CN107706481B - A method of anode material of lithium battery is recycled based on hollow microsphere solid phase - Google Patents
A method of anode material of lithium battery is recycled based on hollow microsphere solid phase Download PDFInfo
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Abstract
The present invention proposes a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, positive electrode is after base extraction removes copper, aluminium collector, ball mill grinding is carried out to positive electrode, pass through the lithium ion in the modified titanium dioxide hollow microballoon selective absorption positive electrode of crown ether, sintering forms large grained lithium titanate under vibrating conditions, iron, cobalt, nickel metal oxide powder pass through screening separation.This method solve the auxiliary agents that recycling elemental lithium needs to have greater environmental impacts using strong acid etc. in traditional handicraft, pollute in the process without acid solution, have important practical significance to lithium battery recycling.
Description
Technical field
The present invention relates to lithium battery material recovery technology fields, and in particular to one kind is based on hollow microsphere solid phase recycling lithium electricity
The method of pond positive electrode.
Background technique
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 back and forth between a electrode：When charging, Li+ is embedded in cathode from positive deintercalation, by electrolyte, and cathode is in rich lithium
State；It is then opposite when electric discharge.Compared with ni-Cd, nickel-metal hydride battery, lithium ion battery is high with voltage, specific energy is big, cycle life
It grows, have a safety feature, self discharge is small, memory-less effect, can be quickly charged and discharged, many advantages, such as operating temperature range is wide, wide
It is general to be stored up for electric car, electric bicycle, battery-operated motor cycle, photovoltaic and wind power generation energy accumulation system, smart grid
It can system, mobile communication base station, electric power, chemical industry, spare UPS, EPS power supply of hospital, security protection illumination, Portable mobile power source, mine
The multiple fields such as mountain safety equipment.
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 recycling about waste lithium cell.Ingredient and the structure for constituting lithium battery are complex, including
Steel/aluminum hull, aluminium collector anode load cobalt acid lithium/LiFePO4/nickle cobalt lithium manganate etc., gather copper/nickel/steel collector load carbon
Alkene porous septum, lithium hexafluoro phosphate/lithium perchlorate dimethyl carbonate/ethylene carbonate/methyl ethyl carbonate ester solution etc., if not
It is recycled, it will environment is produced a very large impact.And after recycling, it is extracted by technology, many materials can also be by sharp again
With.The considerations of in terms of for environmental protection and resource reutilization, the recycling of dynamic lithium battery is very necessary.
Pyrometallurgical method is one of recycling 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 anode
Material is calcined, ball milling water logging separate and recover nickle cobalt lithium manganate in lithium, with high-temperature roasting through simple and mechanical broken lithium from
Sub- battery, screening obtain the fine powder containing metal and metal oxide.Similar high-temperature calcination technique is relatively easy, is suitble to big
Scale processing, still, calcination process purifying technique complex steps, the energy consumption in high-temperature calcination treatment of battery is high.
Wet processing can recycle dynamic lithium battery active principle, Chinese Patent Application No. 201710388189.X
A kind of lithium battery recycling and reusing method is disclosed, lithium battery mechanical crushing, organic solvent washing, air-flow are ground into separation, sulphur
Acid and hydrogenperoxide steam generator impregnate, utilize alkali solution precipitate to recycle different ions in batches later, increase the receipts of every kind of element
Rate also improves the purity of recycling Co；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 recycling 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 conclusion lithium battery recycling at present is mainly by the means such as high-temperature calcination and soda acid separation, there are energy consumption height, works
The disadvantages 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 recycling.
