CN102208707B - Method for repair and regeneration of waste lithium iron phosphate battery cathode material - Google Patents
Method for repair and regeneration of waste lithium iron phosphate battery cathode material Download PDFInfo
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- CN102208707B CN102208707B CN2011101218965A CN201110121896A CN102208707B CN 102208707 B CN102208707 B CN 102208707B CN 2011101218965 A CN2011101218965 A CN 2011101218965A CN 201110121896 A CN201110121896 A CN 201110121896A CN 102208707 B CN102208707 B CN 102208707B
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for repair and regeneration of waste lithium iron phosphate battery cathode materials, which allows a lithium-source solution or a suspension to react with a recovered waste lithium iron phosphate battery material by a hydrothermal reaction or a solvent-thermal reaction, or allows the recovered waste lithium iron phosphate battery material to be processed by solid-phase ball-milling and calcination with the lithium source, performs liquid-phase or solid-phase direct lithium-supplementing repair of delithiated waste lithium iron phosphate, and then performs pertinent repair and regeneration by coating conductive agents or coating conductive agents and doping metal ions. The invention adopts a direct repair and regeneration method; the repaired waste lithium iron phosphate battery cathode material has excellent performance, and the specific capacity can reach above 90% of the specific capacity before discard; the method not only can effectively reduce environmental pollution of waste batteries, but also can make full use of waste resources and changes waste into valuables.
Description
One, technical field
The present invention relates to the recycling of old and useless battery, specifically a kind of method of waste lithium iron phosphate battery positive electrode reparative regeneration.
Two, background technology
Lithium ion battery is used widely in portable type electronic product, communication tool and electric bicycle in recent years as a kind of high performance secondary green power supply, and progressively is developed as the electrical source of power of electric automobile, novel energy-storing equipment.LiFePO4 (the LiFePO of olivine-type structure wherein
4) as a kind of novel anode material for lithium-ion batteries, have material source extensively, low price, theoretical specific capacity high (170mAh/g), Heat stability is good, the advantage such as environmentally friendly, be expected to become the first-selected lithium ion secondary battery anode material of a new generation.Along with promoting the use of of ferric phosphate lithium cell, must be accompanied by a large amount of waste and old iron phosphate lithium electrode materials, before for processing and the utilization of old and useless battery, after all being based on an old and useless battery material resources, reclaim Li wherein, Fe utilizes coprecipitation again to prepare LiFePO4 after the valuable element such as P or resource.
The a large amount of waste material Mechanical Crushing that produce in the processes such as patent CN 10138441A (a kind of comprehensive recovering process of positive pole waste tablet from ferric phosphate lithium cell) and patent CN 10394015A (a kind of renovation process of iron phosphate lithium positive pole waste material) be the useless sheet of positive pole collected in producing or batching, mixedly starch, sieve, coating, scraping blade, then most conductive agent and binding agent are removed in heat treatment, grind afterwards and make the iron phosphate lithium positive pole reclaimed materials.Above-mentioned two pieces of patents only relate to the recovery of the waste phosphoric acid iron lithium anode material that produces in production, rather than in waste battery after repeatedly recycling, the recoverying and utilizing method of the waste lithium iron phosphate that changes has all occured in material chemical composition and micro-structural.
Patent CN 101359756A (a kind of recovery method of lithium iron phosphate anode material from lithium ionic cell waste), after conductive agent and binding agent are removed in waste material heat treatment, add source of iron and/or lithium source and/or phosphorus source after mixing, calcine under inert gas atmosphere, reclaim and obtain lithium iron phosphate positive material.Though relate to the recovery of the waste lithium iron phosphate after recycling in this patent, be not based on the material failure Analysis on Mechanism, the waste lithium iron phosphate that lacks the lithium attitude is directly mended lithium, then coated conductive agent and/or doped metal ion carry out reparative regeneration.
