CN105186058A - Method for environmentally-friendly resource recycling of lithium ion battery electrodes - Google Patents
Method for environmentally-friendly resource recycling of lithium ion battery electrodes Download PDFInfo
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- CN105186058A CN105186058A CN201410267159.XA CN201410267159A CN105186058A CN 105186058 A CN105186058 A CN 105186058A CN 201410267159 A CN201410267159 A CN 201410267159A CN 105186058 A CN105186058 A CN 105186058A
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- electrode
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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 environmentally-friendly resource recycling of lithium ion battery electrodes. The method comprises the following steps: putting the lithium ion battery electrodes in a high temperature liquid to make electrode materials be disengaged from electrode current collectors and enter the high temperature liquid, adding water to the high temperature liquid, dissolving, and filtering to obtain a filter cake only containing the electrode current collectors and a mixed filtrate containing the high temperature liquid and the electrode materials, or filtering to obtain a mixture containing the electrode materials and the electrode current collectors and a filtrate containing the high temperature liquid, wherein the temperature of the high temperature liquid is not lower than the separation or decomposition temperature of a bonding agent for bonding and fixing the electrode materials, and the electrodes are positive electrodes or negative electrodes. The method has the advantages of high separation efficiency, simple process, environmental protection and low cost, and can solve the pollution and recycling problems of the waste lithium ion battery electrodes.
Description
Technical field
The present invention relates to a kind of recovery method of battery, specifically, relate to a kind of method of lithium ion cell electrode being carried out to resource environmental protection recovery.
Background technology
Now because scrapping of electronic product is more and more, the learies for the lithium ion cell electrode of electronic product is also increasing, and it is also more and more important how lithium ion cell electrode is reclaimed in resource environmental protection.The existing relevant recovery technology about lithium ion cell electrode in prior art; as: Chinese patent application CN01130735.8, denomination of invention are disclose a kind of recovery method in the invention of the method for Footwall drift " from the used Li ion cell "; although this invention also can reach the object reclaiming wherein metal; but in removal process, have employed high temperature furnace roasting; and have employed the means adding acid-soluble erosion; new environmental pollution is not only created in removal process; and cost is high, complex process, is not suitable for scale and reclaims requirement! Therefore, research and develop the resource environmental protection recycling method about lithium ion cell electrode that a kind of efficiency is high, pollution-free, cost is low, by the pollution and resource problem that solve waste lithium ion electrode, there is important value and social effect.
Summary of the invention
The object of the invention is to the defect overcoming prior art, the resource environmental protection recycling method of the lithium ion cell electrode that a kind of separative efficiency is high, technique is simple, pollution-free, cost is low is provided.
For achieving the above object, the present invention adopts following technical scheme:
A resource environmental protection recycling method for lithium ion cell electrode, described lithium ion cell electrode comprises electrode material and electrode current collecting body; Described method is that lithium ion cell electrode is put into high-temp liquid, by the heat effect of high-temp liquid, electrode material is separated from electrode current collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain only containing the filter cake of electrode current collecting body and containing the mixing filtrate of high-temp liquid and electrode material; Cleaning, drying is carried out to the filter cake obtained, namely obtains electrode current collecting body; Secondary filter is carried out to the mixing filtrate containing high-temp liquid and electrode material, namely obtains the filter cake containing electrode material and the filtrate containing high-temp liquid; The temperature of described high-temp liquid is not less than separation for the bonding agent of the electrode material that is adhesively fixed or decomposition temperature, and described electrode is negative or positive electrode.
Another kind of method of lithium ion cell electrode being carried out to resource environmental protection recovery, described lithium ion cell electrode comprises electrode material and electrode current collecting body; Described method is that lithium ion cell electrode is put into high-temp liquid, by the heat effect of high-temp liquid, electrode material is separated from electrode current collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain the mixture filter cake containing electrode material and electrode current collecting body and the filtrate containing high-temp liquid; Carry out screening process after cleaning, drying is carried out to the mixture filter cake obtained again, namely obtain electrode material and the electrode current collecting body of separation; The temperature of described high-temp liquid is not less than separation for the bonding agent of the electrode material that is adhesively fixed or decomposition temperature, and described electrode is negative or positive electrode.