Summary of the invention
It is primarily present energy consumption height for the recycling of current lithium battery, process is tedious, and serialization degree is low, Reusability soda acid point
From it is big to body harm the disadvantages 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, is separated later to lithium titanate with other metallic elements by physical means, 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 method of anode material of lithium battery being recycled based on hollow microsphere solid phase, specific preparation method is：
（1）After the electric discharge of discarded lithium battery, the positive electrode of lithium ion battery is taken out from waste and old lithium ion battery, is put
Enter in lye and impregnate 10-13 hours, copper, aluminium collector through filtering removal dissolution 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 is at 0.5-1 microns
When stop, obtaining pretreatment powder；
（3）By titanium dioxide hollow microballoon and crown ether with mass ratio 100:3-5 is uniformly dispersed, and obtains in modifying titanium dioxide
Empty microballoon, the inner surface of titanium dioxide hollow microballoon, outer surface are sufficiently contacted with crown ether, then with step（2）Obtained pre- place
It manages powder to be uniformly mixed, the complete suspended dispersed in airflow machine, titanium dioxide hollow microballoon is selected under crown ether auxiliary with solid phase
The lithium ion of absorption 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 titanium
Sour lithium powder.
Preferably, step（1）NaOH or KOH solution of the lye between pH=9-12, the temperature of the alkaline solution
Degree is 50-62 DEG C.
Preferably, step（2）The partial size of the titanium dioxide hollow microballoon is 50-100 μm, and surface micropore diameter is less than
10nm。
Preferably, step（2）The revolving speed control of the high energy ball mill is controlled in 80-120rpm, the time of ball milling in 2-5
Hour, ball-milling medium selects corundum ball or agate ball.
Preferably, step（3）The modifying titanium dioxide hollow microsphere is 0.1-0.5 with weight ratio with pretreatment powder：1
Investment.
Preferably, step（3）The crown ether is that 15- is preced with (ether) -5,18- is preced with (ether) -6, two thiacyclohexane simultaneously -18- hat (ether) -
At least one of 6.
Preferably, step（3）The high temperature sintering temperature is 800-1000 DEG C, is sintered 30-60min.
Preferably, step（4）The vibrosieve from vibration frequency be 200-3000Hz.
Existing lithium battery recycling is mainly by the means such as high-temperature calcination and soda acid separation, and there are energy consumption height, and process is tedious, even
The disadvantages of continuousization degree is low, and the separation of Reusability soda acid is big to body harm.The present invention proposes a kind of based on hollow microsphere solid phase
The method for recycling anode material of lithium battery, positive electrode use the modified dioxy of crown ether after base extraction removes copper, aluminium collector
Change titanium hollow microsphere, is sintered after being adsorbed to the lithium ion in anode, by vibrosieve from metal compounds such as iron, cobalt, nickel
Object obtains the higher lithium titanate powder of purity.Ball mill grinding is carried out to positive electrode after alkali process removes collector, acquisition
High-temperature roasting after powder is mixed with titanium dioxide hollow microballoon, nano-titanium dioxide hollow microsphere large specific surface area, as solid phase
It is high to metal-lithium ion absorption property to extract adsorbent, elemental lithium recovery efficiency is high, solves and recycles elemental lithium in traditional handicraft
The auxiliary agent having greater environmental impacts using strong acid etc. is needed, is polluted in the process without acid solution, there is important reality to lithium battery recycling
Border meaning.Further, present invention process method is simple, and equipment investment is few, with short production cycle, and cost recovery is low, and recovery efficiency is high,
Removal process does not generate secondary pollution, to battery production cost is reduced, economizes on resources and all plays positive effect.
A kind of method based on hollow microsphere solid phase recycling anode material of lithium battery of the present invention, compared with prior art,
Prominent feature and excellent effect are：
1, the present invention carries out ball mill grinding to positive electrode after alkali process removes collector, mixes later with titanium dioxide
High-temperature roasting afterwards is solved by the lithium ion in the modified titanium dioxide hollow microballoon selective absorption positive electrode of crown ether
The auxiliary agent that elemental lithium needs to have greater environmental impacts using strong acid etc. is recycled in traditional handicraft, is polluted in the process without acid solution, to lithium
Battery recycling has important practical significance.
