CN106410313A - Method for repairing and regenerating nickel cobalt manganese ternary positive electrode material in waste battery - Google Patents

Method for repairing and regenerating nickel cobalt manganese ternary positive electrode material in waste battery Download PDF

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Publication number
CN106410313A
CN106410313A CN201611043795.XA CN201611043795A CN106410313A CN 106410313 A CN106410313 A CN 106410313A CN 201611043795 A CN201611043795 A CN 201611043795A CN 106410313 A CN106410313 A CN 106410313A
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ternary
tertiary cathode
positive electrode
guipure
electrode material
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许开华
张云河
叶建
郭苗苗
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for repairing and regenerating a nickel cobalt manganese ternary positive electrode material in a waste battery. The method comprises the following steps: splitting an positive electrode material from a lithium cobalt oxide waste battery; laying the ternary positive electrode material on a mesh belt, controlling the mesh belt to continuously vibrate, and controlling gas to pass through meshes of the mesh belt from bottom to top; under the conditions that the mesh belt vibrates and gas flows through the meshes of the mesh belt, respectively heating a ternary positive electrode slice at the temperature of 100 to 300 DEG C and the temperature of 380 to 520 DEG C for 10 to 60 minutes, and collecting ternary positive electrode material powder I; sequentially sieving the ternary positive electrode material powder I to remove a broken aluminum foil and performing electromagnetic iron removal on the ternary positive electrode material powder I to obtain ternary positive electrode material powder II, and performing ball milling on the ternary positive electrode material powder II to obtain ternary positive electrode material powder III; dissolving aluminum powder by the ternary positive electrode material powder III under the condition of weak acid, corroding the surface of the ternary positive electrode material to form the ternary positive electrode material with high activity and high dispersity, and synthesizing and repairing the ternary positive electrode material serving as a nucleating agent to obtain a spherical ternary precursor material with uniform particles. The size mixing and coating properties and electrochemical properties of the spherical ternary precursor material prepared by the method provided by the invention are repaired.

Description

The method of nickel-cobalt-manganternary ternary anode material reparative regeneration in old and useless battery
Technical field
The present invention relates to old and useless battery recycles and in particular to nickel-cobalt-manganternary ternary anode material is repaiied in a kind of old and useless battery Multiple regeneration method.
Background technology
Lithium ion battery since commercialization, because its have specific energy height, small volume, light weight, temperature limit wide, Unique advantage such as have extended cycle life, have a safety feature, and is widely used in civilian and military domain, such as video camera, mobile electricity Words, notebook computer and Portable Multifunctional Temperature Measurer etc., lithium ion battery is also the first-selected light high-energy power of electric automobile simultaneously One of battery.
After 500-1000 charge and discharge cycles, its active substance will lose activity lithium ion battery, leads to electricity The capacity in pond declines and so that battery is scrapped.Lithium ion battery recovery technology can be divided into hydrometallurgic recovery and pyrogenic process to reclaim.Wet method includes Pretreatment（Disassemble, classify）And recovery two parts of cobalt and other metals.The anode pole piece of classification, needs aluminium foil and aluminum On paper tinsel, positive electrode powder is separated, and because containing binding agent in positive electrode, needs first in 500 DEG C about heat treatments, makes to glue The volatilizations such as knot agent, on aluminium foil, positive electrode powder just can come off.If aluminium foil separates not exclusively with positive electrode powder, follow-up In leaching process, aluminum and acid reaction discharge a large amount of hydrogen, are also easy to produce blast, and increased the separating difficulty of aluminum and be separated into This.The separation degree of therefore aluminium foil becomes the key of positive electrode Powder Recovery utilization.
Pyrogenic process reclaims, and old and useless battery is discharged, crushes, broken material is smelted through 800 ~ 1500 DEG C in smelting furnace, Co, The heavy metals such as Ni, Mn, Cu form alloy and reclaim, and the slag making such as Li, Al enters slag, and the volatilization of the plastics such as barrier film is collected.Pyrogenic process reclaims Equipment investment is had high demands, environmental protection pressure is big, and metal needs will process further and could utilize, high cost.
In prior art, no matter hydrometallurgic recovery or pyrogenic process reclaims, be all the metals such as Co, the Li in old and useless battery are worked as former Material reclaims, and long flow path, cost recovery are high.
Old and useless battery is disassembled and is reclaimed the tertiary cathode material powder obtaining, and during using in continuous discharge and recharge, has one Partial particulate is broken into fine particle, and distribution of particles broadens, if not carrying out granule reparation, regeneration makes battery and sizes mixing painting Cloth poor performance, coating became uneven, affect battery performance.
Content of the invention
For solving above-mentioned technical problem, the present invention provides nickel-cobalt-manganternary ternary anode material reparative regeneration in a kind of old and useless battery Method, reach more than 99.5% by the separation rate of the method aluminum, size mixing coating performance and chemical property is repaired.
