CN105186059B - Recycling method of graphite material of negative electrode of failed square lithium ion battery - Google Patents
Recycling method of graphite material of negative electrode of failed square lithium ion battery Download PDFInfo
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- CN105186059B CN105186059B CN201510613426.9A CN201510613426A CN105186059B CN 105186059 B CN105186059 B CN 105186059B CN 201510613426 A CN201510613426 A CN 201510613426A CN 105186059 B CN105186059 B CN 105186059B
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- graphite material
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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
Abstract
The invention discloses a method for recycling a graphite material of a negative electrode of a failed square lithium ion battery. The method comprises the steps of firstly, completely discharging an invalid square lithium ion battery, then detaching a negative pole piece, placing the negative pole piece in a dilute hydrochloric acid solution for ultrasonic dissolution, stopping ultrasonic dissolution after a graphite sheet material is completely separated from a current collector, taking out the separated current collector, and completing recovery of the current collector after washing and drying; filtering, low-temperature vacuum drying and sieving the residual graphite slurry to obtain a primarily purified graphite material, placing the primarily purified graphite material in an oxidant solution in a water bath for ultrasonic treatment, centrifuging, washing, low-temperature vacuum drying and sieving to obtain a secondarily purified graphite material; the graphite material is immersed in a reducing solution in a water bath and simultaneously undergoes ultrasonic reaction in a nitrogen atmosphere at a low temperature, then the graphite material is repaired by heat treatment in the nitrogen atmosphere, and the modified graphite powder for the battery grade can be obtained after cooling and sieving. The invention has the advantages of low reaction energy consumption and high recovery efficiency.
Description
Technical field
The present invention relates to a kind of recycling method for the rectangular lithium ion battery negative pole graphite material that fails.
Background technology
Current lithium ion battery industry has been enter into the stage of high speed development, and the battery scrapped every year is innumerable.Negative pole stone
The manufacturing process of ink material has the features such as energy consumption of reaction is high, consersion unit requirement is harsh, the production cycle is long, and graphite resource has
Limit, can cause the graphite material situation that supply falls short of demand.Therefore, recycling graphite material can not only avoid graphite resource
Waste, the in the market graphite material situation that supply falls short of demand can also be alleviated to a certain extent.
In order that the rectangular lithium ion battery negative pole graphite material of failure realizes resource circulation utilization, researchers have opened up
Substantial amounts of exploration and research have been opened, but they mainly realize the recovery of graphite, but the method energy consumption of reaction by high-temperature roasting method
Higher, organic efficiency is low and graphite poor-performing.Therefore, it is necessary to which developing a kind of new approach carrys out recycling failure
Rectangular lithium ion battery negative pole graphite material, to realize recycling for graphite resource.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of recovery for the rectangular lithium ion battery negative pole graphite material that fails
Reuse method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is the rectangular lithium ion battery negative pole stone that fails
The recycling method of ink material, comprises the following steps：
(1) rectangular lithium ion battery of failure is vented completely and the negative of rectangular lithium ion battery of failing is analysed and obtained after electricity
Pole pole piece；
(2) cathode pole piece for obtaining step (1) is placed in ultrasonic dissolution in 0.01mol/L dilute hydrochloric acid solutions, treats graphite flake
Material stops ultrasound after being kept completely separate from collector, takes out collector, and returning for collector is then completed after water washing, drying
Receive；Now then remaining graphite slurry obtains the graphite material purified for the first time through filtering, vacuum drying after sieving separating thickener
Material；
(3) graphite material purified for the first time in step (2) is placed in the oxidizing agent solution in water-bath carry out it is ultrasonically treated,
The metallic compound in graphite material is removed, binding agent is aoxidized and graphite surface is produced functionalization group, then through centrifuging, washing
Wash and vacuum drying, the graphite material of secondary purification is obtained after sieving separating binding agent；
(4) graphite material of the secondary purification obtained by step (3) is impregnated in the reducing solution in water-bath, adjusted
The pH value of system is 7~9,30~60min of ultrasonic reaction in 20~35 DEG C, nitrogen atmosphere, then through heat in nitrogen atmosphere
Processing is repaired to graphite material, and the modified graphite powder of LITHIUM BATTERY can be obtained after cooling sieving；Reducing solution is
The aqueous solution of ethylenediamine or diethylenetriamine or hydrazine.
