CN207602724U - A kind of system for continuously recycling waste and old ternary lithium ion battery - Google Patents
A kind of system for continuously recycling waste and old ternary lithium ion battery Download PDFInfo
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- CN207602724U CN207602724U CN201721696127.7U CN201721696127U CN207602724U CN 207602724 U CN207602724 U CN 207602724U CN 201721696127 U CN201721696127 U CN 201721696127U CN 207602724 U CN207602724 U CN 207602724U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The utility model provides a kind of system for continuously recycling waste and old ternary lithium ion battery, belongs to lithium ion battery recovery technology field.The system comprises pretreatment unit, acidleach unit, an impurity removing unit is co-precipitated unit, secondary impurity removing unit and ammonia recovery unit.Pre-treatment includes pulverizer, pulse dust collector, positive and negative anodes powder feed bin and seperator；Acidleach includes Leach reaction kettle and Microfilter I；Primary removal of impurities includes clean reaction kettle and squeezer, and co-precipitation includes batching kettle, coprecipitation reaction kettle and centrifuge；Secondary removal of impurities includes secondary removal of impurities reaction kettle and Microfilter II；Recovery ammonia includes heater, crystallizing evaporator, condenser and ammoniacal liquor receiving tank.Waste and old ternary lithium ion battery is recycled by Tthe utility model system, the nickel-cobalt-manganese ternary material precursor purity prepared is high, and tap density is big, and grain diameter is small, narrowly distributing and is uniformly mixed；Lithium sulfate solution is used directly for the production of lithium carbonate.
Description
Technical field
The utility model belongs to lithium ion battery recovery technology field, specially a kind of continuously to recycle waste and old ternary lithium ion
The system of battery.
Background technology
In recent years, lithium ion battery is since it is bigger than energy, output voltage is high, can high current charge-discharge, memoryless effect
It answers, have extended cycle life, many advantages, such as self-discharge rate is low, environmentally protective, being widely used in the electron numbers such as mobile phone, tablet computer
In code product, and it is increasingly becoming the electrical source of power of the fields such as energy storage device, electric vehicle first choice.
China has become one of largest production, consumption and exported country of lithium ion battery at present, is ground according to Chinese automobile technology
Study carefully Center Prediction, adding up learies to the year two thousand twenty Electric Cars in China power battery is up to 12 ten thousand to 17 ten thousand tons.Discarded lithium
Containing the valuable metals such as cobalt, lithium, nickel, manganese in ion battery, according to the statistical data of U.S address exploration administration, the cobalt in China, lithium,
Nickel, manganese mineral resources only account for 1.07%, 26.99%, 4.01%, the 7.02% of global reserves, produce needed for lithium ion battery
Metal imbalance between supply and demand it is more and more prominent in China.Meanwhile root is it was predicted that power lithium battery used in commercial car and passenger car
Pond learies will respectively reach 27Gwh and 4.2Gwh in the year two thousand twenty, about 500,000 tons, recycled from waste and old dynamic lithium battery nickel, cobalt,
The market value that the metals such as manganese, lithium, iron, aluminium and copper are created is in the year two thousand twenty up to 13,600,000,000 yuan.If not by this part " urban ore
Production " is recycled, and many environmental problems can be caused simultaneously by not only resulting in the significant wastage of resource.Therefore, high efficiente callback
Valuable metal in waste and old lithium ion battery can provide the metal of replacement for production lithium ion battery, reduce and external metal is provided
The dependence in source promotes sustainable development and the industrial upgrading of lithium ion battery industry.