Patent CN 101847763A (a kind of comprehensive method that reclaims of waste lithium iron phosphate battery) and patent CN 101916889A (method of preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery), the former does not carry out sorting process to the waste lithium iron phosphate battery positive and negative electrode but directly pulverizes positive and negative plate, simultaneously these two patents are all first to utilize sour dissolving phosphoric acid iron lithium, make Fe, Li, PO in solution with NaOH solution or ammoniacal liquor afterwards
4 3-Ion generates precipitation, and adds source of iron, lithium source, P source compound to adjust the mol ratio of Fe, Li, P in sediment, then adds carbon source, and calcining obtains new lithium iron phosphate positive material in ball milling, inert atmosphere.Although relate to the recovery of waste lithium iron phosphate in this two patent, the process of its recovery is first lithium iron phosphate positive material to be dissolved fully, makes its resource, prepares LiFePO4 by co-precipitation, ball milling, calcining more afterwards.It is more complicated that the method reclaims preparation LiFePO4 process, and in process, a large amount of acid of introducing, aqueous slkali not only can cause cost recovery to increase, and, might cause new environmental pollution.
Three, summary of the invention
The present invention is for fear of the existing weak point of above-mentioned prior art, provide that a kind of technique is simple, production cost is low, the method for environment amenable waste lithium iron phosphate battery positive electrode reparative regeneration, to realize the recovery reparation to the old and useless battery positive electrode, reduce the battery production cost and solve problem of environmental pollution.
Technical solution problem of the present invention adopts following technical scheme:
Failure mechanism based on positive electrode, utilize the analysis and testing technology means to characterize to positive electrode to be repaired, the characterization technique means are that X-ray powder diffraction (XRD), inductively coupled plasma spectrum (ICP), heat are analyzed (TG, DSC), Fourier transform infrared (FTIR) etc. one or more is used in conjunction, and determine the chemical composition of material.
waste lithium iron phosphate battery is discharged to 1.8V and discharges fully discharging and recharging on instrument, take the battery external packing apart by hacksaw or cutter, take out battery core, disassemble battery core, sub-elect the positive plate of aluminum foil current collector, described positive plate is placed in solvent to be soaked 2-7 days, positive electrode is separated with the collector aluminium foil, can assist in the process of soaking in addition and stir or ultrasonic or stir and the separating of ultrasonic acceleration positive plate and collector aluminium foil, after taking out, drying obtains the positive electrode powder, add aqueous slkali to remove residual aluminium bits in described positive electrode powder, filter, after drying, the apparent density difference of utilizing active material and conductive agent is processed or the decomposition temperature difference of utilizing both is processed at 500-700 ℃ of calcining 4-8h and removed conductive agent and obtain positive electrode to be repaired (phosphoric acid molysite through 5-10 FLOTATION SEPARATION or air current classifying, be mainly LiFePO4 and ferric phosphate),
Described aqueous slkali is LiOH, NaOH or KOH solution, and concentration is 0.1-10mol/L.
The binding agent that uses when positive plate during as the oil-soluble binding agent described solvent be 1-Methyl-2-Pyrrolidone (NMP), the binding agent that uses when positive plate during as water-soluble binder described solvent be deionized water;
the method of waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention, comprise the discharge of waste lithium iron phosphate battery, disassemble, sub-elect the preliminary treatment of positive plate and positive plate, difference with the prior art is: add lithium source solution or lithium source suspension in the pretreated positive electrode, add simultaneously reducing agent, in 120-300 ℃, 0.1-10MPa stirring reaction 6-48h, dry after filtration or centrifugal desolventizing, add subsequently conductive agent and metal ion or conductive agent, calcine 4-12h in 300-700 ℃ in inert atmosphere or vacuum atmosphere, carry out coated conductive agent and doped metal ion reparative regeneration,
Described lithium source solution or lithium source suspension are take the lithium source as solute, the solution that obtains take water, ethanol, benzene, ethylene glycol or glycerol as solvent or suspension, and concentration is 0.1-10mol/L.
