CN106505273A - The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled - Google Patents
The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled Download PDFInfo
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- CN106505273A CN106505273A CN201710021526.1A CN201710021526A CN106505273A CN 106505273 A CN106505273 A CN 106505273A CN 201710021526 A CN201710021526 A CN 201710021526A CN 106505273 A CN106505273 A CN 106505273A
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- positive pole
- phosphate lithium
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses the method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled.The present invention comprises the steps：The iron phosphate lithium positive pole piece that obtains will be reclaimed first to be placed in alkaline solution, after aluminium foil is kept completely separate, aluminium foil is separated from alkaline solution, then to alkaline solution in iron phosphate lithium positive pole mixing material filter, washing, then dry, ball milling sieves.Iron phosphate lithium positive pole mixing material powder after sieving soaks in organic solvent, and stirring removes the binding agent in mixing material, refilters, carrying out washing treatment, carries out the heat treatments such as roasting and calcining, obtain the lithium iron phosphate positive material of function admirable after drying.Waste product LiFePO4 can be realized repairing by the present invention, obtain the electric property suitable with freshly prepared product, and can farthest retain aluminium foil being easy to aluminium manufacturer to reclaim, and the heat treatment temperature that wants needed for whole flow process is relatively low, process is simple, environmental protection.
Description
Technical field
The present invention relates to field is reclaimed in the process of lithium ion battery waste and scrap, more particularly to a kind of ferric phosphate lithium cell life
Produce the method that the recovery of link positive pole waste and scrap is repaired and recycled.
Background technology
Since being introduced to the market from global first commercial Li-ion battery in 1991 by Sony, lithium ion battery is produced
The development of more than 20 year experienced already, and market scale surmounts other secondary electricity such as nickel-cadmium cell, Ni-MH battery from scratch, successively
Pond and develop into the first-selected battery in 3C electronic products, electric automobile and energy storage field.
In recent years, increasingly serious with environmental problems such as the increasingly minimizing of fossil resource, hazes, Development of EV is obtained
Great attention to national governments.And Development of EV, key is in battery.Lithium ion battery becomes by its excellent performance
The ideal power source of New Generation of Electric Vehicle, with lightweight, energy storage big, power is big, pollution-free, also non-secondary pollution, life-span
Long, self discharge coefficient is little, temperature adaptation wide scope, is the ideal car battery of electric automobile.Arrange from electric automobile
Enter National 863 development in Hi-Tech plan, national seven great strategies new industry, New Energy Sources In China vapour is listed in new-energy automobile industry
Car industry has obtained quick development nearly ten years, and China's new-energy automobile assumes explosive growth, yield 37.9 ten thousand within 2015
, increasing by 3.5 times on a year-on-year basis, be expected within 2016 reach 500,000, China also becomes the increment city of global maximum new-energy automobile
?.In the five-year whole nation, new-energy automobile is by the policy goals up to 5,000,000 recoverable amounts.
The positive electrode that the development of New Energy Sources In China automobile power cell is used generally has LiMn2O4, ternary material, phosphoric acid
Ferrum lithium.LiMn2O4 high-temperature behavior, cycle performance, storge quality are poor, and the service life of set of cells is shorter.And in car load safety
In design, New Energy Sources In China automobile uses ternary lithium electricity as electrokinetic cell, there is certain potential safety hazard.Ternary material de-
Oxygen temperature is 200 DEG C, and exothermic energy cannot be indicated including ternary battery by the perverse experiment of pin more than 800J/g, ternary lithium electricity
In the case of portion's short circuit, it is easy to cause security incident.Ferric phosphate lithium cell is because which is safe and reliable, stable performance and cost are relative
Cheap advantage is favored, and the electrokinetic cell that especially applies on city bus and electric bus, is all mainly iron phosphate
Lithium battery.According to statistics, on pure electric coach, LiFePO4 still accounts for main flow, and the yield (self-produced containing enterprise) of LiFePO4 is compared
Increased by 170.0% in 2015.
As consumption of the ferric phosphate lithium cell on new-energy automobile increases year by year, the iron phosphate of each cell production companies
The yield of lithium battery is also increasing, and it is useless that thing followed lithium iron phosphate positive material factory is present in process of production
Material, and the positive pole waste and scrap that Battery Plant is produced because of broken belt or section inequality in coating tableting processes is also increasingly
Many.If these waste and scraps directly abandoned, undoubtedly a kind of huge wasting of resources.Especially with new-energy automobile pair
The demand of lithium battery is increasing, causes lithium carbonate price to escalate, and battery-level lithium carbonate quotation reaches 13.5 ten thousand yuan/ton.