Utility model content
The purpose of this utility model is to provide a kind of system for continuously recycling waste and old ternary lithium ion battery, by this reality
The nickel cobalt manganese valuable metal in waste and old ternary lithium ion battery can be continuously recycled with novel system, prepares purity height, jolt ramming
Density is big, and grain diameter is small, narrowly distributing and uniformly mixed ternary precursor product；It can continuously recycle waste and old ternary battery simultaneously
In valuable metal lithium prepare high-concentration sulfuric acid lithium solution.The utility model aim is realized by following technical proposals：
The purpose of this utility model is to provide a kind of system for continuously recycling waste and old ternary lithium ion battery, the systems
Including pretreatment unit, acidleach unit, an impurity removing unit is co-precipitated unit, secondary impurity removing unit and ammonia recovery unit：
The pretreatment unit includes pulverizer, pulse dust collector, positive and negative anodes powder feed bin and seperator, the pulse
Deduster and seperator are connected with the pulverizer, and the positive and negative anodes powder feed bin is connected with pulse dust collector and seperator；
The acidleach unit includes Leach reaction kettle and Microfilter I, the Leach reaction kettle and positive and negative anodes powder feed bin
Connection；
Impurity removing unit includes removal of impurities reaction kettle and squeezer, and the removal of impurities reaction kettle is connected with Microfilter I；
The co-precipitation unit includes batching kettle, coprecipitation reaction kettle and centrifuge, and the batching kettle connects with squeezer
It is logical；
The secondary impurity removing unit includes secondary removal of impurities reaction kettle and Microfilter II, the secondary removal of impurities reaction kettle with from
Scheming connects；
The ammonia recovery unit includes the heater being sequentially communicated, crystallizing evaporator, condenser and ammoniacal liquor receiving tank, institute
Heater is stated to connect with Microfilter II.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
Example, the pretreatment unit are additionally provided with loading head I, loading head II and loading head III, loading head I be located at pulse dust collector and
Between positive and negative anodes powder feed bin, loading head II is located between seperator and positive and negative anodes powder feed bin, and loading head III connects with seperator
It is logical.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
Example, the pretreatment unit are additionally provided with the lye spray column connected with pulverizer and the activated carbon connected with lye spray column
Filter.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
Example, the co-precipitation unit are additionally provided with the drying box connected with centrifuge.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
Example, the temperature of the drying box are 80~110 DEG C, drying time for 20~for 24 hours.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
Example, the ammonia recovery unit are additionally provided with the evaporation mother liquor holding tank connected with heater.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
The heating temperature of the example heater is 60~90 DEG C.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
The pH of solution is 4~6 in the example removal of impurities reaction kettle.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
Example, the reaction temperature of the coprecipitation reaction kettle is 45~55 DEG C or so, and pH is 10~11.5.
A specific implementation as a kind of system for continuously recycling waste and old ternary lithium ion battery described in the utility model
The temperature of the example secondary removal of impurities reaction kettle is 30~50 DEG C, and pH is 11~13.
Compared with prior art, the utility model has the advantages that：
1st, the utility model provides a kind of system for continuously recycling waste and old ternary lithium ion battery, is recycling waste and old ternary lithium
Ternary precursor product and high-concentration sulfuric acid lithium solution are prepared while ion battery, before existing tertiary cathode material
Driving body uses cobaltous sulfate, nickel sulfate crystallization that can significantly reduce the manufacturing cost of ternary precursor for primary raw material.
2nd, Tthe utility model system can realize continuity run, and the continuity between each device is good；And the utility model system
Subordination is environmentally friendly, and ammonium hydroxide can be recycled.
3rd, the nickel-cobalt-manganese ternary material precursor purity prepared using utility model system is high, and tap density is big, particle
Grain size is small, narrowly distributing and be uniformly mixed；Lithium concentration is high in the lithium sulfate solution prepared, and impurity content is low, is used directly for
The production of lithium carbonate.
Description of the drawings
Fig. 1 is a kind of system structure diagram for continuously recycling waste and old ternary lithium ion battery of the utility model.
Specific embodiment
In order to make the purpose of the utility model, technical solutions and advantages more clearly understood, below in conjunction with attached drawing and implementation
Example, the present invention is further described in detail.It should be appreciated that specific embodiment described herein is only used to explain
The utility model is not used to limit the utility model.
Below in conjunction with the accompanying drawings, the utility model is described in detail.
In order to make the purpose of the utility model, technical solutions and advantages more clearly understood, below in conjunction with attached drawing and implementation
Example, the present invention is further described in detail.It should be appreciated that specific embodiment described herein is only used to explain
The utility model is not used to limit the utility model.