2, the present invention using large specific surface area titanium dioxide hollow microballoon as solid phase extraction adsorbents to lithium metal from
Sub- absorption property is high, and elemental lithium recovery efficiency is high.
3, present invention process method is simple, and equipment investment is few, with short production cycle, and cost recovery is low, and recovery efficiency is high, recycling
Process does not generate secondary pollution, to battery production cost is reduced, economizes on resources and all plays positive effect.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method 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 recycles is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese conjunction
It is object, manganese nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, a kind of in lithium iron compound, in the present embodiment with
It is illustrated for waste and old nickle cobalt lithium manganate NCM523 battery.
（1）After discarded nickle cobalt lithium manganate NCM523 battery discharge, by the positive electrode of lithium ion battery from waste and old lithium from
It is taken out in sub- battery, it is 50 DEG C that the pretreated positive electrode, which is put into temperature, is impregnated in the KOH solution lye of pH=9
13 hours, copper, aluminium collector through filtering removal dissolution obtained 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 revolving speed of high energy ball mill is controlled in 120rpm, ball
The time control of mill was at 2 hours, and corundum ball is selected in the choosing of spheroidal graphite medium, and the powder diameter after ball milling stops at 1 micron, obtains
To pretreatment powder；
（3）By titanium dioxide hollow microballoon and 15- hat (ether) -5 with mass ratio 100:3 are uniformly dispersed, and obtain modified dioxy
Change titanium hollow microsphere, contact the inner surface of titanium dioxide hollow microballoon, outer surface sufficiently with crown ether, then with step（2）?
The pretreatment powder arrived is uniformly mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere and pretreatment powder
Body is with weight ratio for 0.1：1 investment, titanium dioxide hollow microballoon select absorption pretreatment powder under crown ether auxiliary with solid phase
Lithium ion, then high temperature sintering under vibrating conditions；High temperature sintering temperature is 800 DEG C, is sintered 30min；
（4）After the completion of to be sintered, setting vibrosieve from vibration frequency be respectively 1000Hz, 3000 Hz are by vibration
Sieve separation nickel oxide, cobalt oxide powder, obtain lithium titanate powder.The powder composition of recycling test as shown in table 1.
Embodiment 2
The waste and old lithium ion battery that the present invention recycles is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese conjunction
It is object, manganese nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, a kind of in lithium iron compound, in the present embodiment with
It is illustrated for waste and old nickle cobalt lithium manganate NCM523 battery.
（1）After discarded nickle cobalt lithium manganate NCM523 battery discharge, by the positive electrode of lithium ion battery from waste and old lithium from
It is taken out in sub- battery, it is 62 DEG C that the pretreated positive electrode, which is put into temperature, is soaked in the NaOH solution lye of pH=12
Bubble 10 hours, copper, aluminium collector through filtering removal dissolution, 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 revolving speed of high energy ball mill is controlled in 80rpm, ball
The time control of mill was at 4 hours, and agate ball is selected in the choosing of spheroidal graphite medium, and the powder diameter after ball milling stops at 0.5 micron,
Obtain pretreatment powder；
（3）By titanium dioxide hollow microballoon and 18- hat (ether) -6 with mass ratio 100:5 are uniformly dispersed, and obtain modified dioxy
Change titanium hollow microsphere, contact the inner surface of titanium dioxide hollow microballoon, outer surface sufficiently with crown ether, then with step（2）?
The pretreatment powder arrived is uniformly mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere and pretreatment powder
Body is with weight ratio for 0.3：1 investment, titanium dioxide hollow microballoon select absorption pretreatment powder under crown ether auxiliary with solid phase
Lithium ion, then high temperature sintering under vibrating conditions；High temperature sintering temperature is 1000 DEG C, is sintered 30min；
（4）After the completion of to be sintered, setting vibrosieve from vibration frequency be respectively 200Hz, 1500 Hz, by vibration
Sieve separation nickel oxide, cobalt oxide powder, obtain lithium titanate powder.The powder composition of recycling test as shown in table 1.