Because electrode material is Powdered, and electrode current collecting body is graininess or sheet, therefore can realize above-mentioned two schemes by the mesh size adjusting screen pack.
Of the present invention also have following improvement to the method that lithium ion cell electrode carries out resource environmental protection recovery:
1, in the container holding high-temp liquid, separation net is provided with.The electrode current collecting body being graininess or sheet can be tackled and only allow pulverous electrode material to pass through by separation net, is taken out from container by separation net and directly can obtain the separated electrode current collecting body got off, can increase work efficiency.
2, described high-temp liquid is fuse salt.Because of fuse salt at high temperature stable performance, cost is low, and fail safe is high.
3, described fuse salt selective chlorination salt or the salt-mixture of chlorate.Because chlorate low price, as sodium chloride, calcium chloride etc., raw material sources are extensive.
4, all there is not chemical reaction, to ensure reclaimed product purity and recycle value in described high-temp liquid and electrode material and electrode current collecting body.
5, when the electrode material obtained is positive electrode, the bonding agent wherein remained is made to decompose removing by heated oxide.Because separating obtained positive electrode can remain the decompose residues of some bonding agents or bonding agent as carbon etc., it can be made to become carbon dioxide by the oxidation processes of high temperature and vapor away, thus improve gained positive electrode as the purity of lithium salts.Certainly, oxygen can be added when high temperature oxidation process to improve the effect of oxidation processes.
6, when described electrode current collecting body is aluminium foil, the temperature of described high-temp liquid is higher than the fusing point of aluminium.Because the thickness of aluminium foil is very thin, adopt conventional method to reclaim in atmosphere, as heating recovery is easily oxidized, the rate of recovery is low, causes the wasting of resources.After the temperature of described high-temp liquid is higher than the fusing point of aluminium, aluminium foil will be fused into alumina particles, when alumina particles fusing is reclaimed, has that loss is little, rate of finished products advantages of higher, thus can improve its recovery value.
7, evaporation and concentration is carried out to the filtrate containing high-temp liquid, to recycle high-temp liquid.
Compared with prior art, the present invention has following beneficial effect:
1, environmental protection: in removal process, does not have waste water, waste gas and waste residue to produce.
2, resource: electrode current collecting body wherein and electrode material are all recycled.
3, cost is low: owing to not adding in whole removal process and consuming any chemicals, cost recovery is low.
Accompanying drawing explanation
Fig. 1 is a kind of process chart lithium ion cell positive being carried out to resource environmental protection recovery that embodiment 1 provides.
Fig. 2 is a kind of process chart lithium ion battery negative being carried out to resource environmental protection recovery that embodiment 2 provides.
Fig. 3 is another kind that embodiment 3 provides carries out resource environmental protection recovery process chart to lithium ion cell positive.
Fig. 4 is another kind that embodiment 4 provides carries out resource environmental protection recovery process chart to lithium ion battery negative.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is further elaborated:
Embodiment 1
With reference to shown in Fig. 1: the present embodiment provide a kind of to carry out the technological process of resource environmental protection recovery to lithium ion cell positive as follows: put into by lithium ion cell positive in high-temp liquid, the temperature of described high-temp liquid is greater than the fusing point of aluminium; By the heat effect of high-temp liquid, plus plate current-collecting body aluminium foil fusing wherein, the positive electrode sticked to above plus plate current-collecting body enters in high-temp liquid as cobalt acid lithium will separate; Water is added in high-temp liquid, form the aqueous solution by the dissolving of water, once filter, so-called once filtration is exactly the mesh size by controlling filter screen, make that positive electrode can filter and aluminum shot can not filter, obtain aluminum shot filter cake and the mixing filtrate containing positive electrode and high-temp liquid; Aluminum shot filter cake is carried out cleaning, drying, namely obtains aluminium block; Secondary filter is carried out to mixing filtrate, namely obtains containing positive electrode as the filter cake of lithium salts and the filtrate containing high-temp liquid; Cleaning, drying is carried out to filter cake, then heated oxide process, namely obtain the positive electrode of high-load, as: cobalt acid lithium powder; Carry out evaporation and concentration process to containing the filtrate of high-temp liquid, recyclablely obtain high-temp liquid, to recycle.