The characteristics of the method for waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention also are: described reducing agent is hydrazine (N
2H
4) or vitamin C, addition is the 0.1-10% of positive electrode quality to be repaired.
The method of waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention, comprise waste lithium iron phosphate battery discharge, disassemble, sub-elect the preliminary treatment of positive plate and positive plate, difference with the prior art is: add lithium source and conductive agent in the pretreated positive electrode or add lithium source, conductive agent and metal ion, 2-12h mixes with the 200-400r/min ball milling, in 300-700 ℃ of calcining 6-24h, carry out coated conductive agent and doped metal ion reparative regeneration in inert atmosphere or vacuum atmosphere; The addition in described lithium source is the 0.1-15% of positive electrode quality to be repaired.
The characteristics of the method for waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention are: described lithium source is lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium phosphate or lithium dihydrogen phosphate.
The characteristics of the method for waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention are: described conductive agent (being carbon source) is one or more in cellulose acetate, vitamin C, Carbon SP, glucose, sucrose, carbon nano-tube, Graphene, and addition is the 1-15% of positive electrode quality to be repaired.
The characteristics of the method for waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention are: described metal ion adds with the form of slaine and/or metal oxide, and the addition of described metal ion is the 0.1-10% of positive electrode molal quantity to be repaired; Wherein slaine is one or more in the acetate, carbonate, nitrate of nickel, copper, magnesium, titanium, zinc, manganese, cobalt, niobium, thorium, vanadium, and metal oxide is one or more in the oxide of nickel, copper, magnesium, titanium, zinc, manganese, cobalt, niobium, thorium, vanadium.
The characteristics of the method for waste lithium iron phosphate battery positive electrode reparative regeneration of the present invention are: described inert atmosphere is nitrogen, helium, neon or argon gas.
The failure mechanism of positive electrode mainly contain following some:
Battery makes active material fail to take full advantage of through repeatedly making inert substance be coated on active material after circulation; Stress causes internal break, reduces active material and conductive agent and active material and contacts with electronics between the collector aluminium foil, the impedance increase; Lithium and negative pole Graphene form LiC
6After circulation repeatedly, after discharge, the lithium of negative pole can not all be got back to positive pole, and forms SEI film (solid electrolyte interface, the solid electrolyte interface film) lithium that loses, one or more that make positive electrode become to lack the lithium attitude gather together.
In the present invention, the reparative regeneration lithium iron phosphate positive material can be repaired two kinds of methods by liquid phase reparation or solid phase, and wherein the liquid phase reparation need not to determine to add the total amount in lithium source, as long as there is the concentration gradient of lithium, according to K
SPAnd the Gibbs energy of whole reaction, will produce LiFePO4.Utilize lithium source solution or suspension and phosphoric acid molysite (being mainly LiFePO4 and ferric phosphate) hydro-thermal reaction to be repaired or solvent thermal reaction or generate LiFePO4 with lithium source ball milling calcining, the waste lithium iron phosphate that lacks the lithium attitude is carried out liquid phase hydro-thermal/solvent heat or solid-phase ball milling is directly mended the lithium reparation.
Old and useless battery is carried out complete discharge process, the one, occur dangerous in disassembling process for fear of the waste lithium iron phosphate battery that contains remaining capacity; The 2nd, make the lithium on negative pole get back to as much as possible in positive electrode, repair to mend lithium for next step and save the lithium source.Take waste lithium iron phosphate battery after discharge fully apart by means of hacksaw or cutter, remove external packing and obtain the cell core, reclaim the battery outer packing shell in this process.Disassemble battery, obtain positive and negative electrode and barrier film.Barrier film can directly reclaim, and negative pole is placed in water and soaks a period of time, then by stirring and/or ultrasonic method makes it separate with copper foil of affluxion body, filters afterwards, drying obtains Copper Foil and contain the electrographite of binding agent.
