CN1206765C - Recovery method for leftover and residue of positive electrode of lithium ion battery - Google Patents
Recovery method for leftover and residue of positive electrode of lithium ion battery Download PDFInfo
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- CN1206765C CN1206765C CNB031299725A CN03129972A CN1206765C CN 1206765 C CN1206765 C CN 1206765C CN B031299725 A CNB031299725 A CN B031299725A CN 03129972 A CN03129972 A CN 03129972A CN 1206765 C CN1206765 C CN 1206765C
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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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention relates to a recycling method for positive active materials in leftover materials and fragments in the manufacture process of a secondary lithium ion battery. The positive leftover materials and the fragments of the secondary lithium ion battery are broken mechanically, and positive active materials attached to an aluminum foil substrate, an additive agent (an electrical conduction agent) and a cementing agent are disengaged from the substrate by ultrasonic vibration or mechanical stirring, etc. in water or a specific organic solvent at certain temperature. The positive active materials are separated, washed, dried and processed at high temperature to obtain positive materials with good performance, and the positive materials can be directly used. The present invention processes leftover materials and the fragments generated in the manufacture process of a secondary lithium ion battery for battery manufacturers and recycles positive active materials, and thus, the present invention has important significances for lowering battery costs and preventing environmental pollution.
Description
Technical field
The present invention relates to the recycling of active material in lithium ion secondary battery positive electrode leftover pieces and the relic.
Background technology
In recent years, along with developing rapidly of mobile communication product and various portable type electronic products, the needs of secondary cell are growing, between the more than ten years since Sony Corporation in 1991 at first releases the practicability lithium rechargeable battery, the development of lithium rechargeable battery is swift and violent, has high power capacity, high discharge voltage, higher specific energy, advantages such as memory-less effect replace the main flow that nickel-cadmium cell and Ni-MH battery become commercial high-grade secondary cell gradually in the small-sized secondary batteries field, and in electric tool and electric automobiles, it also has remarkable advantages, sustainable growth along with output, leftover pieces and the relic of the thing followed in the secondary lithium battery manufacturing also sharply increases, most producers only obtain cobalt salt to handle at a low price to give relevant unit or adopt soda acid to handle to these leftover pieces relics, and this not only can make the economic benefit of battery producer be subjected to very big loss, but also can cause a large amount of wastings of resources and environmental pollution.
It is negative material that present most secondary lithium battery all adopts carbon, LiCoO
2, LiNiO
2, LiCo
xNi
1-xO
2Deng being positive electrode, it is simple, with low cost that carbon material negative pole reclaims technology, so the recovery of positive electrode has bigger economic worth and benefit relatively.
Summary of the invention
The purpose of this invention is to provide the method that a kind of lithium ion secondary battery positive electrode leftover pieces and relic reclaim active material.Technology of the present invention is simple, and production cost is low, can make the active material in anodal leftover pieces and the relic obtain farthest utilizing again, economizes on resources, and reduces environmental pollution.
Comprise in the anodal leftover pieces of lithium rechargeable battery and the relic: the active material LiCoO that adheres on aluminium foil matrix and the matrix
2, LiNiO
2, LiCo
xNi
1-xO
2Deng, adhesive, conductive agent (carbon black).Wherein, active substances in cathode materials comprises: LiCoO
2, LiNiO
2Or LiCo
xNi
1-xO
2, 0≤x≤1 wherein.
The present invention includes following steps:
1) under the normal temperature with anodal leftover pieces and relic mechanical means fragmentation;
2) at normal temperatures, the relic after the Mechanical Crushing is put into water, the active material in the positive pole is taken off with the method for mechanical agitation or ultrasonic oscillation; Perhaps
Relic after the fragmentation being put into organic solvent under the condition of 140-150 ℃ of temperature control of heating carries out mechanical agitation or takes off with the method for the ultrasonic oscillation active material with positive pole;
3) active material that takes off is washed with water, remove water-soluble binder of part and additive, separate obtaining active material, bake drying in air.
4) with flotation or method for screening, further remove the additive in the positive active material;
5) active material of crossing after 38.5 μ m sieve promptly got recycling positive electrode in 6 hours through 750 ℃ of-850 ℃ of following roastings in air atmosphere or oxygen atmosphere.
Described organic solvent is N-methyl pyrrolidone or dimethylacetylamide.
Concrete implementation step of the present invention is, after anodal leftover pieces and relic employing mechanical means (cutting or pulverizing) fragmentation, in distilled water or in specific organic solvent, control at a certain temperature will be attached to the positive active material on the aluminium foil matrix with methods such as mechanical agitation or ultrasonic oscillations, additive (conductive agent), adhesive and substrate break away from, again positive active material is separated, the product of gained with the distilled water washing repeatedly, to remove water-soluble adhesive and organic solvent, bake drying, isolate positive active material with mechanical means again, carry out high-temperature process subsequently, obtain to utilize the positive electrode active materials of making electrode once more.