In old and useless battery, the method for nickel-cobalt-manganternary ternary anode material reparative regeneration, comprises the following steps：
Step 1, waste and old lithium ion battery is cleaned, discharges, and sub-elects nickel-cobalt-manganese ternary battery；
Step 2, nickel-cobalt-manganese ternary battery is disassembled in cleaning, sub-elects tertiary cathode pole piece, electrolyte, cathode pole piece, shell；
Step 3, tertiary cathode pole piece is laid on high temperature resistant guipure with the thickness of 1-5cm, controls guipure with 5 ~ 50Hz frequency Sustained vibration, controls gas with 1 ~ 500m simultaneously3/ h flow velocity passes through guipure mesh from the bottom to top；Keeping guipure vibration, guipure Under conditions of mesh has gas circulation, by tertiary cathode pole piece at 100 ~ 300 DEG C after predrying 10 ~ 60 minutes, continue 380 ~ 520 DEG C sinter 10 ~ 60 minutes, collect tertiary cathode material powder I；
Step 4, tertiary cathode material powder I is screened out fragmentation aluminium foil successively and electromagnetism removes ferrum, obtain tertiary cathode material powder II, then sampling detects the content of Li, Co, Ni, Mn, Al in tertiary cathode material powder II；
Step 5, by tertiary cathode material powder II put in high energy ball mill ratio of grinding media to material be 1:1 ~ 3, rotational speed of ball-mill 300 ~ Ball milling 1 ~ 24h under conditions of 800r/min, obtains tertiary cathode material powder III；
Step 6, prepares ternary precursor material；
Step 6.1, prepares ternary liquid using tertiary cathode material powder III：
Tertiary cathode powder is put into priming reaction 0.5 ~ 10h in the weakly acidic solution of pH value 3.5 ~ 5.0, be filtrated to get filtration molten Liquid and filtering residue, filtering residue hot pure water is washed to wash water pH value 6.5 ~ 7.5, and filtering solution adds nickel sulfate, manganese sulfate and cobaltous sulfate Crystal, is configured to Ni：Co：Mn=(1-x-y)：x：y;X=0.1 ~ 0.33, the ternary solution of the mol ratio of y=0.1 ~ 0.33；
Step 6.2, prepares alkaline tertiary cathode material primer solution：
By filtering residue in step 6.1, put in ternary precursor synthesis reaction vessel, filtering residue input amount with reactor volume relationship is 100~300kg/M3；Add pure water, liquid caustic soda and ammonia again and be configured to pH value 10.0 ~ 11.5, ammonia density 3 ~ 10g/l toward in reactor Alkaline solution；
Step 6.3, prepares ternary precursor material：
Sealing aforesaid reaction vessel, is passed through nitrogen or argon inert gas air emptying in kettle, speed of agitator is transferred to 100 ~ 160r/ min；
The ammonia spirit three of the ternary solution prepared in step 6.1, the sodium hydroxide solution of 20 ~ 32wt%, 10 ~ 20wt% is pressed Ternary solution 100 ~ 200l/h, liquid caustic soda 30 ~ 45l/h, ammonia 2 ~ 10l/h add reaction in aforesaid reaction vessel, by reactor interior temperature Degree controls and is passed through the flow of reactor at 45 ~ 65 DEG C, by regulation sodium hydroxide solution and ammonia is passed through the flow of reactor and makes PH value controls ammonia density 3 ~ 10g/l in 10.0 ~ 11.5, reaction mother liquor, successive reaction 10 ~ 50h, obtains ternary precursor, treats Stopped reaction when ternary precursor particle diameter D50 reaches 5 ~ 11 μm, filters, washs, is dried, obtain ternary precursor material；
Step 7, ternary precursor material prepared by step 6 is by Li：M：Al=(1 ~ 1.05)：(1 x)：X, x=0.001 ~ 0.2 Supplement Li and Al element, M is the total amount of metal of Ni, Co, Mn, and 600 ~ 1000 DEG C of roasting 10 ~ 24h, are repaired under pure oxygen atmosphere Regeneration tertiary cathode material.
In above-mentioned steps 3, tertiary cathode pole piece is laid on high temperature resistant guipure with the thickness of 3cm.
In above-mentioned steps 3, guipure vibrator controls guipure with 50Hz frequency sustained vibration, and the vibrating motor of vibrator adopts Frequency conversion motor；Gas is controlled with 20m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh, air intake installation from the bottom to top For aerator or air compressor.
In above-mentioned steps 3, guipure vibrator controls guipure with 25Hz frequency sustained vibration, and the vibrating motor of vibrator adopts Frequency conversion motor；Gas is controlled with 10m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh, air intake installation from the bottom to top For aerator or air compressor.
