CN107706481A - A kind of method based on hollow microsphere solid phase recovery anode material of lithium battery - Google Patents
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention proposes a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, positive electrode is after base extraction peels off copper, aluminium collector, ball mill grinding is carried out to positive electrode, lithium ion in the titanium dioxide hollow microballoon selective absorption positive electrode being modified by crown ether, sintering forms large grained lithium titanate under vibrating conditions, and iron, cobalt, the metal oxide powder of nickel are separated by sieving.This method solve and the elemental lithium auxiliary agent that needs to use strong acid etc. to have greater environmental impacts is reclaimed in traditional handicraft, during polluted without acid solution, there is important practical significance to lithium battery recovery.
Description
Technical field
The present invention relates to lithium battery material recovery technology field, and in particular to one kind is based on hollow microsphere solid phase recovery lithium electricity
The method of pond positive electrode.
Background technology
Along with economic globalization process and energy demand it is continuous surging, find new energy storage device and have become newly
The focus of attention of energy related field.Lithium ion battery(Li-ion, Lithium Ion Battery):It is a kind of secondary cell
(Rechargeable battery), it relies primarily on lithium ion, and movement carrys out work between a positive electrode and a negative electrode.In charge and discharge process, Li+ is two
Insertion and deintercalation are come and gone between individual electrode:During charging, Li+ is embedded in negative pole, negative pole is in rich lithium from positive pole deintercalation by electrolyte
State;It is then opposite during electric discharge.Compared with NI-G, Ni-MH battery, lithium ion battery has that voltage is high, cycle life bigger than energy
Grow, have a safety feature, self discharge is small, memory-less effect, can fast charging and discharging, many advantages, such as operating temperature range is wide, it is wide
It is general to be used for electric automobile, electric bicycle, battery-operated motor cycle, photovoltaic and wind power generation energy accumulation system, intelligent grid storage
Can system, mobile communication base station, electric power, chemical industry, standby UPS, EPS power supply of hospital, security protection illumination, Portable mobile power source, ore deposit
The multiple fields such as mountain safety means.
While battery production increasingly increases, product is largely launched, one urgent the problem of can not be ignored
Pendulum is in face of us, that is, the recovery on waste lithium cell.It is complex to form composition and the structure of lithium battery, including
Steel/aluminum hull, aluminium collector positive pole load cobalt acid lithium/LiFePO4/nickle cobalt lithium manganate etc., copper/nickel/steel collector load carbon, gather
Dimethyl carbonate/ethylene carbonate/methyl ethyl carbonate ester solution etc. of alkene porous septum, lithium hexafluoro phosphate/lithium perchlorate, if not
Reclaimed, it will environment is produced a very large impact.And after reclaiming, extracted by technology, many materials can also be by sharp again
With.For the consideration in terms of environmental protection and resource reutilization, the recovery of dynamic lithium battery is very necessary.
Pyrometallurgical method is one of recovery main processing ways of dynamic lithium battery, Chinese Patent Application No.
201611186511.2 disclose a kind of recovery method of lithium in waste lithium cell positive electrode, by by waste lithium cell positive pole
Material is calcined, ball milling water logging separation and recovery nickle cobalt lithium manganate in lithium, with high-temperature roasting through simple and mechanical broken lithium from
Sub- battery, screening obtain the fine powder body containing metal and metal oxide.Similar high-temperature calcination technique is relatively easy, is adapted to big
Scale processing, still, calcination process purifying technique complex steps, the high energy consumption in high-temperature calcination treatment of battery.
Wet processing can reclaim to dynamic lithium battery active principle, Chinese Patent Application No. 201710388189.X
A kind of lithium battery recycling method is disclosed, lithium battery mechanical crushing, organic solvent washing, air-flow are ground into separation, sulphur
Acid and hydrogenperoxide steam generator immersion, different ions is reclaimed in batches using alkali solution precipitate afterwards, add the receipts of every kind of element
Rate, also improve recovery Co purity;After waste battery is crushed, with suitable chemical reagent selective dissolution, separation is leached
Metallic element in liquid.The technology stability of hydrometallurgical is good, the recovery of suitable middle and small scale waste lithium cell, but technique
Reusability soda acid auxiliary agent is needed in method, has certain harm to health of human body and ecological environment.
In summary, mainly by the means such as high-temperature calcination and soda acid separation there is high energy consumption, work in lithium battery recovery at present
The shortcomings of sequence is cumbersome, and serialization degree is low, and the separation of Reusability soda acid is big to body harm.Therefore, it is simple to develop a kind of process,
Process is harmless, and environment amenable recovery method has important practical significance to lithium battery recovery.
