CN104485492A - Method for separating electrode material and current collector of waste lithium ion battery - Google Patents

Method for separating electrode material and current collector of waste lithium ion battery Download PDF

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Publication number
CN104485492A
CN104485492A CN201410722580.5A CN201410722580A CN104485492A CN 104485492 A CN104485492 A CN 104485492A CN 201410722580 A CN201410722580 A CN 201410722580A CN 104485492 A CN104485492 A CN 104485492A
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China
Prior art keywords
electrode
collector
lithium ion
ion battery
current
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CN201410722580.5A
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CN104485492B (en
Inventor
蒋力
高云芳
林炜
章嘉纯
朱云
罗威
李德鹏
徐羚
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention discloses a method for separating an electrode material and a current collector of a waste lithium ion battery. The method comprises following steps: (1) adding water into an electrolytic tank, and adding a supporting electrolyte, wherein the supporting electrolyte is nitrate or sulfate; (2) putting a waste lithium ion battery electrode slice into the two poles of the electrolytic tank, wherein the battery electrode slice comprises the current collector and an electrode material; (3) applying a current with characteristic change to the two poles of the electrolytic tank for electrolyzing for 10-100 min, wherein the current with characteristic change is periodical-change rectangular wave current or triangular wave current, the current density is 1mA/cm<2>-500mA/cm<2>; and (4) electrolyzing until the electrode material falls from the surface of the current collector, taking out the current collector and the electrode material from the electrolytic tank, and separating the current collector and the electrode material. The method for separating the electrode material and current collector of the waste lithium ion battery can be used for effectively lowering the cost and improving the separation effect, and is favorable in environmental friendliness.