With putting into operation in a large number for the electric automobile being used as power using LiFePO4, thing followed LiFePO4 old and useless battery amount
Quick increase, it is contemplated that from the beginning of 2017, the yield of the annual old and useless battery of China is up to 17～210,000 tons.Therefore for phosphoric acid
The recovery reparation of lithium iron battery positive pole waste and scrap and recycling meaning are very great.
Mainly there is following several method currently for the recovery in iron phosphate lithium positive pole waste and scrap.Chinese patent
CN101383441A discloses a kind of comprehensive recovering process of iron phosphate lithium positive pole waste paper, by mechanical separation and or ultrasound shake
Aluminium foil is separated by method first that swing, obtains the mixture of LiFePO4, conductive agent and adhesive residue thing；This is mixed
Compound toasts 8～24h under conditions of 80～150 DEG C；Material pulverizing classification after by baking, control particle diameter are not more than 15 μm.
Obtain final product iron phosphate lithium positive pole salvage material.The method does not account for the binding agent of mixture residual, electrification of the conductive agent to material
Learn the impact of performance.
Chinese patent CN104362408A discloses the recovery that a kind of ferric phosphate lithium cell manufactures link LiFePO4 waste material
The method of recycling.The pole piece of recovery is placed in Muffle furnace at a high temperature of 400～600 DEG C and toasts 2
～3h, active compound lithium iron phosphate and conductive agent depart from from aluminium foil；Then 650～800 DEG C high in Muffle furnace
Sieve after temperature 4～6h of baking and obtain LiFePO4 powder；LiFePO4 powder is washed with deionized, and adds ethanol profit after washing
Humectant makes suspension；Soluble lithium salt, iron salt, phosphate are mixed in proportion in ethanol solution, 120～140 DEG C of vacuum
Dry；Under inert atmosphere protection, 650～850 DEG C bake 3～6h, obtain passing material.The method is not examined in removal process
The recovery of worry aluminium foil, and the oxidation of LiFePO4 can be caused under conditions of higher temperature calcination, cause the phosphoric acid for obtaining
Ferrum lithium material performance is substantially inferior to certified products iron phosphate material.
The present invention is reclaimed, is repaired positive material of waste lithium iron phosphate, in removal process using a kind of simple method
In greatly can preserve aluminium foil so as to its reclaim, meanwhile, be relatively low in the heat treatment temperature needed for whole process, institute
The energy consumption for needing is relatively low, and repairs the product for obtaining, with the chemical property close with brand-new certified products iron phosphate material.
Content of the invention
In for the manufacture process of ferric phosphate lithium cell, usually can be because in the coating tableting processes of lithium iron phosphate positive material
Substantial amounts of leftover pieces are produced when broken belt or section, the positive pole waste paper that part does not meet technological requirement can be also produced sometimes, and
Waste lithium iron phosphate battery positive plate, and these waste and scraps cannot often be dealt carefully with, the present invention provides a kind of iron phosphate
The method that the recovery of lithium battery production link positive pole waste and scrap is repaired and recycled.
The technical scheme is that：
The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled, including as follows
Step：
(1) the LiFePO4 production link anode waste and scrap of recovery is placed in alkaline solution and is stirred, made
Active compound lithium iron phosphate material is kept completely separate from aluminium foil；
(2) after separate the aluminium foil that isolates in step (1) alkali liquor, to remaining LiFePO4 in alkali liquor, conductive agent, viscous
Knot agent mixing material is carried out filtering, is washed；
(3) mixing material after step (2) washing is dried；
(4) dried for step (3) mixing material is carried out ball milling, to ball milling after powder vibration screening, control
Particle diameter is below 15 μm；
(5) the mixing material powder for obtaining step (4) soaks in organic solvent, stirs and 1～4h of ultrasound, removes which
In binding agent；
(6) will step (5) resulting materials filter, dry after, be placed in reaction kiln in carry out roasting remove part carbon；
(7) material after step (6) roasting is calcined under inert gas shielding, obtains the iron phosphate lithium positive pole material that repairs
Material；
(8) lithium iron phosphate positive material for obtaining step (7) and conductive agent, binding agent mix homogeneously are coated with after homogenate
On aluminium foil, ferric phosphate lithium cell is reassembled into.
Further, the rotating speed of ball mill is 300～600rpm.