Good effect of the present invention is: 1) whole process of production technology is simple, and production cost is low, remarkable in economical benefits.2) positive active material that reclaims with this method has identical structure and chemical property with the material of making lithium ion secondary battery positive electrode.3) this method can make the active material in anodal leftover pieces and the relic obtain farthest utilizing again.4) organic solvent can be recycled, and the anodal aluminium foil substrate of getting rid of behind the active material also can effectively be reclaimed.5) make battery production producer avoid unnecessary economic loss as far as possible.6) this method can not cause secondary pollution to environment.
Substantive distinguishing features that the present invention gives prominence to and marked improvement can be embodied from following example.But they can not impose any restrictions the present invention.
Description of drawings
Fig. 1 reclaims gained active material charging and discharging curve (the 10th week).
Fig. 2: reclaim gained active material XRD test result.
Embodiment
Embodiment 1:
Getting with the aluminium foil is the anodal leftover pieces relic 200g of matrix, carry out Mechanical Crushing after, in 1000mLN-methyl pyrrolidone solution, soaked one day under the room temperature, be warming up to 140 ℃ then, make active material LiCoO with the mechanical agitation method
2, conductive agent, adhesive separate with matrix.Leave standstill, decant goes out upper solution, water repeatedly washs the lower sediment thing, remove water-soluble binder of part and conductive agent, separate product 100 ℃ of oven dry down in air of back gained, its mixing quality is 150g, remove carbon black and insoluble adhesive with the mechanical flotation method, 850 ℃ of following roastings 6 hours, obtain the 110g active material, account for 73.3% of said mixture quality.XRD structure chart such as Fig. 1 of products obtained therefrom.As positive electrode, lithium metal be to electrode, is prepared into button cell, charges 15 hours under 0.1C, is discharged to 3V under 0.2C with the active material that reclaims gained, its discharge curve as shown in Figure 2, the efficiency for charge-discharge and the capacity in preceding 10 weeks see Table 1.
Embodiment 2:
With the aluminium foil is the anodal leftover pieces and the relic 30g of matrix, carry out mechanical crushing after, (20 ℃) soaked one day in the 1000mL dimethylacetylamide under the room temperature, temperature control makes active material LiCoO at 100 ℃ with the ultrasonic oscillation method then
2, conductive agent, adhesive separate with matrix.Leave standstill, decant repeatedly washs the lower sediment thing with distilled water after going out upper solution, remove water-soluble binder of part and conductive agent, decant goes out distilled water then, 100 ℃ of oven dry down in air, and its mixing quality is 23g, remove carbon black and insoluble adhesive with the mechanical flotation method, 850 ℃ of following roastings 6 hours, obtain the 18g active material, account for 78.3% of said mixture quality.The XRD test result of products obtained therefrom is identical with Fig. 1.As positive electrode, lithium metal be to electrode, is prepared into button cell with the active material that reclaims gained, and charging is 15 hours under 0.1C, is discharged to 3V under 0.2C, and initial capacity is 140mAh/g, still is 135mAh/g when being circulated to for the 10th week.Positive electrode active material material with this method recycling has identical structure and close chemical property with raw material.
Table 1: reclaim gained active material preceding 10 all charge/discharge capacities and efficient
| Sequence number | Charging mAh/g | Discharge mAh/g | Efficient/% |
| 1 | 150.8 | 141.2 | 93.6 |
| 2 | 142.7 | 140.9 | 98.7 |
| 3 | 142.1 | 140.9 | 99.2 |
| 4 | 141.2 | 140.5 | 99.5 |
| 5 | 140.7 | 139.8 | 99.3 |
| 6 | 140.0 | 139.3 | 99.5 |
| 7 | 139.1 | 138.6 | 99.6 |
| 8 | 138.1 | 137.3 | 99.4 |
| 9 | 136.3 | 135.3 | 99.3 |
| 10 | 135.0 | 134.7 | 99.7 |
Claims (3)
1, a kind of lithium ion secondary battery positive electrode leftover pieces and relic reclaim the method for active material, and active substances in cathode materials comprises: LiCo
xNi
1-xO
2, 0≤x≤1 wherein is characterized in that it is through following steps:
1) under the normal temperature with anodal leftover pieces and relic mechanical means fragmentation;
2) at normal temperatures, the relic after the Mechanical Crushing is put into water, the active material in the positive pole, additive and adhesive are separated with matrix with the method for mechanical agitation or ultrasonic oscillation; Perhaps
Relic after the fragmentation being put into organic solvent under the condition of 140-150 ℃ of temperature control of heating carries out mechanical agitation or separates with matrix with the method for ultrasonic oscillation active material, additive and the adhesive with positive pole;
3) wash with water with material after matrix separates, remove water miscible binder of part and additive, separate bake drying in air;
4) with flotation or method for screening, further remove non-water-soluble adhesive and additive;
5) after 38.5 μ m sieve excessively, in air atmosphere or oxygen atmosphere, promptly got recycling positive electrode active materials in 6 hours through 750 ℃ of-850 ℃ of following roastings.