In above-mentioned steps 3, tertiary cathode pole piece, continues to sinter 30 minutes at 450 DEG C after predrying 30 minutes at 200 DEG C.
In above-mentioned steps 6.1, weakly acidic solution is dilute hydrochloric acid or dilute sulfuric acid；
In above-mentioned steps 7, ternary precursor material prepared by step 6 is by Li：M：Al=1.05：0.8：0.2 mol ratio is mended Fill Li element and Al element, M is the total amount of metal of Ni, Co, Mn.
In above-mentioned steps 7, ternary precursor material prepared by step 6 is by Li：M：Al=1：0.99：0.01 mole Than supplementary Li element and Al element, M is the total amount of metal of Ni, Co, Mn.
In above-mentioned steps 7, ternary precursor material prepared by step 6 is by Li：M：Al=1.02：0.999：0.001 Mol ratio supplements Li element and Al element, and M is the total amount of metal of Ni, Co, Mn.
In above-mentioned steps, by adding lithium carbonate to supplement Li element, by adding aluminium oxide supplement Al element.
Compared with prior art, the invention has the advantages that：
Waste and old lithium ion battery is disassembled in cleaning, does not introduce impurity.
Positive plate fast eliminating binding agent in the air-flow sintering process of step 3, positive plate supersonic vibration effect under, just Pole material powder is separated with aluminium foil, it is to avoid positive plate oversintering phenomenon, prevents aluminium foil fragmentation, effectively increases aluminum and positive pole material The separation degree at feed powder end, the separation rate of aluminum reaches more than 99.5%（Measurement result shows, the tertiary cathode material reclaiming in step 4 Al in feed powder end II（wt.%）Content is respectively less than 0.5%）, the separation rate of aluminum is according to 1-Al（wt.%）It is calculated.
The positive electrode isolated through high-energy ball milling refine activation, the ternary material after ball milling weak acid effect under, granule Surface acid corrosion, forms many micropores, increased the specific surface area of granule, and when synthesizing under the conditions of subsequently alkalescence, nickel cobalt manganese can In its porous surface continued growth, without forming new nucleus, form the ternary precursor material of hydroxide nickel cobalt manganese parcel, It sizes mixing coating performance and chemical property is repaired.
Brief description
Fig. 1 is the cycle performance figure of the material obtaining in example 1,2,3,4.
Specific embodiment
Embodiment 1
Step 1, puts into electric discharge in sodium chloride solution by clean for the surface clean of waste and old lithium ion battery, by battery, by positive pole material Gauge lattice cobalt acid lithium, nickel-cobalt-manganese ternary material, LiMn2O4, LiFePO4 etc. are classified, and sub-elect nickel-cobalt-manganese ternary battery；
Step 2, the good nickel-cobalt-manganese ternary battery of above-mentioned classification is disassembled in cleaning, sub-elects tertiary cathode pole piece, electrolyte, negative pole pole Piece, shell, concrete operations are first battery to be cut open, take out battery core, then battery core both positive and negative polarity, barrier film classification；
Step 3, takes the tertiary cathode pole piece 100Kg of above-mentioned sorting to be laid on high temperature resistant guipure with the thickness of 5cm, by guipure Vibrator controls guipure with 50Hz frequency sustained vibration, and the vibrating motor of vibrator adopts frequency conversion motor, power of motor 5.5Kw, Motor operation frequency 50Hz；Gas is controlled with 20m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh from the bottom to top, Air intake installation is aerator or air compressor, and mesh aperture is 10mm；
Under conditions of keeping guipure vibration, guipure mesh to have gas circulation, guipure enters temperature control under the drive of rotary shaft Make the first temperature control area at 100 DEG C, tertiary cathode pole piece is predrying 60 minutes at 100 DEG C；Subsequently, guipure is in the drive of rotary shaft In 380 DEG C of the second temperature control area, tertiary cathode pole piece continues to sinter 60 minutes at 380 DEG C the lower temperature control that enters；
In predrying and sintering process, tertiary cathode material powder I comes off from guipure mesh, collects these tertiary cathode materials Powder I；
Step 4, the tertiary cathode material powder I of above-mentioned collection is screened out the aluminium foil of fragmentation by ultrasonic screening machine, weighs sieve The gross weight of the aluminium foil separating；Then carry out electromagnetism and remove ferrum, obtain tertiary cathode material powder II, weigh tertiary cathode material powder The gross weight at end II；Resampling detects the content of Li, Co, Ni, Mn, Al in tertiary cathode material powder II, and aluminum separation rate reaches 98.8%；
Step 5, by tertiary cathode material powder II put in high energy ball mill ratio of grinding media to material be 1:3rd, rotational speed of ball-mill 300r/min Under conditions of ball milling 24h, obtain tertiary cathode material powder III；