Be assembled into battery with repairing the proportioning of successful lithium iron phosphate positive material according to active material and conductive agent and binding agent in former old and useless battery, charge and discharge electrical measurement, the ferric phosphate lithium cell material after relatively repairing and the ferric phosphate lithium cell of scrapping and the chemical property of scrapping front ferric phosphate lithium cell.
The present invention directly mends lithium to waste and old LiFePO4, and coated with conductive agent and doping metals reparation activate it once again, directly uses as new lithium iron phosphate positive material.So not only economize on resources, reduce energy consumption but also alleviate pollution to environment.
Compared with the prior art beneficial effect of the present invention is embodied in:
1, recycle object of the present invention is not the waste slurry that the processes such as the useless sheet that produces in production process or coating produce, but reclaim the LiFePO 4 material of scrapping after reparation recycles in automobile or large-scale energy storage device, the object that such recovery is repaired clear and definite (the battery famous brand is clear), be easy to positive and negative electrode and barrier film separates, and it is large to reclaim the reparation amount, economize on resources, alleviate old and useless battery to the pollution of environment.
2, the present invention is in removing the waste lithium iron phosphate positive plate during conductive agent, adopts repeatedly flotation or air current classifying to process or calcination processing is removed conductive agent, can keep to greatest extent the original chemical composition of waste lithium iron phosphate positive electrode.
3, the present invention does not adopt in processing the reparative regeneration process and first utilizes acid dissolving positive electrode, makes it become Li, Fe, PO
4 3-The aqueous solution, make Li, Fe, PO by coprecipitation more afterwards
4 3-Ion precipitation get off (with the process of its resource), through calcining preparation lithium iron phosphate positive material thinking, and be based on the lithium iron phosphate positive material failure mechanism, adopt the calcining of liquid phase water thermal response or solvent thermal reaction or solid-phase ball milling directly to mend lithium to positive electrode, coated conductive agent or coated conductive agent and doped metal ion are repaired afterwards, renovation technique is simple, and energy consumption is low.
4, reparation of the present invention is based on ferric phosphate lithium cell is recycled on the failure Mechanism basis, utilize lithium source solution or suspension and ferric phosphate salt hydro-thermal to be repaired or solvent thermal reaction or generate LiFePO4 with lithium source ball milling calcining, the waste lithium iron phosphate that lacks the lithium attitude is carried out liquid phase hydro-thermal/solvent heat or solid-phase ball milling is directly mended the lithium reparation, reparative regeneration is motivated, and the renovation technique parameter is accurate.Make the lower specific capacity of old and useless battery material, polarization is large, through reparative regeneration, reaches higher specific capacity and polarizes littlely, and platform is good, compares with the specific capacity level before scrapping, and makes the specific capacity of the electrode material of reparative regeneration bring up to more than 90% of original level.
Four, description of drawings
The XRD diffraction pattern of the lithium iron phosphate positive material that Fig. 1 is to be repaired.
The XRD diffraction pattern of the lithium iron phosphate positive material of carbon is wrapped in the reparation of Fig. 2 liquid phase afterwards.
The XRD diffraction pattern of the lithium iron phosphate positive material of carbon, copper doped ion is wrapped in the reparation of Fig. 3 liquid phase afterwards.
The XRD diffracting spectrum of the lithium iron phosphate positive material after Fig. 4 solid phase is repaired.
The lithium iron phosphate positive material charging and discharging curve of carbon is wrapped in the reparation of Fig. 5 liquid phase afterwards.
The lithium iron phosphate positive material charging and discharging curve of carbon, copper doped ion is wrapped in the reparation of Fig. 6 liquid phase afterwards.
The curve of the lithium iron phosphate positive material charging after Fig. 7 solid phase is repaired.
The lithium iron phosphate positive material charging and discharging curve that Fig. 8 scraps.
Lithium iron phosphate positive material charging and discharging curve before Fig. 9 scraps.