Further, the described screen cloth sieved using 300～600 mesh.
Further, the alkaline solution be sodium hydroxide, Lithium hydrate, potassium hydroxide solution one or two with
On；Its concentration is 0.05～1mol/L.
Further, described organic solvent be acetone, N-Methyl pyrrolidone (NMP), in dimethylformamide (DMF)
One or more.
Further, the temperature of the roasting is 100～300 DEG C, and the time is 2～5h.
Further, the temperature of the calcining is 400～800 DEG C, and the time is 2～6h.
Further, described calcining is carried out in tube furnace, and the heating mode of tube furnace heats up for staged, and which heats up
Speed is 1～5 DEG C of min-1.
Further, the noble gases are the mixed gas of argon and hydrogen, and the volume accounting of argon is 80～99%,
Hydrogen is 1～20%.
Further, in step (8), the mass ratio of lithium iron phosphate positive material, conductive agent and binding agent is 8：0.5～1：
0.5～1.
The beneficial effects of the present invention is：
The present invention can reclaim well in producer's production process produced by iron phosphate lithium positive pole waste material, and reclaim and
Repair process is simple, can dramatically preserve the aluminium foil in separation process, is easy to aluminium manufacturer to reclaim.Institute in heat treatment process
The temperature for needing is relatively low, and energy consumption is little, and the material recycled after repairing has and freshly prepd lithium iron phosphate positive material
Close chemical property.
Description of the drawings
XRD figure of the Fig. 1 for 1 preprosthetic lithium iron phosphate positive material of embodiment.
Fig. 2 is schemed for the SEM of 1 preprosthetic lithium iron phosphate positive material of embodiment.
Fig. 3 is the XRD figure of the lithium iron phosphate positive material after the reparation of embodiment 1.
Fig. 4 is the SEM figures of the lithium iron phosphate positive material after the reparation of embodiment 1.
Fig. 5 first charge-discharge curves under different multiplying for the lithium iron phosphate positive material after the reparation of embodiment 1.
Fig. 6 is cycle performance figure of the lithium iron phosphate positive material after the reparation of embodiment 1 in 1C, 2C and 5C.
Fig. 7 is the lithium iron phosphate positive material high rate performance curve chart after the reparation of embodiment 1.
Specific embodiment
The present invention is further described by the following examples, so that those skilled in the art more fully understand this
Bright, but the present invention is not limited to following examples.
Experimental technique in following embodiments, if no special instructions, is conventional method.
Embodiment 1
(1) the waste lithium iron phosphate positive plate of 500g is put in order the sodium hydroxide solution for being put into 500mL 0.05mol/L
In, start to stir after immersion 10min, after material is kept completely separate from aluminium foil, remove aluminium foil；
(2) mixing materials such as remaining LiFePO4, conductive agent, binding agent in step (1) alkali liquor filtered, washed；
(3) the LiFePO4 mixing material after step (2) washing is put in 80 DEG C of baking ovens and dries 24h.
(4) LiFePO4 mixing material dried for step (3) is carried out ball milling, described rotational speed of ball-mill is 500rpm,
Powder vibration screening after ball milling, using the screen cloth of 500 mesh；
(5) the LiFePO4 mixing material powder for obtaining step (4) is immersed in NMP, is stirred and supersound process 4h, is removed
Remove binding agent therein；
(6) LiFePO 4 material that obtains step (5) filters, dry after, roast under the conditions of being placed in 250 DEG C in reaction kiln
Burn 4h and remove part carbon；
(7) by the LiFePO 4 material after step (6) roasting under inert gas shielding according to 5 DEG C/min heating rate liters
To 400 DEG C, 2h is calcined, obtains repairing recycling LiFePO 4 material；Described inert atmosphere is：Argon volume accounting
95%, hydrogen 5%；
(8) LiFePO 4 material that obtains step (7), conductive agent, binding agent are by 8：0.7：0.7 mass ratio mixing is
Even, homogenate is coated on aluminium foil, is assembled into ferric phosphate lithium cell.