Embodiment 3
The waste and old lithium ion battery that the present invention recycles is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese conjunction
It is object, manganese nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, a kind of in lithium iron compound, in the present embodiment with
It is illustrated for waste lithium iron phosphate battery LFP.
（1）After the electric discharge of discarded ferric phosphate lithium cell, by the positive electrode of lithium ion battery from waste and old lithium ion battery
It taking out, it is 55 DEG C that the pretreated positive electrode, which is put into temperature, it is impregnated 11 hours in the NaOH solution lye of pH=10,
Copper, aluminium collector through filtering removal dissolution, 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 revolving speed of high energy ball mill is controlled in 90rpm, ball
The time control of mill was at 4 hours, and spheroidal graphite medium selects agate ball, and the powder diameter after ball milling stops at 0.6 micron, obtains
To pretreatment 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 obtain
To modifying titanium dioxide hollow microsphere, contact the inner surface of titanium dioxide hollow microballoon, outer surface sufficiently with crown ether, then with
Step（2）Obtained pretreatment powder is uniformly mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere with
Powder is pre-processed with weight ratio as 0.5：1 investment, titanium dioxide hollow microballoon is under crown ether auxiliary with the pre- place of solid phase selection absorption
The lithium ion of powder is managed, then high temperature sintering under vibrating conditions；High temperature sintering temperature is 800 DEG C, is sintered 30min；
（4）After the completion of to be sintered, vibrosieve from vibration frequency be 1000Hz, by vibrosieve from brown iron oxide
End obtains lithium titanate powder.The powder composition of recycling test as shown in table 1.
Embodiment 4
（1）The waste and old lithium ion battery that the present invention recycles is positive electrode cobalt compound containing lithium, lithium nickel compound, lithium manganese
Object, manganese nickel cobalt complex chemical compound, manganese nickel aluminium complex chemical compound, lithium vanadium compound, a kind of in lithium iron compound is closed, in the present embodiment
It is illustrated by taking waste lithium iron phosphate battery as an example.
（1）After the electric discharge of discarded ferric phosphate lithium cell, by the positive electrode of lithium ion battery from waste and old lithium ion battery
It takes out, it is 55 DEG C that the pretreated positive electrode, which is put into temperature, is impregnated 12 hours in the KOH solution of pH=11, through filtering
Copper, the aluminium collector for removing dissolution, 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 revolving speed of high energy ball mill is controlled in 110rpm, ball
The time control of mill was at 3 hours, and spheroidal graphite medium selects corundum ball, and the powder diameter after ball milling stops at 0.6 micron, obtains
To pretreatment powder；
（3）By titanium dioxide hollow microballoon and 15- hat (ether) -5 with mass ratio 100:- 5 are uniformly dispersed, and obtain modified dioxy
Change titanium hollow microsphere, contact the inner surface of titanium dioxide hollow microballoon, outer surface sufficiently with crown ether, then with step（2）?
The pretreatment powder arrived is uniformly mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere and pretreatment powder
Body is with weight ratio for 0.4：1 investment, titanium dioxide hollow microballoon select absorption pretreatment powder under crown ether auxiliary with solid phase
Lithium ion, then high temperature sintering under vibrating conditions；High temperature sintering temperature is 800 DEG C, is sintered 60min；
（4）After the completion of to be sintered, vibrosieve from vibration frequency be 1200Hz, by vibrosieve from brown iron oxide
End obtains lithium titanate powder.The powder composition of recycling test as shown in table 1.