Description

A kind of method of separating waste, worn lithium ion battery electrode material and collector
Technical field
The invention belongs to the recycling field of waste and old lithium ion battery, be specifically related to a kind of method of separating waste, worn lithium ion battery electrode material and collector.
Background technology
Lithium ion battery is since 20 end of the centurys realized commercialization, it, to have that energy density is large, quality is light, the life-span is long and the plurality of advantages such as without memory, is widely used in the portable electric appts such as mobile phone, notebook computer, camera and electric automobile.Usually containing cobalt, nickel, lithium, organic solvent, plastic or other material in waste and old lithium ion battery, there is higher recycling and be worth.In addition, also containing noxious substances such as lithium hexafluoro phosphates, can cause severe contamination to environment and the ecosystem, the metals such as cobalt, nickel, lithium, copper, aluminium also can pass through biomagnification harm humans self.Along with lithium ion battery applications is increasingly extensive, in Co, Ni in recovery lithium ion battery, Mn, Li, Cu, Al, electrolyte, organic solvent etc. have valency material, reduce pollution on the environment, alleviate the problems such as scarcity of resources and there is important society and economic implications.
Lithium ion battery generally comprises with lower component: positive pole, negative pole, electrolyte, barrier film, anode ear, negative electrode lug, insulating trip, safety valve, center terminal, battery case etc., both positive and negative polarity barrier film separates rear winding and forms.Positive pole is containing about 88% (mass fraction, positive active material down together), the acetylene black conductor of 7% ~ 8%, the organic binder bond of 3% ~ 4%, main component is Kynoar (PVDF), polytetrafluoroethylene (PTFE) etc.Positive electrode is coated in 20 μm of thick aluminum foil current collector.Negative pole contains the negative electrode active material carbon materials of about 90%, and the acetylene black conductor of 4% ~ 5%, the binding agent of 6% ~ 7%, coats in the copper foil current collector of thick 15 μm.Diaphragm material is porous polyethylene or polypropylene.Electrolyte is made up of electrolyte and organic solvent, and electrolyte is generally 1mol/L lithium hexafluoro phosphate, and organic solvent is carbonates.
For the recycling of waste and old lithium ion battery, particularly the method for separating waste, worn lithium ion battery electrode material and collector, is in the stage of fumbling.As the waste lithium ion battery electrode material of application publication number involved by the patents such as CN102208706A, CN102347521A, CN102403553A, CN101383441B and the separation method of collector, mainly contain three classes: (1) is by organic solvent dissolution binding agent, thus electrode material is come off from collection liquid surface, this method not only easily brings various pollution, and organic solvent price is high, is difficult to practical application; (2) by high-temperature heating de-carbon, except binding agent, thus make electrode material come off from collection liquid surface, this method energy consumption is large, and separating effect is very poor; (3) collector is dissolved by acid or alkali, thus separate mesh electrode material and collector, this method destroys collector, and the use of soda acid can produce a large amount of pollutant.
Summary of the invention
In order to the deficiency that the cost of the separate mode overcoming existing waste lithium ion battery electrode material and collector is high, separating effect is poor, the feature of environmental protection is poor, the invention provides the method a kind ofly effectively reducing costs, promote the good separating waste, worn lithium ion battery electrode material of separating effect, the feature of environmental protection and collector.
The technical solution adopted for the present invention to solve the technical problems is:
A method for separating waste, worn lithium ion battery electrode material and collector, said method comprising the steps of:
(1) add water in a cell, then add supporting electrolyte, described supporting electrolyte is nitrate or sulfate;
(2) waste and old lithium ion battery electrode slice is placed in electrolytic cell the two poles of the earth, described battery electrode sheet comprises collector and electrode material;
(3) the current electroanalysis 10 ~ 100min of changing features is added at electrolytic cell the two poles of the earth; The electric current of described changing features is periodically variable square wave current or triangular current, current density size 1mA/cm 2~ 500mA/cm 2;
(4) after electrolysis to electrode material comes off from collection liquid surface, collector, electrode material are taken out from electrolysis tank, disjoint set fluid and electrode material.
Further, in described step (4), the method for separation adopts bolting, FLOTATION SEPARATION or sonic oscillation.
Further again, described waste and old lithium ion battery electrode slice is positive plate or negative plate, and size is 0.1cm 2~ 400cm 2; Described negative plate comprises Cu collector and negative material, and described positive plate comprises Al collector and positive electrode.
Described electrode material comprises electrode active material, conductive agent and binding agent.
Beneficial effect of the present invention is mainly manifested in: effectively reduce costs, promote separating effect, the feature of environmental protection is good.
Accompanying drawing explanation
The I-t figure of adoptable square wave current when Fig. 1 is electrolysis.
The I-t figure of adoptable triangular current when Fig. 2 is electrolysis.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
See figures.1.and.2, a kind of method of separating waste, worn lithium ion battery electrode material and collector, said method comprising the steps of:
(1) add water in a cell, then add supporting electrolyte, described supporting electrolyte is nitrate or sulfate.
(2) waste and old lithium ion battery electrode slice is placed in electrolytic cell the two poles of the earth, described battery electrode sheet comprises collector and electrode material;
(3) the current electroanalysis 10 ~ 100min of changing features is added at electrolytic cell the two poles of the earth; The electric current of described changing features is periodically variable square wave current or triangular current, current density size 1mA/cm 2~ 500mA/cm 2;
(4) after electrolysis to electrode material comes off from collection liquid surface, collector, electrode material are taken out from electrolysis tank, disjoint set fluid and electrode material.
Further, in described step (4), the method for separation adopts bolting, FLOTATION SEPARATION or sonic oscillation.
Further again, described waste and old lithium ion battery electrode slice is positive plate or negative plate, and size is 0.1cm 2~ 400cm 2; Described negative plate comprises Cu collector and negative material, and described positive plate comprises Al collector and positive electrode.
Described electrode material comprises electrode active material, conductive agent and binding agent.
Described supporting electrolyte is Na 2sO 4or KNO 3, certainly, also can be other nitrate or sulfate.
Example 1: add water in a cell, then add Na 2sO 4to saturated; Get two panels battery cathode sheet (containing Cu collector and negative material), claim two electrode slice quality are 1.1g, size is 0.1cm 2; Got battery cathode sheet is placed in electrolytic cell the two poles of the earth, adds square wave current as shown in Figure 1 and carry out electrolysis, controlling copper current collector surface current density size is-30mA/cm 2~+30mA/cm 2, after electrolysis 10min, electrode material is substantially complete to come off from collection liquid surface, collector, electrode material is taken out from electrolysis tank, with bolting, and disjoint set fluid and electrode material.Described electrode material comprises electrode active material, conductive agent and binding agent.
The collector rate of recovery is 88%, and the electrode material rate of recovery is 99%.
Example 2: add water in a cell, then add KNO 3to saturated; Get two panels battery cathode sheet (containing Cu collector and negative material), claim two electrode slice quality are 1.3g, size is 10cm 2; Got battery cathode sheet is placed in electrolytic cell the two poles of the earth, adds triangular current as shown in Figure 2 and carry out electrolysis, controlling copper current collector surface current density size is-100mA/cm 2~+100mA/cm 2, after electrolysis 100min, electrode material is substantially complete to come off from collection liquid surface, collector, electrode material is taken out from electrolysis tank, by FLOTATION SEPARATION, and disjoint set fluid and electrode material.Described electrode material comprises electrode active material, conductive agent and binding agent.
The collector rate of recovery is 92%, and the electrode material rate of recovery is 98%.
Example 3: add water in a cell, then add Na 2sO 4to saturated; Get two panels battery anode slice (containing Al collector and positive electrode), claim two electrode slice quality are respectively 0.54g, 0.56g, size is 100cm 2; Got battery anode slice is placed in electrolytic cell the two poles of the earth, adds saw-tooth current as shown in Figure 2 and carry out electrolysis, controlling copper current collector surface current density size variation interval is-1A/cm 2~+1mA/cm 2, after electrolysis 20min, electrode material is substantially complete to come off from collection liquid surface, collector, electrode material is taken out from electrolysis tank, ultrasonic vibration mechanical agitation 10min, then uses floatation disjoint set fluid and electrode material.Described electrode material comprises electrode active material, conductive agent and binding agent.
The collector rate of recovery is 82%, and the electrode material rate of recovery is 95%.
Example 4: add water in a cell, then add Na 2sO 4to saturated; Get two panels battery anode slice (containing Al collector and positive electrode), claim two electrode slice quality are respectively 0.54g, 0.56g, size is 400cm 2; Got battery anode slice is placed in electrolytic cell the two poles of the earth, adds square wave current as shown in Figure 1 and carry out electrolysis, controlling copper current collector surface current density size variation interval is-500A/cm 2~+500mA/cm 2, after electrolysis 100min, electrode material is substantially complete to come off from collection liquid surface, collector, electrode material is taken out from electrolysis tank, ultrasonic vibration mechanical agitation 5min, then uses floatation disjoint set fluid and electrode material.Described electrode material comprises electrode active material, conductive agent and binding agent.
The collector rate of recovery is 89%, and the electrode material rate of recovery is 94%.

