretical amount of iron powder into leachate, cupric filter residue is removed after filtering, then in filtrate
The middle appropriate potassium hydroxide of addition adjusts pH and is equal to 4, makes Al3+With Al (OH)3Form be precipitated, ferric lithium phosphate precursor is obtained by filtration
Solution.Then suitable potassium phosphate is supplemented into obtained precursor solution, so that the molar ratio of lithium, iron, phosphorus is adjusted to 1.2: 1
: 1, it adds appropriate potassium hydroxide and adjusts pH equal to 6, raw phosphoric acid iron lithium precipitating is obtained by filtration, 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.Through 50 circle circulations
Afterwards, the specific capacity of the ferric phosphate lithium cell is 102mAh/g.
Claims (9)
1. a kind of method for regenerating positive active material from waste lithium iron phosphate battery, which comprises the following steps:
Step (1): waste lithium iron phosphate battery be substantially discharged after, disassemble to obtain core；
Step (2): it is roasted under air atmosphere after the core is broken；The product of roasting is screened to obtain copper, aluminium foil and work
Property substance；
Step (3): the active material that step (2) obtains is immersed in acid solution, and the pH of the acid solution is less than or equal to 2；Dipping
Leachate is separated by solid-liquid separation to obtain after processing；It include Li in the leachate+、Fe3+、Al3+、Cu2+、PO4 3-；The acid solution is
Hydrochloric acid or sulfuric acid solution；
Step (4): being added iron into the leachate of step (3), with Fe3+And Cu2+Reduction reaction is carried out, through being separated by solid-liquid separation after reaction
It obtains and removes copper liquid；The mole that adds of the iron makes Fe3+And Cu2+1~1.2 times of the theoretical molar amount of reduction；
Step (5): adjustment removes copper liquid pH to 3~5, is then separated by solid-liquid separation comprising Li+、Fe2+、PO4 3-Precursor solution；
Step (6): adjustment precursor solution in lithium, iron, phosphorus molar ratio be 1~1.2:1:1, then under pH=5~7 precipitation
It precipitates, be separated by solid-liquid separation to obtain ferric lithium phosphate precursor；The ferric lithium phosphate precursor calcines to obtain phosphoric acid under protective atmosphere again
Iron lithium.
2. the method for positive active material is regenerated from waste lithium iron phosphate battery as described in claim 1, which is characterized in that
In step (2), the temperature of roasting is 400~600 DEG C；Calcining time is 1~10h.
3. the method for positive active material is regenerated from waste lithium iron phosphate battery as described in claim 1, which is characterized in that
In step (3), in acid solution leaching process, pH≤1 is controlled.
4. the method for positive active material is regenerated from waste lithium iron phosphate battery as claimed in claim 3, which is characterized in that
In step (5), regulation is 3.5~4.5 except the pH of copper liquid.
5. the method for positive active material is regenerated from waste lithium iron phosphate battery as claimed in claim 4, which is characterized in that
In step (6), pH value is 5.5~6.5.
6. the method for positive active material is regenerated from waste lithium iron phosphate battery as described in claim 1, which is characterized in that
In step (6), the molar ratio of the phosphorus source regulation lithium, iron, phosphorus is filled into precursor solution；The phosphorus source is water solubility
Phosphate.
7. the method for positive active material is regenerated from waste lithium iron phosphate battery as described in claim 1, which is characterized in that
The protective atmosphere is nitrogen and/or inert gas；The temperature of calcining is 600~900 DEG C.
8. the method for positive active material is regenerated from waste lithium iron phosphate battery as described in claim 1, which is characterized in that
In step (1), the size controlling of product is in 2.5mm~10mm after being crushed；Described is substantially discharged finger: by waste lithium iron phosphate electricity
Pond is discharged to final voltage lower than 1V through salt water；The salt water is the sodium-chloride water solution of 10~30g/L.
9. the method as described in any one of claims 1 to 8 that positive active material is regenerated from waste lithium iron phosphate battery,
It is characterized in that, regenerating LiFePO4 obtained is LITHIUM BATTERY.
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