Waste and old ternary lithium ion battery system is continuously recycled with reference to concrete principle and process are a kind of to the utility model
System is described in detail：
A kind of system for continuously recycling waste and old ternary lithium ion battery, as shown in Figure 1, the system comprises pre-treatment lists
Member, acidleach unit, an impurity removing unit are co-precipitated unit, secondary impurity removing unit and ammonia recovery unit.
The pretreatment unit includes pulverizer, pulse dust collector, positive and negative anodes powder feed bin and seperator, the pulse
Deduster and seperator are connected with the pulverizer, and the positive and negative anodes powder feed bin is connected with pulse dust collector and seperator.
Specifically, the pulverizer in pretreatment unit is used for crushing waste and old ternary lithium ion battery, so as to make electricity
Positive and negative pole material and metal in pond are detached；Pulse dust collector is used for (main to the positive and negative anodes dust generated in crushing process
Refer to that some particles are tiny, the dust of floating) absorb and guide into, the dust that positive and negative pole material is crushed to generation by it is defeated
It send to positive and negative anodes powder feed bin and is stored；Positive and negative anodes powder feed bin is used for receiving positive and negative anodes powder caused by crushing
Collection, seperator are used for detaching the positive and negative anodes powder in crushed material and metal.Pretreatment unit is used for waste and old ternary lithium
Ion battery crushes processing, and the positive and negative anodes powder and metal that are obtained after crushing are detached, obtained positive and negative anodes powder into
Enter and stored in positive and negative anodes powder feed bin, subsequently to use.
Further, the pretreatment unit is additionally provided with loading head I, loading head II and loading head III, and loading head I is located at
Between pulse dust collector and positive and negative anodes powder feed bin, loading head II is located between seperator and positive and negative anodes powder feed bin, loading head
III connects with seperator.Loading head I and loading head II temporarily store, and pass through it by positive and negative anodes powder for providing positive and negative anodes powder
End is aggregated into positive and negative anodes powder feed bin.Loading head III is used for storing metal, and the metal after seperator detaches is led to
Enter and placed in loading head III.
Further, the pretreatment unit be additionally provided with the lye spray column that is connected with pulverizer and with lye spray column
The activated carbon filter of connection.Lye spray column is used for absorbing the lithium hexafluoro phosphate generated in old and useless battery crushing process
Processing, activated carbon filter are used for absorbing to volatilizing electrolyte solvent.
The acidleach unit includes Leach reaction kettle and Microfilter I, the Leach reaction kettle and positive and negative anodes powder feed bin
Connection.Leach reaction kettle is used for, to realizing positive and negative anodes powder, sulfuric acid solution and the leaching of hydrogenperoxide steam generator, passing through after leaching
Nickel, cobalt, manganese, lithium, aluminium sulfate mixing leachate is obtained by filtration in Microfilter I.
Impurity removing unit includes removal of impurities reaction kettle and squeezer, and the removal of impurities reaction kettle is connected with Microfilter I.
Removal of impurities reaction kettle is used for cleaning to leachate, removes hydroxide impurity therein, obtains nickel, cobalt, manganese, lithium sulfate and mix
Close solution.Squeezer is used for detaching impurity and primary removal of impurities liquid, and the primary removal of impurities liquid after removal of impurities is passed through batching kettle.
The co-precipitation unit includes batching kettle, coprecipitation reaction kettle and centrifuge, and the batching kettle connects with squeezer
It is logical.Batching kettle is used for adding in nickel cobalt manganese molar ratio in appropriate nickel cobalt mn sulphate adjusting solution into primary removal of impurities liquid.It is coprecipitated
Shallow lake reaction kettle is used for realizing the reaction of primary removal of impurities liquid and complex precipitant (sodium hydroxide and ammonia solution), generates nickel cobalt manganese three
First material precursor.Centrifuge is used for realizing the separation of solid and mother liquor.