Embodiment 5
（1）It is after 1kg cylinder is discarded NCM111 battery discharge, the positive electrode of lithium ion battery is electric from applying waste lithium ionic
It is taken out in pond, it is 58 DEG C that the pretreated positive electrode, which is put into temperature, impregnates 11 hours, passes through in the NaOH lye of pH=9
Copper, the aluminium collector of filtering removal dissolution, 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 revolving speed of high energy ball mill is controlled in 400rpm, ball
The time control of mill was at 4.5 hours, and spheroidal graphite medium is agate ball, and the powder diameter after ball milling stops at 0.8 micron, obtains
To pretreatment 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 obtain
To modifying titanium dioxide hollow microsphere, contact the inner surface of titanium dioxide hollow microballoon, outer surface sufficiently with crown ether, then with
Step（2）Obtained pretreatment powder is uniformly mixed, the complete suspended dispersed in airflow machine, modifying titanium dioxide hollow microsphere with
Powder is pre-processed with weight ratio as 0.2：1 investment, titanium dioxide hollow microballoon is under crown ether auxiliary with the pre- place of solid phase selection absorption
The lithium ion of powder is managed, then high temperature sintering under vibrating conditions；High temperature sintering temperature is 800 DEG C, is sintered 40min；
（4）After the completion of to be sintered, setting vibrosieve from vibration frequency be respectively 400Hz, 1600 Hz, by vibration
Sieve separation nickel oxide, cobalt oxide powder, obtain lithium titanate powder.The powder composition of recycling test as shown in table 1.
Comparative example 1
Using pyrometallurgical method, 1kg cylinder is discarded into NCM111 cell positive material and is calcined, ball milling water logging separates back
The lithium in nickle cobalt lithium manganate is received, with high-temperature roasting through simple and mechanical broken lithium ion battery, screening is obtained containing metal and gold
The powder composition of recycling test as shown in table 1 by the fine powder for belonging to oxide.
Comparative example 2
Using wet processing, 1kg cylinder is discarded into the crushing of NCM111 battery lithium battery machine, organic solvent washing, air-flow
It grinds separation, the hydrogenperoxide steam generator immersion that the sulfuric acid that concentration is 4M and mass fraction are 25%, is using alkali soluble modulation PH later
7.5 liquid obtain Kocide SD, iron hydroxide, aluminum hydroxide precipitation, and being subsequently added into sodium hydroxide and washing filtrate to PH is 12, obtain
To cobalt hydroxide, nickel hydroxide, manganous hydroxide mixture, be added sodium carbonate liquor lithium carbonate is obtained by filtration, by the powder of recycling
Material ingredient test as shown in table 1.
Table 1：
Claims (8)
1. a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, specific preparation method are：
（1）After the electric discharge of discarded lithium battery, the positive electrode of lithium ion battery is taken out from waste and old lithium ion battery, is put into alkali
It is impregnated 10-13 hours in liquid, copper, aluminium collector through filtering removal dissolution 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 at 0.5-1 microns
Only, pretreatment powder is obtained；
（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 contacts the inner surface of titanium dioxide hollow microballoon, outer surface sufficiently with crown ether, then with step（2）Obtained pretreatment
Powder is uniformly 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 recycling anode material of lithium battery, feature exist according to claim 1
In：Step（1）NaOH or KOH solution of the lye between pH=9-12, the temperature of the lye are 50-62 DEG C.
3. a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, feature exist according to claim 1
In：Step（2）The partial size of the titanium dioxide hollow microballoon is 50-100 μm, and surface micropore diameter is less than 10nm.
4. a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, feature exist according to claim 1
In：Step（2）The revolving speed control of the high energy ball mill is in 80-120rpm, and at 2-5 hours, ball milling was situated between for the time control of ball milling
Matter selects corundum ball or agate ball.
5. a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, feature exist according to claim 1
In：Step（3）The modifying titanium dioxide hollow microsphere is 0.1-0.5 with weight ratio with pretreatment powder：1 investment.
6. a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, 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 recycling anode material of lithium battery, feature exist according to claim 1
In：Step（3）The high temperature sintering temperature is 800-1000 DEG C, is sintered 30-60min.
8. a kind of method based on hollow microsphere solid phase recycling anode material of lithium battery, feature exist according to claim 1
In：Step（4）The vibrosieve from vibration frequency be 200-3000Hz.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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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| 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 |
| 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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