Preferably, the collector that graphite material described in step (2) is selected is copper foil.
Preferably, the ultrasonic power in step (2) is 40~100W.
Preferably, in step (2) and (3), the design temperature of drying graphite material is 50~80 DEG C.
Preferably, oxidizing agent solution is one in the nitration mixture of nitric acid, perchloric acid or nitric acid and perchloric acid in step (3)
Kind.
Preferably, the power of ultrasonic reaction is 30~50W in step (3), ultrasonic reaction temperature is 25~45 DEG C.
Preferably, in step (4), using the pH value of pH value regulator regulation system, the pH value regulator is
0.1mol/L NaOH solution.
Preferably, in step (4), the power of the ultrasonic reaction is 60~100W.
Preferably, heat treatment temperature described in step (4) is 650~750 DEG C, the reaction time of the heat treatment is
0.5~1h.
The beneficial effects of the invention are as follows：
Compared with existing recycling method, the present invention is square using the failure of twice ultrasonic auxiliary acidization hydrometallurgic recovery
Graphite material at negative, has the advantages that energy consumption of reaction is relatively low, it is efficient to reclaim；Have by ultrasonic wave added in-situ preparation
There is the graphite of surface modification, then through high-temperature process, the modified graphite powder of LITHIUM BATTERY can be obtained after cooling sieving, it is real
The resource circulation utilization of existing graphite material.The capacity of this method recycling negative material, high rate performance, first charge-discharge effect
The chemical property such as rate and cycle life is suitable with the performance of LITHIUM BATTERY graphite.
Embodiment
Embodiment 1
The rectangular lithium ion battery of failure is vented after electricity completely and analysed, resulting cathode pole piece is placed in 0.01mol/L
Ultrasonic dissolution in dilute hydrochloric acid solution, ultrasonic power is 60W, stops ultrasound after graphite sheet stock is kept completely separate from collector, takes
Go out collector, the recovery of collector is then completed after water washing, drying, now remaining graphite slurry is through at filtering, 50 DEG C
Vacuum drying, then obtains the graphite material purified for the first time after sieving separating thickener；The graphite material of the first purification of gained
Be placed in the oxidizing agent solution in 35 DEG C of water-bath and carry out ultrasonically treated, ultrasonic power is 40W, then through centrifugation, washing and
The graphite material of secondary purification is obtained after vacuum drying at 50 DEG C, sieving separating binding agent；The graphite material of the secondary purification of gained
Material is impregnated in the reducing solution in water-bath, and the pH value with 0.1mol/L NaOH solution regulation system is 7, in 25 DEG C, nitrogen
Ultrasonic reaction 30min in gas atmosphere, ultrasonic power is 60W, cooled then through 650 DEG C of high-temperature process in nitrogen atmosphere
The modified graphite I of LITHIUM BATTERY can be obtained after sieve.
Embodiment 2
The rectangular lithium ion battery of failure is vented after electricity completely and analysed, resulting cathode pole piece is placed in 0.01mol/L
Ultrasonic dissolution in dilute hydrochloric acid solution, ultrasonic power is 40W, stops ultrasound after graphite sheet stock is kept completely separate from collector, takes
Go out collector, the recovery of collector is then completed after water washing, drying, now remaining graphite slurry is through at filtering, 60 DEG C
Vacuum drying, then obtains the graphite material purified for the first time after sieving separating thickener；The graphite material of the first purification of gained
Be placed in the oxidizing agent solution in 45 DEG C of water-bath and carry out ultrasonically treated, ultrasonic power is 50W, then through centrifugation, washing and
The graphite material of secondary purification is obtained after vacuum drying at 60 DEG C, sieving separating binding agent；The graphite material of the secondary purification of gained
Material is impregnated in the reducing solution in water-bath, and the pH value with 0.1mol/L NaOH solution regulation system is 9, in 35 DEG C, nitrogen
Ultrasonic reaction 30min in gas atmosphere, ultrasonic power is 100W, cooled then through 750 DEG C of high-temperature process in nitrogen atmosphere
The modified graphite II of LITHIUM BATTERY can be obtained after sieve.