Step 6, prepares ternary precursor material；
Step 6.1, prepares ternary liquid using tertiary cathode material powder III：
Tertiary cathode powder is put into priming reaction 10h in the dilute hydrochloric acid solution of pH value 5.0, be filtrated to get filtering solution and filter Slag, filtering residue hot pure water is washed to wash water pH value 7.5, and filtering solution adds nickel sulfate, manganese sulfate and cobaltous sulfate crystal, is configured to Ni：Co：Mn=1:1:The ternary solution of 1 mol ratio；
Step 6.2, prepares alkaline tertiary cathode material primer solution：
By filtering residue in step 6.1, put in ternary precursor synthesis reaction vessel, filtering residue input amount with reactor volume relationship is 100kg/M3；Add pure water, liquid caustic soda and ammonia again and be configured to pH value 11.5, the alkaline solution of ammonia density 3g/l toward in reactor；
Step 6.3, prepares ternary precursor material：
Sealing aforesaid reaction vessel, is passed through nitrogen or argon inert gas air emptying in kettle, speed of agitator is transferred to 160r/min；
Will be molten by ternary for the ammonia spirit three of the ternary solution prepared in step 6.1, the sodium hydroxide solution of 32wt%, 20wt% Liquid 200l/h, liquid caustic soda 45l/h, ammonia 2l/h add aforesaid reaction vessel in reaction, by reactor temperature control 65 DEG C, pass through Adjust that sodium hydroxide solution is passed through the flow of reactor and ammonia is passed through the flow of reactor so that pH value is controlled female in 11.5, reaction Ammonia density 3g/l in liquid, successive reaction 50h, obtain ternary precursor, stop anti-when ternary precursor particle diameter D50 reaches 5 μm Should, filter, wash, be dried, obtain ternary precursor material；
Step 7, ternary precursor material prepared by step 6 is by Li：M：Al=(1 ~ 1.05)：(1 x)：X, x=0.001 supplement Li and Al element, M is the total amount of metal of Ni, Co, Mn, and 1000 DEG C of roasting 24h under pure oxygen atmosphere obtain reparative regeneration tertiary cathode Material.
Embodiment 2
Step 1, puts into electric discharge in sodium chloride solution by clean for the surface clean of waste and old lithium ion battery, by battery, by positive pole material Gauge lattice cobalt acid lithium, nickel-cobalt-manganese ternary material, LiMn2O4, LiFePO4 etc. are classified, and sub-elect nickel-cobalt-manganese ternary battery；
Step 2, the good nickel-cobalt-manganese ternary battery of above-mentioned classification is disassembled in cleaning, sub-elects tertiary cathode pole piece, electrolyte, negative pole pole Piece, shell, concrete operations are first battery to be cut open, take out battery core, then battery core both positive and negative polarity, barrier film classification；
Step 3, takes the tertiary cathode pole piece 100Kg of above-mentioned sorting to be laid on high temperature resistant guipure with the thickness of 1cm, by guipure Vibrator controls guipure with 5Hz frequency sustained vibration, and the vibrating motor of vibrator adopts frequency conversion motor, power of motor 0.75Kw, Motor operation frequency 5Hz；Gas is controlled with 1m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh from the bottom to top, enters Device of air is aerator or air compressor, and mesh aperture is 5mm；
Under conditions of keeping guipure vibration, guipure mesh to have gas circulation, guipure enters temperature control under the drive of rotary shaft Make the first temperature control area at 300 DEG C, tertiary cathode pole piece is predrying 10 minutes at 300 DEG C；Subsequently, guipure is in the drive of rotary shaft In 520 DEG C of the second temperature control area, tertiary cathode pole piece continues to sinter 10 minutes at 520 DEG C the lower temperature control that enters；
In predrying and sintering process, tertiary cathode material powder I comes off from guipure mesh, collects these tertiary cathode materials Powder I；
Step 4, the tertiary cathode material powder I of above-mentioned collection is screened out the aluminium foil of fragmentation by ultrasonic screening machine, weighs sieve The gross weight of the aluminium foil separating；Then carry out electromagnetism and remove ferrum, obtain tertiary cathode material powder II, weigh tertiary cathode material powder The gross weight at end II；Resampling detects the content of Li, Co, Ni, Mn, Al in tertiary cathode material powder II, and aluminum separation rate reaches 97.5%；
Step 5, by tertiary cathode material powder II, putting into high energy ball mill interior is 1 in ratio of grinding media to material:1st, rotational speed of ball-mill 800r/min Under conditions of ball milling 1h, obtain tertiary cathode material powder III；
Step 6, prepares ternary precursor material；
Step 6.1, prepares ternary liquid using tertiary cathode material powder III：