The content of the invention
High energy consumption is primarily present for the recovery of current lithium battery, tedious process, serialization degree is low, Reusability soda acid point
From to body harm it is big the shortcomings of, by the present invention in that being burnt after carrying out selective absorption to lithium ion with titanium dioxide hollow microballoon
Knot prepares lithium titanate, and lithium titanate is separated with other metallic elements by physical means afterwards, and process is simple, and no acid solution is dirty
Dye, production cost are low.
To solve the above problems, the present invention uses following technical scheme:
A kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, specific preparation method are:
(1)After discarded lithium battery is discharged, the positive electrode of lithium ion battery is taken out from waste and old lithium ion battery, is put into alkali
Soaked in liquid 10-13 hours, the filtered copper for removing dissolving, aluminium collector, obtain the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the powder diameter after ball milling stops in 0.5-1 microns
Only, obtain pre-processing powder;
(3)By titanium dioxide hollow microballoon and crown ether with mass ratio 100:3-5 is uniformly dispersed, and it is hollow micro- to obtain modifying titanium dioxide
Ball, the inner surface of titanium dioxide hollow microballoon, outer surface fully contact with crown ether, then with step(2)Obtained pretreatment powder
Body is well mixed, the complete suspended dispersed in airflow machine, and titanium dioxide hollow microballoon selects to adsorb under crown ether auxiliary with solid phase
The lithium ion of powder is pre-processed, then high temperature sintering under vibrating conditions;
(4)After the completion of to be sintered, the metal oxide powder of de-iron, cobalt, nickel is removed by vibrosieve, obtains bulky grain lithium titanate
Powder.
Preferably, step(1)NaOH or KOH solution of the alkali lye between pH=9-12, the temperature of the alkaline solution
Spend for 50-62 DEG C.
Preferably, step(2)The particle diameter of the titanium dioxide hollow microballoon is 50-100 μm, and surface micropore footpath is less than
10nm。
Preferably, step(2)The rotating speed of the high energy ball mill is controlled in 80-120rpm, and the time control of ball milling is in 2-5
Hour, ball-milling medium selects corundum ball or agate ball.
Preferably, step(3)The modifying titanium dioxide hollow microsphere is with pretreatment powder using weight ratio as 0.1-0.5:1
Input.
Preferably, step(3)The crown ether be 15- be preced with (ether) -5,18- be preced with (ether) -6, two thiacyclohexane simultaneously -18- be preced with (ether) -
At least one of 6.
Preferably, step(3)The high temperature sintering temperature is 800-1000 DEG C, sinters 30-60min.
Preferably, step(4)The vibrosieve from vibration frequency be 200-3000Hz.
Mainly by the means such as high-temperature calcination and soda acid separation, high energy consumption be present, tedious process, connect in existing lithium battery recovery
The shortcomings of continuousization degree is low, and the separation of Reusability soda acid is big to body harm.The present invention proposes that one kind is based on hollow microsphere solid phase
The method for reclaiming anode material of lithium battery, positive electrode are modified dioxy after base extraction peels off copper, aluminium collector, using crown ether
Change titanium hollow microsphere, sintered after being adsorbed to the lithium ion in positive pole, by vibrosieve from metal compounds such as iron, cobalt, nickel
Thing, obtain the higher lithium titanate powder of purity.Ball mill grinding is carried out to positive electrode after alkali process peels off collector, acquisition
High-temperature roasting after powder mixes with titanium dioxide hollow microballoon, nano titanium oxide hollow microsphere specific surface area is big, as solid phase
It is high to metal-lithium ion absorption property to extract adsorbent, elemental lithium organic efficiency is high, solves and elemental lithium is reclaimed in traditional handicraft
The auxiliary agent for needing to use strong acid etc. to have greater environmental impacts, during without acid solution pollute, to lithium battery recovery there is important reality
Border meaning.Further, present invention process method is simple, and equipment investment is few, with short production cycle, and cost recovery is low, and organic efficiency is high,
Removal process does not produce secondary pollution, to reducing battery production cost, economizes on resources and all plays positive role.
A kind of method based on hollow microsphere solid phase recovery anode material of lithium battery of the present invention, compared with prior art, its
The characteristics of prominent and excellent effect are:
1st, the present invention carries out ball mill grinding after alkali process peels off collector to positive electrode, high after being mixed afterwards with titanium dioxide
Temperature roasting, by the lithium ion in the titanium dioxide hollow microballoon selective absorption positive electrode of crown ether modification, solves tradition
In technique reclaim elemental lithium need to use the auxiliary agent that strong acid etc. has greater environmental impacts, during without acid solution pollute, to lithium battery
Recovery has important practical significance.
