CN105355998A - Recovery method of LiFePO4 positive electrode material - Google Patents
Recovery method of LiFePO4 positive electrode material Download PDFInfo
- Publication number
- CN105355998A CN105355998A CN201510741625.8A CN201510741625A CN105355998A CN 105355998 A CN105355998 A CN 105355998A CN 201510741625 A CN201510741625 A CN 201510741625A CN 105355998 A CN105355998 A CN 105355998A
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- China
- Prior art keywords
- positive electrode
- black powder
- lifepo
- described step
- recovery method
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
Belonging to the technical field of lithium ion batteries, the invention provides a recovery method of an LiFePO4 positive electrode material. The method is characterized by comprising the steps of: (1) crushing an LiFePO4 positive electrode waste sheet, then mixing the crushed LiFePO4 positive electrode waste sheet with a mixed solution of DMF and water, performing rapid stirring, conducting vacuum pumping and filtration to obtain black powder and filtrate, and collecting black powder; (2) mixing the obtained filtrate with an aluminum foil, conducting rapid stirring, separating the black powder from the aluminum foil again, and carrying out vacuum pumping and filtration so as to obtain black powder and filtrate, collecting the black powder, and repeating the step (2) until the residue on the aluminum foil is little; (3) mixing the collected black powder, and then performing vacuum drying; (4) crushing the dried black powder and conducting separation to obtain a mixture of LiFePO4 positive electrode powder and carbon; and (5) subjecting the separated mixture of LiFePO4 positive electrode powder and carbon to heat treatment. The method provided by the invention has the characteristics of green and environmental protection, and no pollution, the recovered LiFePO4 positive electrode material has considerable electrochemical performance, the recovery rate is high, and the cost is saved.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of LiFePO
4the recovery method of positive electrode.
Background technology
At present, the research of reclaiming lithium battery is not also very deep.Wherein some method of finding in research process is only suitable for for the recovery containing the such digital lithium ion battery of the element such as cobalt, nickel, such as: the types such as LiCoO2, Ni-Co-Mn ternary, such method is learnt after deliberation and is not available to recycle the lithium ion battery not containing the element such as cobalt, nickel, and the method for this recycling is pretty troublesome, run in process that the case is extremely complicated, also cost can be increased, and the requirement reaching high efficiency usury useless, be easy to the destruction of causing environment and the ecosystem.Therefore, need to seek a kind of efficient, cost is low, can not to the recovery method of environment.
Adopting dry technique in currently available technology, is isolate cobalt and acetylene black and cobalt ions battery recycling treatment technology by the method for reduction roasting.Dry technique battery is placed on one do not have water, do not have in the environment of air, that is carry out under inflated with nitrogen or ammonia, then battery is burned, and will obtain various metal by burning.Lithium ion battery is broken into pieces, then to the waste and old heat treatment of lithium battery fragment under row different temperatures, 0 DEG C, 150 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, then some materials that can burn carried out volatilization process and leave LiCoC02, then carry out the water bath with thermostatic control of 75 DEG C, liquid-solid volume mass dissolves LiCoO2 than in 20L/g, concentration of nitric acid 1mol/L, 1.7% solution, the leaching rate of Li and Co all can reach 85%.But it is very high that its shortcoming is exactly the energy consumed, the electrolyte in battery and shell etc. all can generate because of burning and release some toxic gases and waste material.
Summary of the invention
The problem to be solved in the present invention is: overcome the deficiencies in the prior art, provides a kind of environmental protection, pollution-free, the LiFePO of recovery
4positive electrode chemical property is considerable, and the rate of recovery is high, cost-saving LiFePO
4the recovery method of positive electrode.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of LiFePO
4the recovery method of positive electrode, comprises the steps:
(1) by LiFePO
4positive pole waste paper mixes with the mixed solution of water with DMF after pulverizing, rapid stirring, and black powder separates from aluminium foil and obtains suspension-turbid liquid, vacuumizing filtration, obtains black powder and filtrate, collects black powder;
(2) filtrate step (1) obtained and aluminium foil mixing, rapid stirring, black powder again separates from aluminium foil and obtains suspension-turbid liquid, vacuumizing filtration, obtain black powder and filtrate, collect black powder, repeating said steps (2), until the residue on aluminium foil is little;
(3) the black powder mixing final vacuum collected in described step (1), (2) is dry;
(4) dried for described step (3) black powder pulverizing, separation are obtained LiFePO
4the mixture of positive mix and carbon;
(5) described step (4) is separated the LiFePO obtained
4the mixture of positive mix and carbon is heat-treated in vacuum, nonoxidizing atmosphere.
Further, in described step (1), the volume of DMF and water is 1:1.
Further, the mixing time in described step (1) is 0.5h.
Further, the mixing time in described step (2) is 0.5h.
Further, the vacuumize temperature in described step (3) is 85 DEG C, and drying time is 0.5h.
Further, the black powder ball mill in described step (4) carries out the ball mill grinding of 15min, and is separated with 400 object sieves.
Further, in described step (5), heat treatment is that the mist being filled with argon gas and hydrogen in tube furnace burns.