Further, the co-precipitation unit is additionally provided with the drying box connected with centrifuge.Drying box is used for centrifuge
Isolated solid is dried, and solid is sent after elution to dry 20-24h obtains ternary at 80-110 DEG C in drying box
Material precursor product.
The secondary impurity removing unit includes secondary removal of impurities reaction kettle and Microfilter II, the secondary removal of impurities reaction kettle with from
Scheming connects.Secondary removal of impurities reaction kettle is used for the mother liquor after being detached to centrifuge and carries out secondary removal of impurities, removes wherein micro nickel
Cobalt manganese impurity；Microfilter II is used for being filtered the slurry after removal of impurities, detaches solid and liquid, by impurity with the shape of solid
Formula removes, and obtains the secondary removal of impurities liquid of liquid.
The ammonia recovery unit includes the heater being sequentially communicated, crystallizing evaporator, condenser and ammoniacal liquor receiving tank, institute
Heater is stated to connect with Microfilter II.Heater is used for heating the secondary removal of impurities liquid after removal of impurities, makes Ammonia valatilization, heats
Device heating and temperature control is between 60-90 DEG C.The ammonia volatilized is sprayed by evaporation knot by the jet port of heater after heating
Brilliant device forms liquefied ammonia, and flow into ammoniacal liquor receiving tank and stored after last condensed device condensation.Ammonia valatilization is made simultaneously using heating
Enter the concentration that crystallizing evaporator can effectively improve ammonia in finished product ammonia solution by way of injection, Tthe utility model system obtains
To ammonia solution in ammonia density be more than 20%, can be recycled to coprecipitation reaction recycling.
Further, the ammonia recovery unit is additionally provided with the evaporation mother liquor holding tank connected with heater.Specifically, work as heating
When the ammonia density of lithium sulfate solution is less than 0.005g/L in device, is squeezed into evaporation mother liquor holding tank, detect solution lithium concentration, when
The lithium sulfate solution is circularly used for preparing sodium hydroxide solution when lithium concentration is less than 21g/L, is somebody's turn to do when lithium concentration is more than 21g/L
Lithium sulfate solution is used directly for the production of lithium carbonate.
The technique that waste and old ternary lithium ion battery is continuously recycled using the utility model, before the technique includes battery
Processing, acidleach is primary to clean, co-precipitation, secondary removal of impurities and recovery ammonia：
The battery pre-treatment crushes the positive and negative anodes of generation for waste and old ternary lithium ion battery is crushed through pulverizer
Powder enters positive and negative anodes powder feed bin by pulse dust collector, and crushed material is passed through seperator and is divided metal and positive and negative anodes powder
From positive and negative anodes powder enters positive and negative anodes powder feed bin
Specifically, the battery pre-treatment is crushed and is generated for waste and old ternary lithium ion battery is crushed through pulverizer
Positive and negative anodes dust loading head I is entered by pulse dust collector, then enter back into positive and negative anodes powder feed bin and stored；Crushed material
Metal and positive and negative anodes powder are detached by seperator, metal enters loading head III, and positive and negative anodes powder enters loading head II,
Then positive and negative anodes powder feed bin is entered back into be stored；The lithium hexafluoro phosphate that crushing generates is passed through lye spray column and is absorbed,
The electrolyte solvent volatilized is passed through activated carbon filter and is absorbed.
The acidleach is that positive and negative anodes powder is delivered to Leach reaction kettle, and adds in sulfuric acid and hydrogenperoxide steam generator progress instead
Should, the slurry after reaction obtains leachate after the filtering of Microfilter I.
Specifically, the acidleach is that positive and negative anodes powder is delivered to Leach reaction kettle, adds in certain density sulfuric acid solution
And nickel, cobalt, manganese, lithium, aluminium sulfuric acid is obtained by filtration through Microfilter I after leaching in hydrogenperoxide steam generator, the leaching at 30~50 DEG C
Salt mixing leachate.Wherein, the concentration of sulfuric acid and hydrogen peroxide can be selected according to specific requirements, preferably 2~5mol/L
Sulfuric acid solution and 10~30% hydrogenperoxide steam generator.