2nd, the present invention using the big titanium dioxide hollow microballoon of specific surface area as solid phase extraction adsorbentses to lithium metal from
Sub- absorption property is high, and elemental lithium organic efficiency is high.
3rd, present invention process method is simple, and equipment investment is few, with short production cycle, and cost recovery is low, and organic efficiency is high, recovery
Process does not produce secondary pollution, to reducing battery production cost, economizes on resources and all plays positive role.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The waste and old lithium ion battery that the present invention reclaims is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese compound, manganese
It is a kind of in nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, lithium iron compound, with waste and old in the present embodiment
Illustrated exemplified by nickle cobalt lithium manganate NCM523 batteries.
(1)After discarded nickle cobalt lithium manganate NCM523 battery discharges, by the positive electrode of lithium ion battery from waste and old lithium from
Taken out in sub- battery, it is 50 DEG C that the positive electrode of the pretreatment is put into temperature, is soaked in the KOH solution alkali lye of pH=9
13 hours, the filtered copper for removing dissolving, aluminium collector, obtain the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the rotating speed of high energy ball mill is controlled in 120rpm, ball milling
For time control at 2 hours, spheroidal graphite medium selected corundum ball, and the powder diameter after ball milling stops at 1 micron, obtains pre-
Handle powder;
(3)Titanium dioxide hollow microballoon and 15- are preced with (ether) -5 with mass ratio 100:3 are uniformly dispersed, and obtain modifying titanium dioxide
Hollow microsphere, the inner surface of titanium dioxide hollow microballoon, outer surface is fully contacted with crown ether, then with step(2)Obtain
Pretreatment powder be well mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere with pretreatment powder with
Weight ratio is 0.1:1 input, titanium dioxide hollow microballoon crown ether auxiliary under with solid phase select absorption pretreatment powder lithium from
Son, then high temperature sintering under vibrating conditions;High temperature sintering temperature is 800 DEG C, sinters 30min;
(4)After the completion of to be sintered, set vibrosieve from vibration frequency be respectively 1000Hz, 3000 Hz pass through vibrosieve
From nickel oxide, cobalt oxide powder, lithium titanate powder is obtained.The powder composition of recovery test as shown in table 1.
Embodiment 2
The waste and old lithium ion battery that the present invention reclaims is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese compound, manganese
It is a kind of in nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, lithium iron compound, with waste and old in the present embodiment
Illustrated exemplified by nickle cobalt lithium manganate NCM523 batteries.
(1)After discarded nickle cobalt lithium manganate NCM523 battery discharges, by the positive electrode of lithium ion battery from waste and old lithium from
Taken out in sub- battery, it is 62 DEG C that the positive electrode of the pretreatment is put into temperature, is soaked in the NaOH solution alkali lye of pH=12
Bubble 10 hours, the filtered copper for removing dissolving, aluminium collector, obtains the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the rotating speed of high energy ball mill is controlled in 80rpm, ball milling
For time control at 4 hours, spheroidal graphite medium selected agate ball, and the powder diameter after ball milling stops at 0.5 micron, obtains
Pre-process powder;
(3)Titanium dioxide hollow microballoon and 18- are preced with (ether) -6 with mass ratio 100:5 are uniformly dispersed, and obtain modifying titanium dioxide
Hollow microsphere, the inner surface of titanium dioxide hollow microballoon, outer surface is fully contacted with crown ether, then with step(2)Obtain
Pretreatment powder be well mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere with pretreatment powder with
Weight ratio is 0.3:1 input, titanium dioxide hollow microballoon crown ether auxiliary under with solid phase select absorption pretreatment powder lithium from
Son, then high temperature sintering under vibrating conditions;High temperature sintering temperature is 1000 DEG C, sinters 30min;
(4)After the completion of to be sintered, set vibrosieve from vibration frequency be respectively 200Hz, 1500 Hz, by vibrosieve
From nickel oxide, cobalt oxide powder, lithium titanate powder is obtained.The powder composition of recovery test as shown in table 1.
Embodiment 3
The waste and old lithium ion battery that the present invention reclaims is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese compound, manganese
It is a kind of in nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, lithium iron compound, with waste and old in the present embodiment
Illustrated exemplified by ferric phosphate lithium cell LFP.