Fig. 2, Fig. 4 are SEM figure of the LiFePO 4 material before and after reparation in embodiment 1 respectively, wherein, correspond to before reparation
Step (4), corresponds to step (7) after reparation.As it is clear from fig. 2 that due to the presence of binding agent, material agglomeration is than more serious；
After NMP immersions and heat treatment, the agglomeration of Fig. 4 is significantly reduced.Fig. 1 and Fig. 3 are LiFePO 4 materials before reparation
XRD figure afterwards, it can be seen that after repairing LiFePO4 product XRD figure, the intensity of each diffraction maximum is higher, and peak shape is sharp, says
LiFePO 4 material after bright recycling has high-crystallinity.With the lithium iron phosphate positive material group after reparation in the present embodiment
Button cell is dressed up, is found by electrochemical property test, as shown in figure 5, the material is in 2.0～4.3V voltage conditions and 0.2C
Under electric current density, first discharge specific capacity is 159mAh g-1.And can be seen that after reparation from the cycle life curve of Fig. 6
Good cyclical stability is shown when LiFePO 4 material is as lithium ion cell positive, under 1C, 2C and 5C electric current density,
Its first discharge specific capacity is up to 148,139 and 128mAh g respectively-1, after 200 charge and discharge cycles, its specific capacity is protected
Holdup is respectively 94.0%, 92.1% and 89%.Meanwhile, from Fig. 7 it can also be seen that the LiFePO 4 material after repairing is used as lithium
There is during ion battery positive pole excellent high rate performance, under the high magnification of 10C, its specific discharge capacity still there are 103mAh g-1.
Embodiment 2
(1) the waste lithium iron phosphate positive plate of 500g is put in order the potassium hydroxide solution for being put into 500mL 0.5mol/L
In, start to stir after immersion 10min, after material is kept completely separate from aluminium foil, remove aluminium foil；
(2) mixing materials such as remaining LiFePO4, conductive agent, binding agent in step (1) alkali liquor filtered, washed；
(3) the LiFePO4 mixing material after step (2) washing is put in 100 DEG C of baking ovens and dries 24h；
(4) LiFePO4 mixing material dried for step (3) is carried out ball milling, described rotational speed of ball-mill is 400rpm,
Powder vibration screening after ball milling, using the screen cloth of 400 mesh；
(5) the LiFePO4 mixing material powder for obtaining step (4) is immersed in DMF, is stirred and ultrasound 2h, is removed which
In binding agent；
(6) LiFePO 4 material that obtains step (5) filters, dry after, roast under the conditions of being placed in 200 DEG C in reaction kiln
Burn 3h and remove part carbon；
(7) by the LiFePO 4 material after step (6) roasting under inert gas shielding according to 5 DEG C/min heating rate liters
To 500 DEG C, 6h is calcined, obtains repairing recycling lithium iron phosphate positive material；Described inert atmosphere is：Argon volume is accounted for
Than 95%, hydrogen 5%；
(8) lithium iron phosphate positive material that obtains step (7), conductive agent, binding agent are by 8：1：0.7 mass ratio mixing
Uniformly, homogenate is coated on aluminium foil, is assembled into ferric phosphate lithium cell.
Shown by electrochemical property test result, the material is under 2.0～4.3V voltage conditions and 0.2C electric current densities
First discharge specific capacity is 138mAh g-1, under 2C electric current densities, its first discharge specific capacity is 128mAh g-1
Embodiment 3
(1) the waste lithium iron phosphate positive plate of 500g is put in order sodium hydroxide solution first that be put into 500mL 1mol/L
In, start to stir after immersion 10min, after material is kept completely separate from aluminium foil, remove aluminium foil.
(2) mixing materials such as remaining LiFePO4, conductive agent, binding agent in step (1) alkali liquor filtered, washed.
(3) the LiFePO4 mixing material after step (2) washing is put in 80 DEG C of baking ovens and dries 24h.
(4) LiFePO4 mixing material dried for step (3) is carried out ball milling, described rotational speed of ball-mill is 600rpm,
Powder vibration screening after ball milling, using the screen cloth of 600 mesh.
(5) the LiFePO4 mixing material powder for obtaining step (4) is immersed in DMF, is stirred and ultrasound 1h, is removed which
In binding agent；
(6) LiFePO 4 material that obtains step (5) filters, dry after, roast under the conditions of being placed in 300 DEG C in reaction kiln
Burn 2h and remove part carbon；
(7) by the LiFePO 4 material after step (6) roasting under inert gas shielding according to 5 DEG C/min heating rate liters
To 800 DEG C, 3h is calcined, obtains repairing recycling lithium iron phosphate positive material.Described inert atmosphere is：Argon volume is accounted for
Than 95%, hydrogen 5%.
(8) lithium iron phosphate positive material that obtains step (7), conductive agent, binding agent are by 8：1：1 mass ratio mixing is
Even, homogenate is coated on aluminium foil, is assembled into ferric phosphate lithium cell.