The primary removal of impurities is that leachate is passed through in removal of impurities reaction kettle, sodium hydrate regulator solution pH is added in, after reaction
Slurry is passed through squeezer and the liquid that once cleans is obtained after squeezing.
Specifically, leachate is passed through in removal of impurities reaction kettle, adds in sodium hydroxide solution and adjust pH to 4~6,40~50
Hydroxide impurity is removed after squeezer squeeze and filter is passed through after being reacted at DEG C, obtains nickel, cobalt, manganese, lithium sulfuric acid mixed salt solution.
If pH is more than 6 in primary removal of impurities, the yield of Ni, Co, Mn can be influenced, can not be removed if less than 4, Al, presoma can be made
Al content exceeds the requirement of national standard 0.015% in product.
The co-precipitation is primary removal of impurities liquid to be passed through in batching kettle, and add in nickel cobalt mn sulphate and adjust nickel cobalt in solution
Manganese molar ratio then passes to coprecipitation reaction kettle, and adds in complex precipitant and carry out coprecipitation reaction, and the slurry after reaction is led to
Enter centrifuge, the mother liquor and solid obtained after centrifugation.
Specifically, the primary removal of impurities liquid after removal of impurities is passed through in batching kettle, and add in appropriate nickel cobalt mn sulphate
It is 1 to adjust nickel cobalt manganese molar ratio in solution:1:1,5:2:3,6:2:2 or 8:1:1, it then passes in coprecipitation reaction kettle, and add
Enter complex precipitant (sodium hydroxide and ammonia solution), controlling reaction temperature is 50 DEG C or so, and pH is 10~11.5.It will after reaction
Slurry is passed through centrifuge, and mother liquor and solid are obtained after centrifuge detaches.Solid obtains ternary material nickel cobalt after eluting, drying
Manganese precursor product.Nickel cobalt manganese molar ratio is depending on the raw material and product of ternary material nickel cobalt manganese precursor wherein in solution
's.
The secondary removal of impurities is that the mother liquor obtained after being centrifuged in being co-precipitated is passed through secondary removal of impurities reaction kettle, and add
Enter sodium hydrate regulator solution pH, the slurry after reaction obtains secondary removal of impurities liquid after the filtering of Microfilter II.
Specifically, will co-precipitation mother liquor be passed through secondary removal of impurities reaction kettle, and add in sodium hydroxide solution adjust pH to 11~
13, it is reacted at 30~50 DEG C, the slurry after reaction removes micro nickel cobalt manganese impurity, and obtain secondary through the filtering of Microfilter II
Clean liquid.
If without secondary removal of impurities, will directly be co-precipitated obtained mother liquor and be passed through in heater, the inside have remaining Ni,
Co, Mn ion, this solution can not carry out cycle and have precipitation generation with alkali, is also not used to after lithium concentration reaches 21g/L
Lithium carbonate production line, because having carbonic acid when reacting generation lithium carbonate with sodium carbonate without Ni, Co, Mn ion, solution in producing line
Nickel, cobalt carbonate, manganese carbonate generate, and can influence the quality of product.
The recovery ammonia is that secondary removal of impurities liquid is passed through after heater is heated to be passed through crystallizing evaporator, and condensed device is cold
Ammoniacal liquor receiving tank is flowed into after solidifying.
Specifically, secondary removal of impurities liquid is passed through heater to heat, the temperature for controlling heater is 60~90 DEG C, heating
The ammonia volatilized is sprayed by crystallizing evaporator by the jet port of heater afterwards, liquefied ammonia is formed after last condensed device condensation,
And it flows into ammoniacal liquor receiving tank and is stored.Heating is used to make Ammonia valatilization and enters crystallizing evaporator by way of injection can be with
The concentration of ammonia in finished product ammonia solution is effectively improved, ammonia density is more than 20% in obtained ammonia solution, and it is anti-can to be recycled to co-precipitation
It should recycle.