(1)After discarded ferric phosphate lithium cell is discharged, by the positive electrode of lithium ion battery from waste and old lithium ion battery
Taking out, it is 55 DEG C that the positive electrode of the pretreatment is put into temperature, is soaked 11 hours in the NaOH solution alkali lye of pH=10,
The filtered copper for removing dissolving, aluminium collector, obtain the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the rotating speed of high energy ball mill is controlled in 90rpm, ball milling
For time control at 4 hours, spheroidal graphite medium selected agate ball, and the powder diameter after ball milling stops at 0.6 micron, obtains pre-
Handle powder;
(3)By titanium dioxide hollow microballoon and two thiacyclohexanes, simultaneously -18- is preced with (ether) -6 with mass ratio 100:3 are uniformly dispersed, and are changed
Property titanium dioxide hollow microballoon, makes the inner surface of titanium dioxide hollow microballoon, outer surface fully be contacted with crown ether, then with step
(2)Obtained pretreatment powder is well mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere and pre- place
Powder is managed using weight ratio as 0.5:1 input, titanium dioxide hollow microballoon select absorption pretreatment powder under crown ether auxiliary with solid phase
The lithium ion of body, then high temperature sintering under vibrating conditions;High temperature sintering temperature is 800 DEG C, sinters 30min;
(4)After the completion of to be sintered, vibrosieve from vibration frequency be 1000Hz, by vibrosieve from croci, obtain
To lithium titanate powder.The powder composition of recovery test as shown in table 1.
Embodiment 4
(1)The waste and old lithium ion battery that the present invention reclaims is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese conjunction
It is a kind of in thing, manganese nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, lithium iron compound, in the present embodiment with
Illustrated exemplified by waste lithium iron phosphate battery.
(1)After discarded ferric phosphate lithium cell is discharged, by the positive electrode of lithium ion battery from waste and old lithium ion battery
Take out, it is 55 DEG C that the positive electrode of the pretreatment is put into temperature, is soaked 12 hours in the KOH solution of pH=11, filtered
Copper, the aluminium collector of dissolving are removed, obtains the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the rotating speed of high energy ball mill is controlled in 110rpm, ball milling
For time control at 3 hours, spheroidal graphite medium selected corundum ball, and the powder diameter after ball milling stops at 0.6 micron, obtains pre-
Handle powder;
(3)Titanium dioxide hollow microballoon and 15- are preced with (ether) -5 with mass ratio 100:- 5 are uniformly dispersed, and obtain modifying titanium dioxide
Hollow microsphere, the inner surface of titanium dioxide hollow microballoon, outer surface is fully contacted with crown ether, then with step(2)Obtain
Pretreatment powder be well mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere with pretreatment powder with
Weight ratio is 0.4:1 input, titanium dioxide hollow microballoon crown ether auxiliary under with solid phase select absorption pretreatment powder lithium from
Son, then high temperature sintering under vibrating conditions;High temperature sintering temperature is 800 DEG C, sinters 60min;
(4)After the completion of to be sintered, vibrosieve from vibration frequency be 1200Hz, by vibrosieve from croci, obtain
To lithium titanate powder.The powder composition of recovery test as shown in table 1.
Embodiment 5
(1)After 1kg cylinders are discarded into NCM111 battery discharges, by the positive electrode of lithium ion battery from waste and old lithium ion battery
Take out, it is 58 DEG C that the positive electrode of the pretreatment is put into temperature, is soaked 11 hours in the NaOH alkali lye of pH=9, filtered
Copper, the aluminium collector of dissolving are removed, obtains the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the rotating speed of high energy ball mill is controlled in 400rpm, ball milling
For time control at 4.5 hours, spheroidal graphite medium was agate ball, and the powder diameter after ball milling stops at 0.8 micron, obtains pre-
Handle powder;
(3)By titanium dioxide hollow microballoon and two thiacyclohexanes, simultaneously -18- is preced with (ether) -6 with mass ratio 100:4 are uniformly dispersed, and are changed
Property titanium dioxide hollow microballoon, makes the inner surface of titanium dioxide hollow microballoon, outer surface fully be contacted with crown ether, then with step
(2)Obtained pretreatment powder is well mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere and pre- place
Powder is managed using weight ratio as 0.2:1 input, titanium dioxide hollow microballoon select absorption pretreatment powder under crown ether auxiliary with solid phase
The lithium ion of body, then high temperature sintering under vibrating conditions;High temperature sintering temperature is 800 DEG C, sinters 40min;
(4)After the completion of to be sintered, set vibrosieve from vibration frequency be respectively 400Hz, 1600 Hz, by vibrosieve
From nickel oxide, cobalt oxide powder, lithium titanate powder is obtained.The powder composition of recovery test as shown in table 1.