Further, the heat treatment time of described step (5) is 1h.
Further, the heat treatment temperature of described step (5) is 0-350 DEG C.
Further, the aluminium foil after described step (2) process reclaims after washing.
The advantage that the present invention has and good effect are:
Environmental protection of the present invention, pollution-free, the LiFePO of recovery
4positive electrode chemical property is considerable, and the rate of recovery is high, cost-saving.
Accompanying drawing explanation
Fig. 1 is LiFePO of the present invention
4the flow chart of the recovery of positive electrode.
Fig. 2 is the LiFePO reclaimed at different heat treatment temperature
4the cycle performance figure of positive mix.
Fig. 3 is the LiFePO reclaimed
4positive mix is schemed through the XRD of heat treatments at different.
Embodiment
As shown in Figure 1, a kind of LiFePO
4the recovery method of positive electrode, comprises the steps:
(1) by LiFePO
4positive pole waste paper is poured in the large beaker of the mixed solution filling 200mLDMF and water after pulverizing, and the volume of DMF and water is 1:1, rapid stirring 0.5h, black powder separates from aluminium foil and obtains suspension-turbid liquid, vacuumizing filtration, obtains black powder and filtrate, collects black powder;
(2) filtrate step (1) obtained and aluminium foil join in large beaker, rapid stirring 0.5h, black powder again separates from aluminium foil and obtains suspension-turbid liquid, vacuumizing filtration, obtain black powder and filtrate, collect black powder, repeating said steps (2), until the residue on aluminium foil is little;
(3) the black powder mixing final vacuum collected in described step (1), (2) is dry, and vacuumize temperature is 85 DEG C, and drying time is 0.5h;
(4) described step (3) dried black powder ball mill is carried out the ball mill grinding of 15min, and carry out separation with 400 object sieves and obtain LiFePO
4the mixture of positive mix and carbon;
(5) described step (4) is separated the LiFePO obtained
4the mixture of positive mix and carbon in vacuum, be filled with in the tube furnace of mist of argon gas and hydrogen, carry out burning heat treatment at 0 DEG C, 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C respectively, heat treatment 1h, the LiFePO be recycled
4positive mix.
Test one
Fig. 2 is the LiFePO reclaimed at different heat treatment temperature
4the cycle performance figure of positive mix.Test condition is: voltage range from 2.5-4.2V, current density 30mAhg
-1.
Can be clear that from Fig. 1, the LiFePO of recovery
4the specific discharge capacity of positive mix can reach about 140mAhg
-1, reach when 250 DEG C in heat treatment temperature, the LiFePO of recovery
4the specific discharge capacity of positive mix can reach the highest 145mAhg
-1, and capacity after 90 cycle detection always conservation rate be greater than 96%, the image that this data statistics obtains makes us see the LiFePO of recovery very clearly
4positive mix has very considerable chemical property.When it can also be seen that from image heat-treating temperature is greater than 350 DEG C, the LiFePO of recovery
4the specific discharge capacity that positive mix shows reduces (140mAg at a terrific speed
-1).More than statement describes the LiFePO that PVDF (Vingon) binder decomposed through left after heat treatment reclaims for it
4the chemical property of positive mix has a great impact, even very high heat treatment temperature also can not be repaired the chemical property of the powder scrap of LiFePO4.
Test two
Fig. 3 is the LiFePO that at different heat treatment temperature, (0 DEG C, 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C) reclaim
4the XRD figure of positive mix, wherein, the LiFePO reclaimed at 1. line is 0 DEG C
4the XRD figure of positive mix, the LiFePO reclaimed at 2. line is 150 DEG C
4the XRD figure of positive mix, the LiFePO reclaimed at 3. line is 200 DEG C
4the XRD figure of positive mix, the LiFePO reclaimed at 4. line is 250 DEG C
4the XRD figure of positive mix, the LiFePO reclaimed at 5. line is 300 DEG C
4the XRD figure of positive mix, the LiFePO reclaimed at 6. line is 350 DEG C
4the XRD figure of positive mix.
Can be clear that from Fig. 2, the LiFePO of recovery
4positive mix characteristic diffraction peak and the LiFePO of olivine crystal formation
4standard diffraction peak coincide better, and except 20 ° of sides to the left have an obvious peak to occur, other do not have obvious impurity peaks to occur, illustrates not destroy LiFePO in removal process
4structure, and Low Temperature Heat Treatment can not to LiFePO
4positive mix structure has a huge impact.And LiFePO after Overheating Treatment
4peak have by force certain increase.