Tertiary cathode powder is put into priming reaction 0.5h in the hydrochloric acid solution of pH value 3.5, be filtrated to get filtering solution and filter Slag, filtering residue hot pure water is washed to wash water pH value 6.5, and filtering solution adds nickel sulfate, manganese sulfate and cobaltous sulfate crystal, is configured to Ni：Co：Mn=5:2:The ternary solution of 3 mol ratio；
Step 6.2, prepares alkaline tertiary cathode material primer solution：
By filtering residue in step 6.1, put in ternary precursor synthesis reaction vessel, filtering residue input amount with reactor volume relationship is 300kg/M3；Add pure water, liquid caustic soda and ammonia again and be configured to pH value 10.0, the alkaline solution of ammonia density 10g/l toward in reactor；
Step 6.3, prepares ternary precursor material：
Sealing aforesaid reaction vessel, is passed through nitrogen or argon inert gas air emptying in kettle, speed of agitator is transferred to 100r/min；
Will be molten by ternary for the ammonia spirit three of the ternary solution prepared in step 6.1, the sodium hydroxide solution of 20wt%, 10wt% Liquid 100l/h, liquid caustic soda 30l/h, ammonia 10l/h add reaction in aforesaid reaction vessel, by reactor temperature control 45 DEG C, logical Overregulate that sodium hydroxide solution is passed through the flow of reactor and ammonia is passed through the flow of reactor and so that pH value is controlled in 10.0, reaction Ammonia density 10g/l in mother solution, successive reaction 10h, obtain ternary precursor, treat that ternary precursor particle diameter D50 reaches 11 μm of stoppings Reaction, filters, washs, is dried, obtain ternary precursor material；
The ternary precursor material of step 7, just step 6 preparation is pressed by Li：M：Al=(1 ~ 1.05)：(1 x)：X, x=0.2 benefit Fill Li and Al element, M is the total amount of metal of Ni, Co, Mn, 600 ~ 1000 DEG C of roasting 10 ~ 24h under pure oxygen atmosphere obtain repairing again Raw tertiary cathode material.
Embodiment 3
Step 1, puts into electric discharge in sodium chloride solution by clean for the surface clean of waste and old lithium ion battery, by battery, by positive pole material Gauge lattice cobalt acid lithium, nickel-cobalt-manganese ternary material, LiMn2O4, LiFePO4 etc. are classified, and sub-elect nickel-cobalt-manganese ternary battery；
Step 2, the good nickel-cobalt-manganese ternary battery of above-mentioned classification is disassembled in cleaning, sub-elects tertiary cathode pole piece, electrolyte, negative pole pole Piece, shell, concrete operations are first battery to be cut open, take out battery core, then battery core both positive and negative polarity, barrier film classification；
Step 3, takes the tertiary cathode pole piece 100Kg of above-mentioned sorting to be laid on high temperature resistant guipure with the thickness of 3cm, by guipure Vibrator controls guipure with 25Hz frequency sustained vibration, and the vibrating motor of vibrator adopts frequency conversion motor, power of motor 2.5Kw, Motor operation frequency 25Hz；Gas is controlled with 10m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh from the bottom to top, Air intake installation is aerator or air compressor, and mesh aperture is 8mm；
Under conditions of keeping guipure vibration, guipure mesh to have gas circulation, guipure enters temperature control under the drive of rotary shaft Make the first temperature control area at 200 DEG C, tertiary cathode pole piece is predrying 30 minutes at 200 DEG C；Subsequently, guipure is in the drive of rotary shaft In 450 DEG C of the second temperature control area, tertiary cathode pole piece continues to sinter 30 minutes at 450 DEG C the lower temperature control that enters；
In predrying and sintering process, tertiary cathode material powder I comes off from guipure mesh, collects these tertiary cathode materials Powder I；
Step 4, the tertiary cathode material powder I of above-mentioned collection is screened out the aluminium foil of fragmentation by ultrasonic screening machine, weighs sieve The gross weight of the aluminium foil separating；Then carry out electromagnetism and remove ferrum, obtain tertiary cathode material powder II, weigh tertiary cathode material powder The gross weight at end II；Resampling detects the content of Li, Co, Ni, Mn, Al in tertiary cathode material powder II, and aluminum separation rate reaches 98.1%；
Step 5, by tertiary cathode material powder III, putting into high energy ball mill interior is 1 in ratio of grinding media to material:2 rotational speed of ball-mill 500r/min Under conditions of Ball-milling Time 10h, obtain tertiary cathode material powder IV；
Step 6, prepares ternary precursor material；
Step 6.1, prepares ternary liquid using tertiary cathode material powder III：
Tertiary cathode powder is put into priming reaction 5h in the dilution heat of sulfuric acid of pH value 4.5, is filtrated to get filtering solution and filtering residue, Filtering residue hot pure water is washed to wash water pH value 6.5 ~ 7.5, and filtering solution adds nickel sulfate, manganese sulfate and cobaltous sulfate crystal, prepares Become Ni：Co：Mn=3:1:The ternary solution of 1 mol ratio；