Comparative example 1
Using pyrometallurgical method, 1kg cylinders are discarded into NCM111 cell positive materials and calcined, ball milling water logging separation and recovery nickel
Lithium in cobalt manganic acid lithium, obtained with high-temperature roasting through simple and mechanical broken lithium ion battery, screening containing metal and metal oxygen
The fine powder body of compound, the powder composition of recovery test as shown in table 1.
Comparative example 2
Using wet processing, the discarded NCM111 battery lithiums battery machine crushing of 1kg cylinders, organic solvent washing, air-flow are ground
The hydrogenperoxide steam generator immersion that the sulfuric acid and mass fraction that separation, concentration are 4M are 25%, it is afterwards 7.5 using alkali soluble modulation PH
Liquid obtains Kocide SD, iron hydroxide, aluminum hydroxide precipitation, and it is 12 to be subsequently added into sodium hydroxide and wash filtrate to PH, is obtained
Cobalt hydroxide, nickel hydroxide, the mixture of manganous hydroxide, add sodium carbonate liquor and be filtrated to get lithium carbonate, by the powder of recovery
Composition test as shown in table 1.
Table 1:
Claims (8)
1. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, specific preparation method are:
(1)After discarded lithium battery is discharged, the positive electrode of lithium ion battery is taken out from waste and old lithium ion battery, is put into alkali
Soaked in liquid 10-13 hours, the filtered copper for removing dissolving, aluminium collector, obtain the filter residue containing positive electrode active material;
(2)High energy ball mill crushing will be put into after the filter residue and drying, the powder diameter after ball milling stops in 0.5-1 microns
Only, obtain pre-processing powder;
(3)By titanium dioxide hollow microballoon and crown ether with mass ratio 100:3-5 is uniformly dispersed, and it is hollow micro- to obtain modifying titanium dioxide
Ball, the inner surface of titanium dioxide hollow microballoon, outer surface is fully contacted with crown ether, then with step(2)Obtained pretreatment
Powder is well mixed, the complete suspended dispersed in airflow machine, and titanium dioxide hollow microballoon selects to inhale under crown ether auxiliary with solid phase
The lithium ion of attached pretreatment powder, then high temperature sintering under vibrating conditions;
(4)After the completion of to be sintered, the metal oxide powder of de-iron, cobalt, nickel is removed by vibrosieve, obtains bulky grain lithium titanate
Powder.
2. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(1)NaOH or KOH solution of the alkali lye between pH=9-12, the temperature of the alkaline solution is 50-62 DEG C.
3. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(2)The particle diameter of the titanium dioxide hollow microballoon is 50-100 μm, and surface micropore footpath is less than 10nm.
4. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(2)The rotating speed control of the high energy ball mill is situated between in 80-120rpm, the time control of ball milling in 2-5 hours, ball milling
Matter selects corundum ball or agate ball.
5. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(3)The modifying titanium dioxide hollow microsphere is with pretreatment powder using weight ratio as 0.1-0.5:1 input.
6. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(3)The crown ether be 15- be preced with (ether) -5,18- be preced with (ether) -6, two thiacyclohexane simultaneously -18- be preced with (ether) -6 at least one
Kind.
7. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(3)The high temperature sintering temperature is 800-1000 DEG C, sinters 30-60min.
8. a kind of method based on hollow microsphere solid phase recovery anode material of lithium battery, its feature exist according to claim 1
In:Step(4)The vibrosieve from vibration frequency be 200-3000Hz.
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CN108682916A (en) * | 2018-06-11 | 2018-10-19 | 四会市恒星智能科技有限公司 | The recovery method of lithium in a kind of anode material for lithium-ion batteries |
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CN103449395A (en) * | 2013-08-28 | 2013-12-18 | 北京科技大学 | Method for recycling positive material from water-system waste lithium iron phosphate battery |
CN106590060A (en) * | 2016-11-24 | 2017-04-26 | 宁波卫生职业技术学院 | Method of allowing nano titanium dioxide to be evenly distributed in polymer |
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US20120082893A1 (en) * | 2010-10-01 | 2012-04-05 | GM Global Technology Operations LLC | Lithium ion battery |
CN103154282A (en) * | 2011-05-27 | 2013-06-12 | 英派尔科技开发有限公司 | Effective recovery of lithium from lithium ion battery waste |
CN103449395A (en) * | 2013-08-28 | 2013-12-18 | 北京科技大学 | Method for recycling positive material from water-system waste lithium iron phosphate battery |
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