Shown by electrochemical property test result, the material is under 2.0～4.3V voltage conditions and 0.2C electric current densities
First discharge specific capacity is 130mAh g-1, under 2C electric current densities, its first discharge specific capacity is 120mAh g-1
Embodiment 4
(1) first the waste lithium iron phosphate positive plate of 500g is put in order be put into 500mL 0.2mol/L Lithium hydrate molten
In liquid, start to stir after immersion 10min, after material is kept completely separate from aluminium foil, remove aluminium foil.
(2) mixing materials such as remaining LiFePO4, conductive agent, binding agent in step (1) alkali liquor filtered, washed.
(3) the LiFePO4 mixing material after step (2) washing is put in 80 DEG C of baking ovens and dries 24h.
(4) LiFePO4 mixing material dried for step (3) is carried out ball milling, described rotational speed of ball-mill is 300rpm,
Powder vibration screening after ball milling, using the screen cloth of 300 mesh.
(5) the LiFePO4 mixing material powder for obtaining step (4) is immersed in NMP, is stirred and ultrasound 4h, is removed which
In binding agent.
(6) LiFePO 4 material that obtains step (5) filters, dry after, roast under the conditions of being placed in 100 DEG C in reaction kiln
Burn 5h and remove part carbon.
(7) by the LiFePO 4 material after step (6) roasting under inert gas shielding according to 5 DEG C/min heating rate liters
To 700 DEG C, 4h is calcined, obtains repairing recycling lithium iron phosphate positive material.Described inert atmosphere is：Argon volume is accounted for
Than 99%, hydrogen 1%.
(8) lithium iron phosphate positive material that obtains step (7), conductive agent, binding agent are by 8：0.5：0.5 mass ratio is mixed
Close uniformly, homogenate is coated on aluminium foil, is assembled into ferric phosphate lithium cell.
Shown by electrochemical property test result, the material is under 2.0～4.3V voltage conditions and 0.2C electric current densities
First discharge specific capacity is 135mAh g-1, under 2C electric current densities, its first discharge specific capacity is 117mAh g-1.
Claims (10)
1. a kind of ferric phosphate lithium cell production link positive pole waste and scrap reclaims the method that repairs and recycle, it is characterised in that bag
Include following steps：
(1) the ferric phosphate lithium cell production link positive pole waste and scrap of recovery is placed in alkaline solution and is stirred, make activity
Material LiFePO 4 material is kept completely separate from aluminium foil；
(2) after separate the aluminium foil that isolates in step (1) alkali liquor, to remaining LiFePO4, conductive agent, binding agent in alkali liquor
Mixing material is carried out filtering, is washed；
(3) the LiFePO4 mixing material after step (2) washing is dried；
(4) powder after dried for step (3) LiFePO4 mixing material being carried out ball-milling treatment, ball milling is with vibrated
Sieve, control particle diameter is below 15 μm；
(5) the mixing material powder for obtaining step (4) soaks in organic solvent, stirs and 1～4h of supersound process, removes which
In binding agent；
(6) will step (5) resulting materials filter, dry after, be placed in reaction kiln in carry out roasting remove part carbon；
(7) material after step (6) roasting is calcined under inert gas shielding, obtains the lithium iron phosphate positive material that repairs；
(8) lithium iron phosphate positive material that obtains step (7), conductive agent, binding agent mix homogeneously, are coated on aluminium foil after homogenate
On, it is reassembled into ferric phosphate lithium cell.
2. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：The alkaline solution be sodium hydroxide, Lithium hydrate, potassium hydroxide solution one or more；Its
Concentration is 0.05～1mol/L.
3. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：The temperature of the roasting is 100～300 DEG C, and the time is 2～5h..
4. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：The temperature of the calcining is 400～800 DEG C, and the time is 2～6h.
5. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：Described organic solvent is acetone, N-Methyl pyrrolidone, one or two in dimethylformamide
More than.
6. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：In step (8), the mass ratio of lithium iron phosphate positive material, conductive agent and binding agent is 8：0.5～1：0.5
～1.
7. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：Described calcining is carried out in tube furnace, and the heating mode of tube furnace heats up for staged, its speed that heats up
Rate is 1～5 DEG C of min-1.
8. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：The rotating speed of ball mill is 300～600rpm.
9. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims the side that repairs and recycle
Method, it is characterised in that：The described screen cloth sieved using 200～600 mesh.