Step 6.2, prepares alkaline tertiary cathode material primer solution：
By filtering residue in step 6.1, put in ternary precursor synthesis reaction vessel, filtering residue input amount with reactor volume relationship is 200kg/M3；Add pure water, liquid caustic soda and ammonia again and be configured to pH value 10.8, the alkaline solution of ammonia density 6g/l toward in reactor；
Step 6.3, prepares ternary precursor material：
Sealing aforesaid reaction vessel, is passed through nitrogen or argon inert gas air emptying in kettle, speed of agitator is transferred to 130r/min；
Will be molten by ternary for the ammonia spirit three of the ternary solution prepared in step 6.1, the sodium hydroxide solution of 28wt%, 15wt% Liquid 150l/h, liquid caustic soda 40l/h, ammonia 6l/h add aforesaid reaction vessel in reaction, by reactor temperature control 55 DEG C, pass through Adjust that sodium hydroxide solution is passed through the flow of reactor and ammonia is passed through the flow of reactor so that pH value is controlled female in 10.8, reaction Ammonia density 6g/l in liquid, successive reaction 30h, obtain ternary precursor, stop anti-when ternary precursor particle diameter D50 reaches 10 μm Should, filter, wash, be dried, obtain ternary precursor material；
The ternary precursor material of step 7, just step 6 preparation is pressed by Li：M：Al=(1 ~ 1.05)：(1 x)：X, x=0.05 Supplement Li and Al element, M is the total amount of metal of Ni, Co, Mn, 600 DEG C of roasting 24h under pure oxygen atmosphere obtain reparative regeneration ternary Positive electrode.
Embodiment 4（Comparative example）
Step 1, puts into electric discharge in sodium chloride solution by clean for the surface clean of waste and old lithium ion battery, by battery, by positive pole material Gauge lattice cobalt acid lithium, nickel-cobalt-manganese ternary material, LiMn2O4, LiFePO4 etc. are classified, and sub-elect nickel-cobalt-manganese ternary battery；
Step 2, the good nickel-cobalt-manganese ternary battery of above-mentioned classification is disassembled in cleaning, sub-elects tertiary cathode pole piece, electrolyte, negative pole pole Piece, shell, concrete operations are first battery to be cut open, take out battery core, then battery core both positive and negative polarity, barrier film classification；
Step 3, takes the tertiary cathode pole piece 100Kg of above-mentioned sorting to be laid on high temperature resistant guipure with the thickness of 5cm, by guipure Vibrator controls guipure with 50Hz frequency sustained vibration, and the vibrating motor of vibrator adopts frequency conversion motor, power of motor 5.5Kw, Motor operation frequency 50Hz；Gas is controlled with 20m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh from the bottom to top, Air intake installation is aerator or air compressor, and mesh aperture is 10mm；
Under conditions of keeping guipure vibration, guipure mesh to have gas circulation, guipure enters temperature control under the drive of rotary shaft Make the first temperature control area at 100 DEG C, tertiary cathode pole piece is predrying 60 minutes at 100 DEG C；Subsequently, guipure is in the drive of rotary shaft In 380 DEG C of the second temperature control area, tertiary cathode pole piece continues to sinter 60 minutes at 380 DEG C the lower temperature control that enters；
In predrying and sintering process, tertiary cathode material powder I comes off from guipure mesh, collects these tertiary cathode materials Powder I；
Step 4, the tertiary cathode material powder I of above-mentioned collection is screened out the aluminium foil of fragmentation by ultrasonic screening machine, weighs sieve The gross weight of the aluminium foil separating；Then carry out electromagnetism and remove ferrum, obtain tertiary cathode material powder II, weigh tertiary cathode material powder The gross weight at end II；Resampling detects the content of Li, Co, Ni, Mn, Al in tertiary cathode material powder II, and aluminum separation rate reaches 96.5%；
Step 5, by tertiary cathode material powder II put in high energy ball mill ratio of grinding media to material be 1:3rd, rotational speed of ball-mill 300r/min Under conditions of ball milling 24h, obtain tertiary cathode material powder III；
Step 6, the tertiary cathode material powder III that step 5 is obtained is by Li：M：Al=(1 ~ 1.05)：(1 x)：X, x=0.001 Supplement Li and Al element, M is the total amount of metal of Ni, Co, Mn, 1000 DEG C of roasting 24h under pure oxygen atmosphere obtain reparative regeneration ternary Positive electrode.
Old and useless battery is disassembled and is reclaimed the tertiary cathode material powder II obtaining, and during using in continuous discharge and recharge, has one Point breakage of particles becomes fine particle, and distribution of particles broadens, if not carrying out granule reparation, regeneration makes battery and sizes mixing coating Poor performance, coating became uneven, affect battery performance.