Further, when the ammonia density of lithium sulfate solution in heater is less than 0.005g/L, evaporation mother liquor storage is squeezed into
In tank, detect solution lithium concentration, when lithium concentration be less than 21g/L when the lithium sulfate solution be circularly used for prepare sodium hydroxide it is molten
Liquid, when lithium concentration be more than 21g/L when the lithium sulfate solution can be directly used for production lithium carbonate.
Below by specific example to the utility model a kind of system for continuously recycling waste and old ternary lithium ion battery into one
Step illustrates.
Example 1
Waste and old 18650 lithium ion ternary battery is used on continuous device shown in Fig. 1, to carry out battery successively for raw material
Pre-treatment, acidleach, removal of impurities, dispensing, co-precipitation, secondary removal of impurities, evaporation recovery ammonia process, it is big finally to prepare tap density, pure
Degree is high, and grain diameter is small, narrowly distributing and uniformly mixed ternary material precursor.Process conditions are：The sulfuric acid of 2mol/L,
Nickel, cobalt, manganese, lithium, aluminium sulfate mixing is obtained by filtration in the leaching at 50 DEG C of 10% hydrogen peroxide and positive and negative anodes powder after leaching
Solution adjusts solution ph 6, is reacted at 50 DEG C, filter off dehydrogenation oxide impurity, obtained nickel, cobalt, manganese, lithium sulfate and mix
Close solution.It is 1 to add in appropriate nickel cobalt mn sulphate in the solution and adjust nickel cobalt manganese molar ratio in solution:1:1, then add in hydrogen
Sodium oxide molybdena and ammonium hydroxide are as complex precipitant, 50 DEG C of controlling reaction temperature, pH value 10.5, reaction generation nickel-cobalt-manganese ternary material
Precursor, filtered, wash, be dried to obtain ternary material nickel cobalt manganese precursor, coprecipitated mother liquor adjusts solution ph 12.5,50
It is reacted at DEG C, filtering removes micro nickel cobalt manganese impurity, and control heating temperature is 80 DEG C, and the ammonia concn recycled out is 22%,
Lithium concentration 21.7g/L is incorporated to existing lithium carbonate production line in lithium sulfate solution.
Ternary material nickel cobalt manganese precursor host element and impurity content prepared by 1 example of table
Ternary material nickel cobalt manganese precursor performance prepared by 2 examples of table
From upper table 1 and upper table 2 as can be seen that the nickel-cobalt-manganese ternary material precursor purity height that this example is prepared, jolt ramming
Density is big, grain diameter is small, narrowly distributing and be uniformly mixed.
Example 2
Waste and old Soft Roll lithium ion ternary battery is used as raw material, on continuous device shown in Fig. 1, before carrying out battery successively
Processing, acidleach, removal of impurities, dispensing, co-precipitation, secondary removal of impurities, evaporation finally prepare that tap density is big, and purity is high except ammonia process,
Grain diameter is small, narrowly distributing and uniformly mixed ternary material precursor.Process conditions are：The sulfuric acid of 5mol/L, 30% dioxygen
The leaching at 30 DEG C of water and positive and negative anodes powder, is obtained by filtration nickel, cobalt, manganese, lithium, aluminium sulfate mixed solution after leaching, adjust
Save solution ph 5.5, reacted at 50 DEG C, filter off dehydrogenation oxide impurity, obtain nickel, cobalt, manganese, lithium sulfate mixing it is molten
Liquid.It is 5 to add in appropriate nickel cobalt mn sulphate in the solution and adjust nickel cobalt manganese molar ratio in solution:2:3, then add in hydroxide
Sodium and ammonium hydroxide are as complex precipitant, 50 DEG C of controlling reaction temperature, pH value 10.9, body before reaction generation nickel-cobalt-manganese ternary material
Body, filtered, wash, be dried to obtain ternary material nickel cobalt manganese precursor, coprecipitated mother liquor adjusts solution ph 13, anti-at 30 DEG C
Should, filtering removes micro nickel cobalt manganese impurity, and control heating temperature is 70 DEG C, and the ammonia concn recycled out is 20%, lithium sulfate
Lithium concentration 21.5g/L is used directly for production lithium carbonate in solution.