Claims (4)

1. a method for separating waste, worn lithium ion battery electrode material and collector, is characterized in that, said method comprising the steps of:
(1) add water in a cell, then add supporting electrolyte, described supporting electrolyte is nitrate or sulfate;
(2) waste and old lithium ion battery electrode slice is placed in electrolytic cell the two poles of the earth, described battery electrode sheet comprises collector and electrode material;
(3) the current electroanalysis 10 ~ 100min of changing features is added at electrolytic cell the two poles of the earth; The electric current of described changing features is periodically variable square wave current or triangular current, current density size 1mA/cm 2~ 500mA/cm 2;
(4) after electrolysis to electrode material comes off from collection liquid surface, collector, electrode material are taken out from electrolysis tank, disjoint set fluid and electrode material.
2. the method for separating waste, worn lithium ion battery electrode material as claimed in claim 1 and collector, is characterized in that: in described step (4), and the method for separation adopts bolting, FLOTATION SEPARATION or sonic oscillation.
3. the method for separating waste, worn lithium ion battery electrode material as claimed in claim 1 or 2 and collector, it is characterized in that: described waste and old lithium ion battery electrode slice is positive plate or negative plate, size is 0.1cm 2~ 400cm 2; Described negative plate comprises Cu collector and negative material, and described positive plate comprises Al collector and positive electrode.
4. the method for separating waste, worn lithium ion battery electrode material as claimed in claim 1 or 2 and collector, is characterized in that: described electrode material comprises electrode active material, conductive agent and binding agent.
CN201410722580.5A 2014-12-03 2014-12-03 A kind of separating waste, worn lithium ion battery electrode material and the method for collector Active CN104485492B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099234A (en) * 2016-08-11 2016-11-09 合肥国轩高科动力能源有限公司 Positive electrode and the method for aluminum collector in a kind of electrolytic separation waste and old lithium ion battery
CN106207301A (en) * 2016-08-11 2016-12-07 合肥国轩高科动力能源有限公司 The negative material of a kind of electrolytic recovery waste and old lithium ion battery and the method for Copper Foil
CN106252770A (en) * 2016-08-11 2016-12-21 合肥国轩高科动力能源有限公司 A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101488597A (en) * 2009-02-23 2009-07-22 东南大学 Method for waste lead-acid cell resourcization and lead-acid cell cyclic production
CN102382987A (en) * 2011-10-26 2012-03-21 北京理工大学 Method for recovering and regenerating positive electrode material of lithium ion battery
CN103413990A (en) * 2013-07-22 2013-11-27 浙江工业大学 Method used for recycling current collectors of used lithium ion batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101488597A (en) * 2009-02-23 2009-07-22 东南大学 Method for waste lead-acid cell resourcization and lead-acid cell cyclic production
CN102382987A (en) * 2011-10-26 2012-03-21 北京理工大学 Method for recovering and regenerating positive electrode material of lithium ion battery
CN103413990A (en) * 2013-07-22 2013-11-27 浙江工业大学 Method used for recycling current collectors of used lithium ion batteries

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099234A (en) * 2016-08-11 2016-11-09 合肥国轩高科动力能源有限公司 Positive electrode and the method for aluminum collector in a kind of electrolytic separation waste and old lithium ion battery
CN106207301A (en) * 2016-08-11 2016-12-07 合肥国轩高科动力能源有限公司 The negative material of a kind of electrolytic recovery waste and old lithium ion battery and the method for Copper Foil
CN106252770A (en) * 2016-08-11 2016-12-21 合肥国轩高科动力能源有限公司 A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector

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