Embodiment 2
With reference to shown in Fig. 2: the present embodiment provide a kind of to carry out the technological process of resource environmental protection recovery to lithium ion battery negative as follows: lithium ion battery negative is joined in high-temp liquid, the temperature general control of high-temp liquid is between 450 DEG C ~ 700 DEG C, the bonding agent of bonding negative material can be made at these temperatures to decompose, cause the negative material sticked on negative current collector to separate and enter in high-temp liquid; Water is added in high-temp liquid, by the dissolution of water, form the aqueous solution, once filter, can obtain the filter cake containing negative current collector and the mixing filtrate containing negative material and high-temp liquid, so-called once filtration is exactly allow negative material filters by the size of controlled filter mesh and negative current collector can not filter; After filter cake containing negative current collector is carried out cleaning, drying, namely obtain negative current collector, as: Copper Foil; Mixing filtrate is carried out secondary filter, namely obtains the filter cake containing negative material and the filtrate containing high-temp liquid; Cleaning, drying is carried out to filter cake, namely obtains negative material; Carry out evaporation and concentration process to containing the filtrate of high-temp liquid, recyclablely obtain high-temp liquid, to recycle.
Embodiment 3
With reference to shown in Fig. 3: the technological process that the another kind that the present embodiment provides carries out resource environmental protection recovery to lithium ion cell positive is as follows: put into by lithium ion cell positive in high-temp liquid, the temperature of high-temp liquid is higher than the fusing point of aluminium; By the heat effect of high-temp liquid, make plus plate current-collecting body aluminium foil fusing wherein, cause the positive electrode lithium salts sticked to above plus plate current-collecting body to enter in high-temp liquid as cobalt acid lithium separates; In high-temp liquid, add water, form the aqueous solution by the dissolving of water, filter, obtain the mixture filter cake containing positive electrode and plus plate current-collecting body and contain the filtrate of high-temp liquid; Screening process is carried out again after cleaning, drying is carried out to obtained mixture filter cake; Because positive electrode is Powdered, not identical with proportion with the size of plus plate current-collecting body aluminum shot, therefore both can be separated by screening, obtain aluminum shot and fine powder; Heated oxide process is carried out to fine powder, makes the bonding agent wherein remained be oxidized to carbon dioxide volatilization, namely obtain the positive electrode of high-load, as: cobalt acid lithium powder; Carry out evaporation and concentration process to containing the filtrate of high-temp liquid, recyclablely obtain high-temp liquid, to recycle.
Embodiment 4
With reference to shown in Fig. 4: the technological process that the another kind that the present embodiment provides carries out resource environmental protection recovery to lithium ion battery negative is as follows: joined by lithium ion battery negative in high-temp liquid, the temperature general control of high-temp liquid is between 450 DEG C ~ 700 DEG C, the bonding agent of bonding negative material can be made at these temperatures to decompose, the negative material sticked on negative pole is separated from negative current collector and enters in high-temp liquid; In high-temp liquid, add water, by the dissolution of water, form the aqueous solution, filter, obtain the mixture filter cake containing negative material and negative current collector and contain the filtrate of high-temp liquid; Screening process is carried out again after cleaning, drying is carried out to obtained mixture filter cake; Because negative material is Powdered, not identical with proportion with the size of negative current collector Copper Foil, therefore both can be separated by screening, obtain Copper Foil and the negative material of separation; Carry out evaporation and concentration process to containing the filtrate of high-temp liquid, recyclablely obtain high-temp liquid, to recycle.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (9)
1. lithium ion cell electrode is carried out to a method for resource environmental protection recovery, described lithium ion cell electrode comprises electrode material and electrode current collecting body; It is characterized in that: described method is that lithium ion cell electrode is put into high-temp liquid, by the heat effect of high-temp liquid, electrode material is separated from electrode current collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain only containing the filter cake of electrode current collecting body and containing the mixing filtrate of high-temp liquid and electrode material; Cleaning, drying is carried out to the filter cake obtained, namely obtains electrode current collecting body; Secondary filter is carried out to the mixing filtrate containing high-temp liquid and electrode material, namely obtains the filter cake containing electrode material and the filtrate containing high-temp liquid; The temperature of described high-temp liquid is not less than separation for the bonding agent of the electrode material that is adhesively fixed or decomposition temperature, and described electrode is negative or positive electrode.