2, reclaim the method for active material according to described lithium ion secondary battery positive electrode leftover pieces of claim 1 and relic, it is characterized in that described organic solvent is N-methyl pyrrolidone or dimethylacetylamide.
3, reclaim the method for active material according to described lithium ion secondary battery positive electrode leftover pieces of claim 1 and relic, it is characterized in that described drying is 100 ℃ of oven dry down in the air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031299725A CN1206765C (en) | 2003-05-29 | 2003-05-29 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031299725A CN1206765C (en) | 2003-05-29 | 2003-05-29 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453897A CN1453897A (en) | 2003-11-05 |
| CN1206765C true CN1206765C (en) | 2005-06-15 |
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|---|---|---|---|
| CNB031299725A Expired - Fee Related CN1206765C (en) | 2003-05-29 | 2003-05-29 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
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Families Citing this family (25)
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| CN100355146C (en) * | 2004-11-29 | 2007-12-12 | 潘树明 | Novel method for regenerating positive material waste of lithium secondary cell |
| CN1332475C (en) * | 2005-09-13 | 2007-08-15 | 天津大学 | Production of LixCoO2 from recovering waste lithium ionic battery |
| WO2007088617A1 (en) * | 2006-02-02 | 2007-08-09 | Kawasaki Plant Systems Kabushiki Kaisha | Method of recovering valuable substance from lithium secondary battery, and recovery apparatus therefor |
| CN100440615C (en) * | 2006-11-01 | 2008-12-03 | 浙江工业大学 | A recovery method for waste lithium ion cell |
| CN101383441B (en) * | 2007-09-06 | 2011-10-26 | 深圳市比克电池有限公司 | Synthetic recovering method for positive pole waste tablet from ferric phosphate lithium cell |
| CN102029283B (en) * | 2010-02-05 | 2012-07-25 | 伟翔环保科技发展(上海)有限公司 | Recycling separation system of lithium battery component materials |
| CN102332623B (en) * | 2011-03-22 | 2013-08-21 | 东莞新能源科技有限公司 | Method for recovering anode material of lithium ion battery |
| CN102569939B (en) * | 2011-07-26 | 2015-03-18 | 圣豹电源有限公司 | Method for recycling active substances of scrapped polar plate of storage battery |
| CN102344172B (en) * | 2011-10-14 | 2013-10-16 | 同济大学 | Method for ultrasonically repairing lithium cobaltite material of failed lithium ion battery |
| CN102403553A (en) * | 2011-11-10 | 2012-04-04 | 大连交通大学 | Decomposing and recycling method of lithium battery electrode material |
| CN103311537A (en) * | 2012-03-16 | 2013-09-18 | 宁波杉杉新材料科技有限公司 | Recycling method of battery positive material, positive pole piece and preparation method thereof |
| CN103633393A (en) * | 2013-12-06 | 2014-03-12 | 河南师范大学 | Recycling process for active material of waste cathode piece of lithium ion battery |
| CN103956533A (en) * | 2014-03-28 | 2014-07-30 | 华南师范大学 | Method for preparing cathode material of lithium ion battery |
| 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 |
| CN104659388A (en) * | 2015-02-04 | 2015-05-27 | 中国华能集团清洁能源技术研究院有限公司 | Method for recycling electrode material blanks of molten carbonate fuel cells |
| CN105870529A (en) * | 2016-05-03 | 2016-08-17 | 深圳市沃特玛电池有限公司 | Recovery method for waste lithium ion batteries |
| 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 |
| US10205200B2 (en) * | 2016-07-07 | 2019-02-12 | Grst International Limited | Method for recycling lithium-ion battery |
| CN106299523A (en) * | 2016-08-24 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | The segregation apparatus of a kind of lithium ion battery plus-negative plate active substance and collector and separation method |
| 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 |
| CN108493507A (en) * | 2018-04-28 | 2018-09-04 | 贵州贵航新能源科技有限公司 | The recovery method of non-poling sheet waste material in lithium ion battery production |
| CN108808153A (en) * | 2018-07-10 | 2018-11-13 | 东莞市丹斯迪新能源有限公司 | A kind of anode slice of lithium ion battery recovery and treatment method |
| CN109411844A (en) * | 2018-10-29 | 2019-03-01 | 山西根复科技有限公司 | A kind of separation method of anode slice of lithium ion battery and active material |
| CN112531159B (en) * | 2021-02-05 | 2021-11-26 | 矿冶科技集团有限公司 | Recycling method and application of waste lithium ion battery |
| CN115818607B (en) * | 2021-10-11 | 2023-10-31 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
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- 2003-05-29 CN CNB031299725A patent/CN1206765C/en not_active Expired - Fee Related
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