Embodiment 3
The rectangular lithium ion battery of failure is vented after electricity completely and analysed, resulting cathode pole piece is placed in 0.01mol/L
Ultrasonic dissolution in dilute hydrochloric acid solution, ultrasonic power is 100W, stops ultrasound after graphite sheet stock is kept completely separate from collector, takes
Go out collector, the recovery of collector is then completed after water washing, drying, now remaining graphite slurry is through at filtering, 80 DEG C
Vacuum drying, then obtains the graphite material purified for the first time after sieving separating thickener；The graphite material of the first purification of gained
Be placed in the oxidizing agent solution in 25 DEG C of water-bath and carry out ultrasonically treated, ultrasonic power is 30W, then through centrifugation, washing and
The graphite material of secondary purification is obtained after vacuum drying at 80 DEG C, sieving separating binding agent；The graphite material of the secondary purification of gained
Material is impregnated in the reducing solution in water-bath, and the pH value with 0.1mol/L NaOH solution regulation system is 8, in 25 DEG C, nitrogen
Ultrasonic reaction 60min in gas atmosphere, ultrasonic power is 80W, cooled then through 750 DEG C of high-temperature process in nitrogen atmosphere
The modified graphite III of LITHIUM BATTERY can be obtained after sieve.
The button battery performance data of the LITHIUM BATTERY graphite of table 1 and modified graphite material
The full battery performance of the LITHIUM BATTERY graphite of table 2 and modified graphite material
It was found from Tables 1 and 2, by the capacity of above-described embodiment recycling negative material, high rate performance, fill first
The chemical property such as discharging efficiency and cycle life is suitable with the performance of LITHIUM BATTERY graphite, can be again as LITHIUM BATTERY negative pole material
Expect to use.
The embodiments of the present invention described above are not intended to limit the scope of the present invention.It is any in the present invention
Spirit and principle within the modifications, equivalent substitutions and improvements made etc., should be included in the claim protection model of the present invention
Within enclosing.
Claims (9)
1. the recycling method for the rectangular lithium ion battery negative pole graphite material that fails, comprises the following steps：
(1) rectangular lithium ion battery of failure is vented to the negative pole pole that failure rectangular lithium ion battery is analysed and obtained after electricity completely
Piece；
(2) cathode pole piece for obtaining step (1) is placed in ultrasonic dissolution in 0.01mol/L dilute hydrochloric acid solutions, treat graphite sheet stock from
Stop ultrasound after being kept completely separate on collector, take out collector, the recovery of collector is then completed after water washing, drying；This
When remaining graphite slurry through filtering, vacuum drying, then obtain the graphite material purified for the first time after sieving separating thickener；
(3) graphite material purified for the first time in step (2) is placed in the oxidizing agent solution in water-bath and carries out ultrasonically treated, removing
Metallic compound in graphite material, aoxidize binding agent and graphite surface is produced functionalization group, then through centrifugation, wash simultaneously
The graphite material of secondary purification is obtained after vacuum drying, sieving separating binding agent；
(4) graphite material of the secondary purification obtained by step (3) is impregnated in the reducing solution in water-bath, regulation system
PH value be 7~9,30~60min of ultrasonic reaction in 20~35 DEG C, nitrogen atmosphere；Then it is thermally treated in nitrogen atmosphere
Graphite material is repaired, the modified graphite powder of LITHIUM BATTERY can be obtained after cooling sieving；The reducing solution is
The aqueous solution of ethylenediamine or diethylenetriamine or hydrazine.
2. recycling method according to claim 1, it is characterised in that：Graphite material described in step (2) is selected
Collector be copper foil.
3. recycling method according to claim 1, it is characterised in that：The work(of ultrasonic dissolution described in step (2)
Rate is 40~100W.
4. recycling method according to claim 1, it is characterised in that：In step (2) and (3), graphite is dried
The design temperature of material is 50~80 DEG C.
5. recycling method according to claim 1, it is characterised in that：Oxidizing agent solution is described in step (3)
One kind in the nitration mixture of nitric acid, perchloric acid or nitric acid and perchloric acid.