Five, embodiment
Further describe the present invention below in conjunction with specific embodiments and the drawings.
Take 50g waste lithium iron phosphate battery positive plate and put into the 250mL beaker, add the 1-Methyl-2-Pyrrolidone of 100mL in the beaker, soak and put in ultrasonic cleaning machine ultrasonicly after 7 days, stir on ultrasonic limit, limit, screens out aluminium foil through 40 purpose steel afterwards.Filtrate is centrifugal, first with ethanol washing 4 times, wash afterwards 6 times.Centrifugal product is transferred in the NaOH solution of 1mol/L and soaked 5 minutes, the aluminium bits that removal may contain.Obtain containing afterwards the positive electrode of conductive agent through centrifuge washing, then remove conductive agent through 5 FLOTATION SEPARATION, obtain lithium iron phosphate positive material to be repaired.
Embodiment 1:
Take the lithium iron phosphate positive material to be repaired of 2.5g, be placed in the autoclave of 50mL, adding the lithium concentration of 30mL in the autoclave again is the lithium oxalate solution of 0.3mol/L and the vitamin C of 0.01g, enclosed high pressure still afterwards, react 36h under 170 ℃, after reaction is completed, the centrifugal oven dry of product is obtained liquid phase and mend lithium material, liquid phase is mended lithium material and 0.125g glucose add that in 5mL distilled water, ultrasonic dispersion mixes, then calcine 2h prior to 350 ℃ under nitrogen atmosphere, the lithium iron phosphate positive material that obtains repairing at 550 ℃ of calcining 6h afterwards.
In the LiFePO4 active material: conductive agent: the binding agent mass ratio is that the ratio of 90: 5: 5 is made into electrode slice, and take metal lithium sheet as negative pole, Celgard 2400 polypropylene porous films are barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution (volume ratio is 1: 1) of dimethyl carbonate (DMC) be electrolyte, be assembled into CR2032 type button cell in being full of the dry glove box of argon gas, carry out charge-discharge test, specific discharge capacity is 133mAh/g (Fig. 5) under 0.1C.
Embodiment 2:
Take the lithium iron phosphate positive material to be repaired of 3g, be placed in the autoclave of 50mL, then to add the lithium concentration of 30mL in the autoclave be the lithium chloride solution of 1mol/L and the hydrazine (N of 0.005g
2H
4), enclosed high pressure still afterwards, react 10h under 200 ℃, the reaction complete after with the centrifugal oven dry of product, liquid phase is mended material, 0.3g sucrose and 0.03g one nitric hydrate copper ball milling 3h under the rotating speed of 400r/min after lithium, first 350 ℃ of calcining 3h under nitrogen atmosphere, calcine at 650 ℃ the lithium iron phosphate positive material that 7h obtain repairing afterwards afterwards.
In the LiFePO4 active material: conductive agent: the binding agent mass ratio is that the ratio of 90: 5: 5 is made into electrode slice, and take metal lithium sheet as negative pole, Celgard 2400 polypropylene porous films are barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution (volume ratio is 1: 1) of dimethyl carbonate (DMC) be electrolyte, be assembled into CR2032 type button cell in being full of the dry glove box of argon gas, carry out charge-discharge test, specific discharge capacity is 135mAh/g (Fig. 6) under 0.1C.
Embodiment 3:
Take the lithium iron phosphate positive material to be repaired of 2g, be placed in the ball grinder of 50mL, add the lithium carbonate of 0.096g, glucose and the 0.06g cupric oxide of 0.2g again in ball grinder, according to ratio of grinding media to material 1: 30, add the agate ball of 70g and the ethanol of 5mL, afterwards the closed ball milling tank, ball milling 6h under 400r/min, after reaction is completed, with the product filtering drying, first 350 ℃ of calcining 5h, calcine at 600 ℃ the lithium iron phosphate positive material that 12h obtain repairing afterwards under nitrogen atmosphere.
