CN105226344B - A kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite - Google Patents

A kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite Download PDF

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Publication number
CN105226344B
CN105226344B CN201510749514.1A CN201510749514A CN105226344B CN 105226344 B CN105226344 B CN 105226344B CN 201510749514 A CN201510749514 A CN 201510749514A CN 105226344 B CN105226344 B CN 105226344B
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China
Prior art keywords
mixed material
graphite
lithium ion
fine fraction
cobalt
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CN201510749514.1A
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Chinese (zh)
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CN105226344A (en
Inventor
陈稳
王海锋
张文光
高博
杨兴
张鹏德
吴瑞瑞
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 present invention discloses a kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite, comprises the following steps：A. waste and old lithium ion battery discharged, disassembled, crushed, form mixed material；B. mixed material is sieved, obtains fine fraction mixed material；C. the fine fraction mixed material engaging friction charge device obtained carries out charged；D. the fine fraction mixed material after charged is sorted into electrostatic separator；E. cobalt acid lithium and graphite are collected respectively in electrostatic separator product collecting tank.Preparation is simple before sorting, it is only necessary to crushing and screening, can save many times, and crushing function using size fractionated makes lithium ion battery broken complete, substantially increases the efficiency sorted afterwards；Fine fraction mixed material is obtained after being sieved using particle size differences, then carries out friction electrical selection, can not only fully reclaim the cobalt acid lithium and graphite of lithium ion battery, and is sorted only in fine fraction mixed material, positive effect, it is convenient to collect.

Description

A kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite
Technical field
The present invention relates to a kind of recovery method, more particularly to the recovery of a kind of cobalt in waste lithium ion batteries acid lithium and graphite Method.
Background technology
Country《Prevention and control of environmental pollution by solid wastes method》Described in reply solid waste implement minimizing, recycling, Harmless treatment, scientific utilization electronic waste, it will be that Resources for construction circular form is sustainable as the important supplement of Resources Develop the important measure of society.
Current research method both domestic and external mainly has：Floatation, polishing, pyrogenic process, organic solvent method, the precipitation method, extraction Method, salting out method, ion-exchange, electrochemical process, Bioleaching method.
Chemical agent is largely used in these existing methods that valuable metal is reclaimed from used Li ion cell, such as： Sulfuric acid adds hydrogen peroxide, sodium thiosulfate, hydrochloric acid, the useless LiCoO2 of nitric acid dissolving, is inevitably generated in leaching process containing acid gas Body, Cl2 or NOx waste gas, cause serious secondary pollution in removal process to environment.In addition, the subsequent treatment of leachate Process is more, long flow path causes cost recovery height；Leaching process all uses to improve metal recovery rate and shorten extraction time Higher acid concentration and extraction temperature, this requires very high to leaching equipment corrosion-resistant.Using useless LiCoO2 powder and alkali metal The method that is calcined after the mixing of the salt of sodium and potassium, there is the salt dosage of alkali metallic sodium in roasting process and potassium is big, in removal process Precipitating reagent oxalates dosage is more, the shortcomings that causing cost recovery high；Using useless LiCoO2 materials and natural organic acids and hydrogen peroxide Ball grinding technique after mixing, the shortcomings that removal process is easily corroded ball-grinding machine and introduces impurity be present.
The content of the invention
In view of the above-mentioned problems of the prior art, the present invention provides a kind of cobalt in waste lithium ion batteries acid lithium and graphite Recovery method, it is not necessary to chemicals treatment, meet the requirement of environmental protection now；Technique is simple, power consumption is low and does not have to water, excludes Sewage handling problem, reduces cost.
To achieve these goals, the technical solution adopted by the present invention is：A kind of cobalt in waste lithium ion batteries acid lithium and The recovery method of graphite, comprises the following steps：
A. waste and old lithium ion battery discharged, disassembled, crushed, form mixed material；
B. mixed material is sieved, obtains fine fraction mixed material；
C. the fine fraction mixed material engaging friction charge device obtained carries out charged；
D. the fine fraction mixed material after charged is sorted into electrostatic separator；
E. cobalt acid lithium and graphite are collected respectively in electrostatic separator product collecting tank.
Whole method is using air-flow as material conveying and friction charged carrier.
The adjustable range of described electrostatic separator two-plate voltage is 10-60kv.
There is advantages below compared with prior art：Preparation very simple before sorting, it is only necessary to crush, screening is Can, many times can be saved, improve efficiency, and crushing function using size fractionated makes lithium ion battery broken complete, greatly Improve the efficiency sorted afterwards greatly；Fine fraction mixed material is obtained after being sieved using particle size differences, then carries out friction electricity Choosing, can not only fully reclaim the cobalt acid lithium and graphite of lithium ion battery, and be sorted only in fine fraction mixed material, Positive effect, it is convenient to collect；The present invention utilizes the difference of cobalt acid lithium and Graphite friction charge characteristics in lithium ion battery to realize not With the separation of component, fine fraction mixed material is sorted, waste and old lithium ion battery is recycled, this method is not Chemicals treatment is needed, technique is simple, power consumption is low and does not have to water, will not produce pollution to environment, reduce cost；Will not during sorting Other additional compounds are produced because of chemical change, separating purity is high.In addition, involved device is simple, floor space is small, Generalization is strong, has preferable application prospect.
Brief description of the drawings
Fig. 1 is the workflow diagram of the present invention.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.
As shown in figure 1, the recovery method of this cobalt in waste lithium ion batteries acid lithium and graphite, specifically includes following steps：
A. waste and old lithium ion battery discharged, disassembled, crushed, form mixed material；
B. mixed material is sieved, obtains fine fraction mixed material, this step is sieved for physics, it is therefore an objective to avoids grain Spend when the coarse fraction material to differ greatly separates in the electric field and interfere；
C. the fine fraction mixed material engaging friction charge device progress obtained is charged, and this step is by fine fraction mixture Material carries out friction charged process；
D. the fine fraction mixed material after charged is sorted into electrostatic separator, it is therefore an objective to utilizes material in the electric field The difference of friction charged property sorts to mixed material；
E. cobalt acid lithium and graphite are collected respectively in electrostatic separator product collecting tank.
Whole method is using air-flow as material conveying and friction charged carrier.
Resulting fine particle stage material is mainly the mixture of cobalt acid lithium and graphite after screening, utilizes cobalt acid lithium and graphite particle The difference of friction charged property is separated fine fraction mixed material in the electric field, according to the more of preliminary experiment products therefrom species Design corresponding collection device less, in voltage range be adjusted in 10-60kv, collect final product i.e. can obtain purity compared with High valuable component.
Step a and b can use it is artificial disassemble directly can also be carried out in coarse fraction disintegrating machine it is broken after continue thin Crushed in grade disintegrating machine, obtain fine fraction mixed material, in accordance with the above fine fraction mixed material in method and step c It when carrying out charged, can be carried out in different charge devices charged, increase its charge capacity, give full play to its feature； Fine particle stage material after charged in method and step d in accordance with the above is sorted into electrostatic separator, wherein electrostatic separation Machine can be different pan feeding modes, be designed according to the charge device in step c；In accordance with the above in method and step d The voltage regulation limits of the electrostatic separator of design are 10-60kv, in accordance with the above in each electrostatic separation in method and step e Different materials is collected in machine respectively, is the specific species that material is determined according to trial test, then designs corresponding collection device.
The instantiation that content of the present invention is proposed, only it is used for illustrating technology contents, rather than the limit by invention narrow sense It is fixed under the premise without departing from the principles of the invention, some improvements and modifications to be made in the above-described embodiments, these improvement Protection scope of the present invention is also should be regarded as with retouching.