10. ferric phosphate lithium cell production link positive pole waste and scrap according to claim 1 reclaims and repairs and recycle
Method, it is characterised in that：Described protective atmosphere is the mixed gas of argon and hydrogen, the volume accounting of argon is 80～
99%, hydrogen is 1～20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710021526.1A CN106505273A (en) | 2017-01-11 | 2017-01-11 | The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710021526.1A CN106505273A (en) | 2017-01-11 | 2017-01-11 | The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled |
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| CN106505273A true CN106505273A (en) | 2017-03-15 |
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ID=58345285
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Cited By (11)
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| CN107093724A (en) * | 2017-04-27 | 2017-08-25 | 柳州豪祥特科技有限公司 | The preparation method of anode material of lithium battery |
| CN108110359A (en) * | 2017-12-16 | 2018-06-01 | 淄博国利新电源科技有限公司 | The circulation utilization method of positive electrode |
| CN108417923A (en) * | 2018-03-07 | 2018-08-17 | 合肥工业大学 | A kind of recycling method of retired lithium iron phosphate battery positive material |
| CN108760586A (en) * | 2018-05-23 | 2018-11-06 | 广州能源检测研究院 | A kind of method that overlay material particle size is distributed in detection lithium battery pole slice |
| CN111977627A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Method for recycling lithium iron phosphate anode material of lithium ion battery |
| CN112234272A (en) * | 2020-09-22 | 2021-01-15 | 华中科技大学 | Low-energy-consumption and low-Al-content recovery method for lithium iron phosphate positive plate |
| CN113707893A (en) * | 2021-08-16 | 2021-11-26 | 广西师范大学 | Carbon-based electrocatalyst prepared from waste lithium iron phosphate battery positive electrode material and preparation method and application thereof |
| WO2021253885A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Method for composite delamination |
| CN113991204A (en) * | 2021-10-22 | 2022-01-28 | 国网黑龙江省电力有限公司电力科学研究院 | Short-process recovery method of waste lithium iron phosphate anode material |
| CN114538405A (en) * | 2022-03-30 | 2022-05-27 | 中国科学院过程工程研究所 | Method for preparing lithium iron phosphate from waste lithium iron phosphate anode material |
| CN115818607A (en) * | 2021-10-11 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093724A (en) * | 2017-04-27 | 2017-08-25 | 柳州豪祥特科技有限公司 | The preparation method of anode material of lithium battery |
| CN108110359A (en) * | 2017-12-16 | 2018-06-01 | 淄博国利新电源科技有限公司 | The circulation utilization method of positive electrode |
| CN108417923A (en) * | 2018-03-07 | 2018-08-17 | 合肥工业大学 | A kind of recycling method of retired lithium iron phosphate battery positive material |
| CN108760586A (en) * | 2018-05-23 | 2018-11-06 | 广州能源检测研究院 | A kind of method that overlay material particle size is distributed in detection lithium battery pole slice |
| WO2021253883A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Method for composite delamination |
| WO2021253888A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Method for composite delamination |
| WO2021253887A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Method for composite delamination |
| WO2021253885A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Method for composite delamination |
| WO2021253884A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Method for composite delamination |
| CN111977627A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Method for recycling lithium iron phosphate anode material of lithium ion battery |
| CN112234272A (en) * | 2020-09-22 | 2021-01-15 | 华中科技大学 | Low-energy-consumption and low-Al-content recovery method for lithium iron phosphate positive plate |
| CN112234272B (en) * | 2020-09-22 | 2022-02-18 | 华中科技大学 | Low-energy-consumption and low-Al-content recovery method for lithium iron phosphate positive plate |
| CN113707893A (en) * | 2021-08-16 | 2021-11-26 | 广西师范大学 | Carbon-based electrocatalyst prepared from waste lithium iron phosphate battery positive electrode material and preparation method and application thereof |
| CN113707893B (en) * | 2021-08-16 | 2022-08-12 | 广西师范大学 | Carbon-based electrocatalyst prepared from waste lithium iron phosphate battery positive electrode material and preparation method and application thereof |
| CN115818607A (en) * | 2021-10-11 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
| CN115818607B (en) * | 2021-10-11 | 2023-10-31 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
| CN113991204A (en) * | 2021-10-22 | 2022-01-28 | 国网黑龙江省电力有限公司电力科学研究院 | Short-process recovery method of waste lithium iron phosphate anode material |
| CN114538405A (en) * | 2022-03-30 | 2022-05-27 | 中国科学院过程工程研究所 | Method for preparing lithium iron phosphate from waste lithium iron phosphate anode material |
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