In the LiFePO4 active material: conductive agent: the binding agent mass ratio is that the ratio of 90: 5: 5 is made into electrode slice, and take metal lithium sheet as negative pole, Celgard 2400 polypropylene porous films are barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution (volume ratio is 1: 1) of dimethyl carbonate (DMC) be electrolyte, be assembled into CR2032 type button cell in being full of the dry glove box of argon gas, carry out charge-discharge test, specific discharge capacity is 132mAh/g (Fig. 7) under 0.1C.
Comparative Examples 1:
After the waste lithium iron phosphate battery positive plate vacuum drying after disassembling, with take metal lithium sheet as negative pole, celgard 2400 polypropylene porous films are barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution (volume ratio is 1: 1) of dimethyl carbonate (DMC) be electrolyte, be assembled into CR2032 type button cell in being full of the dry glove box of argon gas, carry out charge-discharge test.Obtain that under 0.1C, specific discharge capacity is 120mAh/g, and serious polarization (Fig. 8).
Comparative Examples 2:
Take the front lithium iron phosphate positive material of scrapping of 1g, in the LiFePO4 active material: conductive agent: the binding agent mass ratio is that the ratio of 90: 5: 5 is made into electrode slice, take metal lithium sheet as negative pole, Celgard 2400 polypropylene porous films are barrier film, 1mol/LLiPF
6Ethylene carbonate (EC) and the mixed solution (volume ratio is 1: 1) of dimethyl carbonate (DMC) be electrolyte, be assembled into CR2032 type button cell in being full of the dry glove box of argon gas, carry out charge-discharge test.Obtain that under 0.1C, specific discharge capacity is 147mAh/g (Fig. 9).
Fig. 1 is the XRD diffraction pattern of lithium iron phosphate positive material to be repaired, contains the phosphoric acid molysite in the waste lithium iron phosphate positive electrode as can be seen from Figure 1, presents to lack the lithium attitude.We obtain the LiFePO4 of pure phase by the benefit lithium reparation of liquid phase water thermal response and coated with conductive agent carbon, see Fig. 2, and mend by the liquid phase water thermal response LiFePO4 that lithium reparation and coated with conductive agent carbon and copper doped ion obtain pure phase, see Fig. 3.Calcine by solid-phase ball milling in addition and directly mend the LiFePO4 that lithium reparation and coated with conductive agent carbon and copper doped ion obtain pure phase, see Fig. 4.
As can be seen from Figure 5, mend lithium reparation and coated with conductive agent carbon by the liquid phase water thermal response and must repair successful lithium iron phosphate positive material and carry out charge-discharge test and obtain that under the 0.1C multiplying power, specific capacity is 133mAh/g, and polarization is very little; As can be seen from Figure 6, mend lithium reparation and coated with conductive agent carbon and copper doped ion by the liquid phase water thermal response and obtain repairing successful lithium iron phosphate positive material and carry out charge-discharge test and obtain that under the 0.1C multiplying power, specific capacity is 135mAh/g, and polarization is very little; As can be seen from Figure 7, calcining lithium iron phosphate positive material specific capacity under the 0.1C multiplying power of directly mending lithium reparation and coated with conductive agent carbon and copper doped ion reparation success by solid-phase ball milling is 132mAh/g; And the lithium iron phosphate positive material chemical property (seeing Fig. 8) of scrapping polarization is large, and under the 0.1C multiplying power, specific capacity is only 120mAh/g.And under the 0.1C multiplying power of three kinds of restorative procedure resulting materials specific capacity can reach scrap before (seeing Fig. 9) 90%, 92% and 90%.