Tertiary cathode material powder II ball milling that embodiment 1,2,3 passes through recovery is obtained becomes evengranular ultra-fine ternary Positive electrode powder III；Aluminium powder is dissolved under faintly acid, invades tertiary cathode material surface by tertiary cathode material powder III Erosion, forms the tertiary cathode material of high activity polymolecularity, and it is uniform that tertiary cathode material repairs into granule as nucleator synthesis Spherical ternary precursor material, size mixing coating performance and chemical property repaired.
Table 1 adopts the material particle size distribution of Malvern laser particle analyzer measurement
D(0.1)（um） D(0.5) (um) D(0.9) (um)
Example 1 final material 2.936 5.012 7.362
Example 2 final material 5.948 10.185 13.925
Example 3 final material 7.041 11.092 15.036
Example 4 final material 0.368 0.678 1.021
Under conditions of the solvent and binding agent of isodose, granule is less, is coated with the slurry adjusted more sticky, in pole piece phase homogeneity Under conditions of amount, pole piece is thicker, and the electronics of pole piece, ionic conduction are more difficult to, and leads to the chemical property of material poorer.
The positive electrode isolated through high-energy ball milling refine activation, the ternary material after ball milling weak acid effect under, granule Surface, by acid corrosion, forms many micropores, increased the specific surface area of granule, when synthesizing under the conditions of subsequently alkalescence, nickel cobalt manganese Without forming new nucleus, the ternary precursor material of hydroxide nickel cobalt manganese parcel can be formed in its porous surface continued growth Material.
The cycle performance of the reparative regeneration tertiary cathode material of preparation in above-described embodiment is tested.Using making battery Routine techniquess and method positive electrode is assembled into battery：Positive electrode is mixed with binding agent, film, cuts into slices, is assembled into electricity Pond, positive pole constructs：Cobalt acid lithium+conductive agent（Acetylene black）+ binding agent（PVDF）+ collector（Aluminium foil）；Battery is in 2.75-4.35V In voltage range, 0.1C tests.
In Fig. 1, curve 1,2,3,4 is the cycle performance figure of the reparative regeneration ternary of embodiment 1,2,3,4 preparation,
4 cycle performance curves of contrast, it is known that the battery of the reparative regeneration tertiary cathode material assembling of embodiment 1-4 preparation, follow When ring number of times is 20, specific capacity respectively reaches 144mAh/g, 147 mAh/g, 155mAh/g, 138mAh/g（Referring to curve in Fig. 1 1、2、3、4）.

Claims (10)

1. in old and useless battery the method for nickel-cobalt-manganternary ternary anode material reparative regeneration it is characterised in that comprising the following steps：
Step 1, waste and old lithium ion battery is cleaned, discharges, and sub-elects nickel-cobalt-manganese ternary battery；
Step 2, nickel-cobalt-manganese ternary battery is disassembled in cleaning, sub-elects tertiary cathode pole piece, electrolyte, cathode pole piece, shell；
Step 3, tertiary cathode pole piece is laid on high temperature resistant guipure with the thickness of 1-5cm, controls guipure with 5 ~ 50Hz frequency Sustained vibration, controls gas with 1 ~ 500m simultaneously3/ h flow velocity passes through guipure mesh from the bottom to top；Keeping guipure vibration, guipure Under conditions of mesh has gas circulation, by tertiary cathode pole piece at 100 ~ 300 DEG C after predrying 10 ~ 60 minutes, continue 380 ~ 520 DEG C sinter 10 ~ 60 minutes, collect tertiary cathode material powder I；
Step 4, tertiary cathode material powder I is screened out fragmentation aluminium foil successively and electromagnetism removes ferrum, obtain tertiary cathode material powder II, then sampling detects the content of Li, Co, Ni, Mn, Al in tertiary cathode material powder II；
Step 5, by tertiary cathode material powder II put in high energy ball mill ratio of grinding media to material be 1:1 ~ 3, rotational speed of ball-mill 300 ~ Ball milling 1 ~ 24h under conditions of 800r/min, obtains tertiary cathode material powder III；
Step 6, prepares ternary precursor material；
Step 6.1, prepares ternary liquid using tertiary cathode material powder III：
Tertiary cathode powder is put into priming reaction 0.5 ~ 10h in the weakly acidic solution of pH value 3.5 ~ 5.0, be filtrated to get filtration molten Liquid and filtering residue, filtering residue hot pure water is washed to wash water pH value 6.5 ~ 7.5, and filtering solution adds nickel sulfate, manganese sulfate and cobaltous sulfate Crystal, is configured to Ni：Co：Mn=(1-x-y)：x：y;X=0.1 ~ 0.33, the ternary solution of the mol ratio of y=0.1 ~ 0.33；
Step 6.2, prepares alkaline tertiary cathode material primer solution：
By filtering residue in step 6.1, put in ternary precursor synthesis reaction vessel, filtering residue input amount with reactor volume relationship is 100~300kg/M3；Add pure water, liquid caustic soda and ammonia again and be configured to pH value 10.0 ~ 11.5, ammonia density 3 ~ 10g/l toward in reactor Alkaline solution；