Passing through the peak further analyzing discovery 20 ° of sides to the left is FePO
4, along with the rising of heat treatment temperature, FePO
4peak value slowly diminishes, and temperature reaches about 350 DEG C, FePO
4peak value also can a little be kept to zero.Why have such phenomenon to occur, reason is wherein LiFePO
4fePO is defined gradually in charge/discharge cycles process
4but heat treatment of the present invention completes, so clearly can know Fe under the gaseous mixture of argon gas and hydrogen
3+because H
2reason be reduced into Fe
2+, Fe
2+the compound formed can be wrapped in LiFePO
4the surface of positive mix forms a housing, affects its chemical property.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiments of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (10)
1. a LiFePO
4the recovery method of positive electrode, is characterized in that: comprise the steps:
(1) by LiFePO
4positive pole waste paper mixes with the mixed solution of water with DMF after pulverizing, rapid stirring, and black powder separates from aluminium foil and obtains suspension-turbid liquid, vacuumizing filtration, obtains black powder and filtrate, collects black powder;
(2) filtrate step (1) obtained and aluminium foil mixing, rapid stirring, black powder again separates from aluminium foil and obtains suspension-turbid liquid, vacuumizing filtration, obtain black powder and filtrate, collect black powder, repeating said steps (2), until the residue on aluminium foil is little;
(3) the black powder mixing final vacuum collected in described step (1), (2) is dry;
(4) dried for described step (3) black powder pulverizing, separation are obtained LiFePO
4the mixture of positive mix and carbon;
(5) described step (4) is separated the LiFePO obtained
4the mixture of positive mix and carbon is heat-treated in vacuum, nonoxidizing atmosphere.
2. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: in described step (1), the volume of DMF and water is 1:1.
3. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the mixing time in described step (1) is 0.5h.
4. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the mixing time in described step (2) is 0.5h.
5. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the vacuumize temperature in described step (3) is 85 DEG C, and drying time is 0.5h.
6. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the black powder ball mill in described step (4) carries out the ball mill grinding of 15min, and is separated with 400 object sieves.
7. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: in described step (5), heat treatment is that the mist being filled with argon gas and hydrogen in tube furnace burns.
8. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the heat treatment time of described step (5) is 1h.
9. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the heat treatment temperature of described step (5) is 0-350 DEG C.
10. a kind of LiFePO according to claim 1
4the recovery method of positive electrode, is characterized in that: the aluminium foil after described step (2) process reclaims after washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510741625.8A CN105355998A (en) | 2015-11-03 | 2015-11-03 | Recovery method of LiFePO4 positive electrode material |
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| CN201510741625.8A CN105355998A (en) | 2015-11-03 | 2015-11-03 | Recovery method of LiFePO4 positive electrode material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895854A (en) * | 2016-06-14 | 2016-08-24 | 天齐锂业股份有限公司 | Recovery method of positive electrode leftover material of lithium-ion battery |
| CN107093724A (en) * | 2017-04-27 | 2017-08-25 | 柳州豪祥特科技有限公司 | The preparation method of anode material of lithium battery |
| CN107919507A (en) * | 2016-10-10 | 2018-04-17 | 中国科学院深圳先进技术研究院 | The method that LiFePO4 is recycled from waste lithium cell |
| CN108232352A (en) * | 2018-01-30 | 2018-06-29 | 南京红太阳新能源有限公司 | A kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode |
| CN108899601A (en) * | 2018-06-11 | 2018-11-27 | 衢州华友钴新材料有限公司 | A method of recycling lithium from LiFePO4 |
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| CN102285673A (en) * | 2011-06-03 | 2011-12-21 | 佛山市邦普循环科技有限公司 | Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile |
| CN102403553A (en) * | 2011-11-10 | 2012-04-04 | 大连交通大学 | Decomposing and recycling method of lithium battery electrode material |
| CN104183888A (en) * | 2014-09-11 | 2014-12-03 | 天津理工大学 | Green method for recovery and disposal of waste lithium iron phosphate power battery |
| CN104347906A (en) * | 2014-09-11 | 2015-02-11 | 天津理工大学 | Green recovery processing method of electrolyte inside waste power battery |
-
2015
- 2015-11-03 CN CN201510741625.8A patent/CN105355998A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285673A (en) * | 2011-06-03 | 2011-12-21 | 佛山市邦普循环科技有限公司 | Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile |
| CN102403553A (en) * | 2011-11-10 | 2012-04-04 | 大连交通大学 | Decomposing and recycling method of lithium battery electrode material |
| CN104183888A (en) * | 2014-09-11 | 2014-12-03 | 天津理工大学 | Green method for recovery and disposal of waste lithium iron phosphate power battery |
| CN104347906A (en) * | 2014-09-11 | 2015-02-11 | 天津理工大学 | Green recovery processing method of electrolyte inside waste power battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895854A (en) * | 2016-06-14 | 2016-08-24 | 天齐锂业股份有限公司 | Recovery method of positive electrode leftover material of lithium-ion battery |
| CN107919507A (en) * | 2016-10-10 | 2018-04-17 | 中国科学院深圳先进技术研究院 | The method that LiFePO4 is recycled from waste lithium cell |
| CN107093724A (en) * | 2017-04-27 | 2017-08-25 | 柳州豪祥特科技有限公司 | The preparation method of anode material of lithium battery |
| CN108232352A (en) * | 2018-01-30 | 2018-06-29 | 南京红太阳新能源有限公司 | A kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode |
| CN108899601A (en) * | 2018-06-11 | 2018-11-27 | 衢州华友钴新材料有限公司 | A method of recycling lithium from LiFePO4 |
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Application publication date: 20160224 |