Claims (2)
1. the method for a waste lithium iron phosphate battery positive electrode reparative regeneration, comprise waste lithium iron phosphate battery discharge, disassemble, sub-elect the preliminary treatment of positive plate and positive plate, it is characterized in that:
The preliminary treatment of described positive plate is positive plate to be placed in solvent soaked 2-7 days, positive electrode is separated with the collector aluminium foil, after taking out, drying obtains the positive electrode powder, add in the described positive electrode powder aqueous slkali to remove residual aluminium bits, filter, dry by 5-10 FLOTATION SEPARATION or air current classifying is processed or 500-700 ℃ of calcining 4-8h processes the removal conductive agent and obtain pretreated positive electrode;
Add lithium source solution or lithium source suspension in the pretreated positive electrode, add simultaneously reducing agent, in 120-300 ℃, 0.1-10MPa stirring reaction 6-48h, dry after filtration or centrifugal desolventizing, add subsequently conductive agent and metal ion or conductive agent, calcine 4-12h in 300-700 ℃ in inert atmosphere or vacuum atmosphere;
Described lithium source solution or lithium source suspension are take the lithium source as solute, the solution that obtains take water, ethanol, benzene, ethylene glycol or glycerol as solvent or suspension, and concentration is 0.1-10mol/L;
Described reducing agent is hydrazine or vitamin C, and addition is the 0.1-10% of positive electrode quality to be repaired;
Described lithium source is lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium phosphate or lithium dihydrogen phosphate;
Described conductive agent is one or more in cellulose acetate, vitamin C, Carbon SP, glucose, sucrose, carbon nano-tube, Graphene, and addition is the 1-15% of positive electrode quality to be repaired;
Described metal ion adds with the form of slaine and/or metal oxide, and the addition of described metal ion is the 0.1-10% of positive electrode molal quantity to be repaired; Wherein slaine is one or more in the acetate, carbonate, nitrate of nickel, copper, magnesium, titanium, zinc, manganese, cobalt, niobium, thorium, vanadium, and metal oxide is one or more in the oxide of nickel, copper, magnesium, titanium, zinc, manganese, cobalt, niobium, thorium, vanadium;
Described inert atmosphere is nitrogen, helium, neon or argon gas.
2. the method for a waste lithium iron phosphate battery positive electrode reparative regeneration, comprise waste lithium iron phosphate battery discharge, disassemble, sub-elect the preliminary treatment of positive plate and positive plate, it is characterized in that:
The preliminary treatment of described positive plate is positive plate to be placed in solvent soaked 2-7 days, positive electrode is separated with the collector aluminium foil, after taking out, drying obtains the positive electrode powder, add in the described positive electrode powder aqueous slkali to remove residual aluminium bits, filter, dry by 5-10 FLOTATION SEPARATION or air current classifying is processed or 500-700 ℃ of calcining 4-8h processes the removal conductive agent and obtain pretreated positive electrode;
Add lithium source and conductive agent in the pretreated positive electrode or add lithium source, conductive agent and metal ion, ball milling 2-12h mixes, in inert atmosphere or vacuum atmosphere in 300-700 ℃ of calcining 6-24h; The addition in described lithium source is the 0.1-15% of positive electrode quality to be repaired;
Described lithium source is lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium phosphate or lithium dihydrogen phosphate;
Described conductive agent is one or more in cellulose acetate, vitamin C, Carbon SP, glucose, sucrose, carbon nano-tube, Graphene, and addition is the 1-15% of positive electrode quality to be repaired;
Described metal ion adds with the form of slaine and/or metal oxide, and the addition of described metal ion is the 0.1-10% of positive electrode molal quantity to be repaired; Wherein slaine is one or more in the acetate, carbonate, nitrate of nickel, copper, magnesium, titanium, zinc, manganese, cobalt, niobium, thorium, vanadium, and metal oxide is one or more in the oxide of nickel, copper, magnesium, titanium, zinc, manganese, cobalt, niobium, thorium, vanadium;
Described inert atmosphere is nitrogen, helium, neon or argon gas.
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| CN101916889B (en) * | 2010-08-16 | 2012-05-30 | 长春劲能锂电池科技有限公司 | Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery |
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