Claims (2)

  1. A kind of 1. recovery method of cobalt in waste lithium ion batteries acid lithium and graphite, it is characterised in that：Comprise the following steps：
    A. waste and old lithium ion battery discharged, disassembled, crushed, form mixed material；
    B. mixed material is sieved, obtains fine fraction mixed material；
    C. the fine fraction mixed material engaging friction charge device obtained carries out charged；
    D. the fine fraction mixed material after charged is sorted into electrostatic separator；
    E. cobalt acid lithium and graphite are collected respectively in electrostatic separator product collecting tank；
    Whole method is using air-flow as material conveying and friction charged carrier.
  2. 2. the recovery method of cobalt in waste lithium ion batteries acid lithium according to claim 1 and graphite, it is characterised in that：Institute The adjustable range for the electrostatic separator two-plate voltage stated is 10-60kv.
CN201510749514.1A 2015-11-09 2015-11-09 A kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite Expired - Fee Related CN105226344B (en)

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CN201510749514.1A CN105226344B (en) 2015-11-09 2015-11-09 A kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite

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Application Number Priority Date Filing Date Title
CN201510749514.1A CN105226344B (en) 2015-11-09 2015-11-09 A kind of recovery method of cobalt in waste lithium ion batteries acid lithium and graphite

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Publication number Priority date Publication date Assignee Title
CN105914419B (en) * 2016-07-04 2018-12-14 首都师范大学 A kind of waste lithium cell efficient separation recyclable device
CN107293817A (en) * 2017-06-08 2017-10-24 深圳市恒创睿能环保科技有限公司 A kind of waste and old lithium ion battery each component is efficiently dissociated and classified reclaiming method
CN107275703A (en) * 2017-06-08 2017-10-20 深圳市恒创睿能环保科技有限公司 A kind of method that electrode material is reclaimed from waste lithium ion
CN108110356B (en) * 2017-12-08 2024-02-06 天齐锂业股份有限公司 Full-automatic waste lithium ion battery recycling process and system
CN111525207B (en) * 2020-04-16 2021-10-08 宁波诺丁汉大学 Lithium ion power battery recovery method
CN112086702B (en) 2020-08-11 2021-12-17 广东邦普循环科技有限公司 Automatic fine and deep sorting method and device for power batteries
CN114700179B (en) * 2022-03-21 2023-09-15 国网河南省电力公司电力科学研究院 Method for separating and recovering positive and negative active substances of waste lithium iron phosphate
CN115911283B (en) * 2022-11-17 2023-09-22 中国矿业大学 Dry modification and quality improvement method for battery cathode production raw material

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CN1247326C (en) * 2003-04-11 2006-03-29 中国矿业大学 Dry physical recovery process for recovering valuable components from waste electronic board card
JP4749118B2 (en) * 2005-10-27 2011-08-17 新日本製鐵株式会社 Electrostatic separation method and electrostatic separation device
CN101011681B (en) * 2006-02-05 2011-11-02 中国矿业大学 Fine granule material friction electrical selection method and device
CN102569940B (en) * 2011-01-20 2014-03-12 常州翔宇资源再生科技有限公司 Method for recycling negative electrode material of waste lithium ion battery
CN104577249B (en) * 2015-01-14 2017-01-11 上海交通大学 Method for recycling waste lithium cobalt oxide lithium ion battery

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