Ternary material nickel cobalt manganese precursor host element and impurity content prepared by 3 examples of table
Ternary material nickel cobalt manganese precursor performance prepared by 4 examples of table
From upper table 3 and upper table 4 as can be seen that the nickel-cobalt-manganese ternary material precursor purity height that this example is prepared, jolt ramming
Density is big, grain diameter is small, narrowly distributing and be uniformly mixed.
The above is only the preferred embodiment of the utility model only, is not intended to limit the utility model, all at this
All any modification, equivalent and improvement made within the spirit and principle of utility model etc., should be included in the utility model
Protection domain within.
Claims (10)
1. a kind of system for continuously recycling waste and old ternary lithium ion battery, which is characterized in that the system comprises pretreatment unit,
Acidleach unit, an impurity removing unit are co-precipitated unit, secondary impurity removing unit and ammonia recovery unit：
The pretreatment unit includes pulverizer, pulse dust collector, positive and negative anodes powder feed bin and seperator, the pulse dust removal
Device and seperator are connected with the pulverizer, and the positive and negative anodes powder feed bin is connected with pulse dust collector and seperator；
The acidleach unit includes Leach reaction kettle and Microfilter I, and the Leach reaction kettle is connected with positive and negative anodes powder feed bin；
Impurity removing unit includes removal of impurities reaction kettle and squeezer, and the removal of impurities reaction kettle is connected with Microfilter I；
The co-precipitation unit includes batching kettle, coprecipitation reaction kettle and centrifuge, and the batching kettle is connected with squeezer；
The secondary impurity removing unit includes secondary removal of impurities reaction kettle and Microfilter II, the secondary removal of impurities reaction kettle and centrifuge
Connection；
The ammonia recovery unit includes the heater being sequentially communicated, crystallizing evaporator, condenser and ammoniacal liquor receiving tank, described to add
Hot device is connected with Microfilter II.
2. a kind of system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that locate before described
Reason unit is additionally provided with loading head I, loading head II and loading head III, and loading head I is located at pulse dust collector and positive and negative anodes powder
Between feed bin, loading head II is located between seperator and positive and negative anodes powder feed bin, and loading head III is connected with seperator.
3. a kind of system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that locate before described
Reason unit is additionally provided with the lye spray column connected with pulverizer and the activated carbon filter connected with lye spray column.
4. a kind of system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that described coprecipitated
Shallow lake unit is additionally provided with the drying box connected with centrifuge.
A kind of 5. system for continuously recycling waste and old ternary lithium ion battery as claimed in claim 4, which is characterized in that the drying
The temperature of case is 80~110 DEG C, drying time for 20~for 24 hours.
6. a kind of system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that the ammonia returns
It receives unit and is additionally provided with the evaporation mother liquor holding tank connected with heater.
A kind of 7. system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that the heating
The heating temperature of device is 60~90 DEG C.
A kind of 8. system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that the removal of impurities
The pH of solution is 4~6 in reaction kettle.
9. a kind of system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that described coprecipitated
The reaction temperature of shallow lake reaction kettle is 45~55 DEG C or so, and pH is 10~11.5.
10. a kind of system for continuously recycling waste and old ternary lithium ion battery as described in claim 1, which is characterized in that described two
The temperature of secondary removal of impurities reaction kettle is 30~50 DEG C, and pH is 11~13.
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| CN201721696127.7U CN207602724U (en) | 2017-12-08 | 2017-12-08 | A kind of system for continuously recycling waste and old ternary lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111755768A (en) * | 2020-07-28 | 2020-10-09 | 韶山润泽新能源科技有限公司 | Waste battery negative electrode powder regeneration treatment system and process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111755768A (en) * | 2020-07-28 | 2020-10-09 | 韶山润泽新能源科技有限公司 | Waste battery negative electrode powder regeneration treatment system and process |
| CN111755768B (en) * | 2020-07-28 | 2021-02-19 | 韶山润泽新能源科技有限公司 | Waste battery negative electrode powder regeneration treatment system and process |
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