Step 6.3, prepares ternary precursor material：
Sealing aforesaid reaction vessel, is passed through nitrogen or argon inert gas air emptying in kettle, speed of agitator is transferred to 100 ~ 160r/ min；
The ammonia spirit three of the ternary solution prepared in step 6.1, the sodium hydroxide solution of 20 ~ 32wt%, 10 ~ 20wt% is pressed Ternary solution 100 ~ 200l/h, liquid caustic soda 30 ~ 45l/h, ammonia 2 ~ 10l/h add reaction in aforesaid reaction vessel, by reactor interior temperature Degree controls and is passed through the flow of reactor at 45 ~ 65 DEG C, by regulation sodium hydroxide solution and ammonia is passed through the flow of reactor and makes PH value controls ammonia density 3 ~ 10g/l in 10.0 ~ 11.5, reaction mother liquor, successive reaction 10 ~ 50h, obtains ternary precursor, treats Stopped reaction when ternary precursor particle diameter D50 reaches 5 ~ 11 μm, filters, washs, is dried, obtain ternary precursor material；
Step 7, ternary precursor material prepared by step 6 is by Li：M：Al=(1 ~ 1.05)：(1 x)：X, x=0.001 ~ 0.2 Supplement Li and Al element, M is the total amount of metal of Ni, Co, Mn, and 600 ~ 1000 DEG C of roasting 10 ~ 24h, are repaired under pure oxygen atmosphere Regeneration tertiary cathode material.
2. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 3, tertiary cathode pole piece is laid on high temperature resistant guipure with the thickness of 3cm.
3. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 3, guipure vibrator controls guipure with 50Hz frequency sustained vibration, and the vibrating motor of vibrator adopts variable-frequency electric Machine；Gas is controlled with 20m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh from the bottom to top, and air intake installation is air blast Machine or air compressor.
4. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 3, guipure vibrator controls guipure with 25Hz frequency sustained vibration, and the vibrating motor of vibrator adopts variable-frequency electric Machine；Gas is controlled with 10m by air intake installation simultaneously3The flow velocity of/h passes through guipure mesh from the bottom to top, and air intake installation is air blast Machine or air compressor.
5. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 3, tertiary cathode pole piece, continues to sinter 30 minutes at 450 DEG C after predrying 30 minutes at 200 DEG C.
6. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 6.1, weakly acidic solution is dilute hydrochloric acid or dilute sulfuric acid.
7. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 7, ternary precursor material prepared by step 6 is by Li：M：Al=1.05：0.8：0.2 mol ratio supplements Li Element and Al element, M is the total amount of metal of Ni, Co, Mn.
8. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 7, ternary precursor material prepared by step 6 is by Li：M：Al=1：0.99：0.01 mol ratio supplements Li Element and Al element, M is the total amount of metal of Ni, Co, Mn.
9. in old and useless battery according to claim 1 nickel-cobalt-manganternary ternary anode material reparative regeneration method, its feature exists In：
In step 7, ternary precursor material prepared by step 6 is by Li：M：Al=1.02：0.999：0.001 mol ratio is mended Fill supplementary Li element and Al element, M is the total amount of metal of Ni, Co, Mn.
10. in the old and useless battery according to any one of claim 6 to 8 nickel-cobalt-manganternary ternary anode material reparative regeneration side Method it is characterised in that：
By adding lithium carbonate to supplement Li element, by adding aluminium oxide supplement Al element.
CN201611043795.XA 2016-11-24 2016-11-24 Method for repairing and regenerating nickel cobalt manganese ternary positive electrode material in waste battery Pending CN106410313A (en)

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CN107419096A (en) * 2017-06-27 2017-12-01 常州市沃兰特电子有限公司 A kind of preparation method of waste lithium cell reclaiming tertiary cathode material
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CN107394199A (en) * 2017-07-20 2017-11-24 北京理工大学 The restoration methods of chemical property after a kind of nickelic tertiary cathode material storage
CN107706477A (en) * 2017-08-31 2018-02-16 长沙佳纳锂业科技有限公司 A kind of waste and old ternary anode material for lithium-ion batteries solid phase regeneration method
CN110098441A (en) * 2018-01-30 2019-08-06 荆门市格林美新材料有限公司 The reparative regeneration method of lithium cobaltate cathode material in old and useless battery
CN110277552A (en) * 2018-03-16 2019-09-24 荆门市格林美新材料有限公司 The reparative regeneration method of nickel-cobalt-manganternary ternary anode material in old and useless battery
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CN112993242A (en) * 2021-05-11 2021-06-18 蜂巢能源科技有限公司 Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material
CN112993242B (en) * 2021-05-11 2021-10-12 蜂巢能源科技有限公司 Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material
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