6. recycling method according to claim 1, it is characterised in that：The power of ultrasonic reaction is in step (3)
30~50W, ultrasonic reaction temperature is 25~45 DEG C.
7. recycling method according to claim 1, it is characterised in that：In step (4), adjusted with pH value regulator
The pH value of system, the pH value regulator is 0.1mol/L NaOH solution.
8. recycling method according to claim 1, it is characterised in that：In step (4), the work(of the ultrasonic reaction
Rate is 60~100W.
9. recycling method according to claim 1, it is characterised in that：Heat treatment temperature is described in step (4)
650~750 DEG C, the reaction time of the heat treatment is 0.5~1h.
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| CN107317048A (en) * | 2017-05-26 | 2017-11-03 | 金川集团股份有限公司 | The method that copper foil and graphite are reclaimed from negative electrode material of waste lithium ion battery |
| CN107959077A (en) * | 2017-11-15 | 2018-04-24 | 何本科 | A kind of reclaiming method of graphite cathode |
| CN107959079B (en) * | 2017-12-28 | 2020-11-20 | 中南大学 | Method for recycling waste lithium ion battery negative electrode material |
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| CN108899608A (en) * | 2018-07-24 | 2018-11-27 | 娈疯 | A kind of ternary cell positive material recovery method of plasma joint sodium hypochlorite |
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| CN109103533A (en) * | 2018-07-24 | 2018-12-28 | 娈疯 | A kind of ternary cell positive material recovery method of plasma joint persulfate |
| CN109065997A (en) * | 2018-07-24 | 2018-12-21 | 娈疯 | A kind of ternary cell positive material recovery method of plasma joint vapor |
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| CN109065998A (en) * | 2018-07-24 | 2018-12-21 | 深圳市前海泓远控股有限公司 | A kind of ternary cell positive material recovery method of plasma joint sulfate |
| CN108963375A (en) * | 2018-07-24 | 2018-12-07 | 娈疯 | A kind of ternary cell positive material recovery method of plasma joint oxygen |
| CN112047335B (en) * | 2020-08-31 | 2022-05-17 | 湖南宸宇富基新能源科技有限公司 | Combined treatment method for black powder of waste lithium ion battery |
| CN112652832A (en) * | 2020-12-22 | 2021-04-13 | 东莞市和鸿升新材料科技有限公司 | Method for preparing negative electrode material by recycling negative electrode slurry |
| CN114447465A (en) * | 2022-01-14 | 2022-05-06 | 清华大学深圳国际研究生院 | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material |
| CN114361639A (en) * | 2022-01-21 | 2022-04-15 | 中国科学院青海盐湖研究所 | Method for efficiently separating and recovering graphite and copper foil in negative electrode of waste lithium ion battery |
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| JPH05258780A (en) * | 1991-08-08 | 1993-10-08 | Akkumulator Es Szarazelemgyar | Method for reproducing active material of storage battery electrode plate from wasteful active material |
| CN103618120B (en) * | 2013-12-06 | 2016-04-27 | 广东邦普循环科技有限公司 | In a kind of negative electrode material of waste lithium ion battery, graphite and copper sheet is separated and recovery method |
| CN104241723B (en) * | 2014-07-11 | 2017-11-17 | 广东邦普循环科技有限公司 | Negative material regeneration method in the unqualified lithium ion battery of graphite system |
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Address after: 230012 E workshop of group A in New Station Industrial Park, Hefei, Anhui. Patentee after: Anhui xunying new energy Co.,Ltd. Address before: 230012 E workshop of group A in New Station Industrial Park, Hefei, Anhui. Patentee before: ANHUI XUNYING NEW ENERGY TECHNOLOGY CO.,LTD. |
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Address after: 230012 No. 8, southeast corner of the intersection of huaitong road and tonghuai Middle Road, Xinzhan District, Hefei City, Anhui Province Patentee after: Anhui xunying New Energy Group Co.,Ltd. Address before: 230012 E workshop of group A in New Station Industrial Park, Hefei, Anhui. Patentee before: Anhui xunying new energy Co.,Ltd. |