2. lithium ion cell electrode is carried out to a method for resource environmental protection recovery, described lithium ion cell electrode comprises electrode material and electrode current collecting body; It is characterized in that: described method is that lithium ion cell electrode is put into high-temp liquid, by the heat effect of high-temp liquid, electrode material is separated from electrode current collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain the mixture filter cake containing electrode material and electrode current collecting body and the filtrate containing high-temp liquid; Carry out screening process after cleaning, drying is carried out to the mixture filter cake obtained again, namely obtain electrode material and the electrode current collecting body of separation; The temperature of described high-temp liquid is not less than separation for the bonding agent of the electrode material that is adhesively fixed or decomposition temperature, and described electrode is negative or positive electrode.
3. method as claimed in claim 1 or 2, is characterized in that: in the container holding high-temp liquid, be provided with separation net.
4. method as claimed in claim 1 or 2, is characterized in that: described high-temp liquid is fuse salt.
5. method as claimed in claim 4, is characterized in that: described fuse salt is the salt-mixture of chlorate or chlorate.
6. method as claimed in claim 1 or 2, is characterized in that: described high-temp liquid and electrode material and electrode current collecting body all chemical reaction do not occur.
7. method as claimed in claim 1 or 2, is characterized in that: when the electrode material obtained is positive electrode, makes the bonding agent wherein remained decompose removing by heated oxide.
8. method as claimed in claim 1 or 2, is characterized in that: when described electrode current collecting body is aluminium foil, and the temperature of described high-temp liquid is higher than the fusing point of aluminium.
9. method as claimed in claim 1 or 2, is characterized in that: carry out evaporation and concentration to the filtrate containing high-temp liquid, to recycle high-temp liquid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410267159.XA CN105186058B (en) | 2014-06-16 | 2014-06-16 | The method that a kind of pair of lithium ion cell electrode carries out recycling environmental protection recycling |
| PCT/CN2015/081421 WO2015192743A1 (en) | 2014-06-16 | 2015-06-15 | Resource reclamation and environmental protection method for recycling lithium ion battery wastes |
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| CN201410267159.XA CN105186058B (en) | 2014-06-16 | 2014-06-16 | The method that a kind of pair of lithium ion cell electrode carries out recycling environmental protection recycling |
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| CN105186058A true CN105186058A (en) | 2015-12-23 |
| CN105186058B CN105186058B (en) | 2019-01-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654433A (en) * | 2016-11-21 | 2017-05-10 | 电子科技大学中山学院 | Method for recovering lithium by adopting waste lithium iron phosphate batteries |
| CN106941198A (en) * | 2016-01-04 | 2017-07-11 | 上海奇谋能源技术开发有限公司 | A kind of method that utilization thermal cracking reclaims lithium ion battery discarded object |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058396A (en) * | 1976-11-26 | 1977-11-15 | Electric Power Research Institute, Inc. | Recovery of lead from batteries |
| CN101336496A (en) * | 2006-02-02 | 2008-12-31 | 川崎设备系统株式会社 | Recycling method and apparatus for precious material recycling from lithium secondary battery |
| CN103311600A (en) * | 2013-05-16 | 2013-09-18 | 清华大学 | Method and device for recycling metal in waste lithium ion batteries by water-soluble ionic liquid |
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2014
- 2014-06-16 CN CN201410267159.XA patent/CN105186058B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058396A (en) * | 1976-11-26 | 1977-11-15 | Electric Power Research Institute, Inc. | Recovery of lead from batteries |
| CN101336496A (en) * | 2006-02-02 | 2008-12-31 | 川崎设备系统株式会社 | Recycling method and apparatus for precious material recycling from lithium secondary battery |
| CN103311600A (en) * | 2013-05-16 | 2013-09-18 | 清华大学 | Method and device for recycling metal in waste lithium ion batteries by water-soluble ionic liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106941198A (en) * | 2016-01-04 | 2017-07-11 | 上海奇谋能源技术开发有限公司 | A kind of method that utilization thermal cracking reclaims lithium ion battery discarded object |
| CN106654433A (en) * | 2016-11-21 | 2017-05-10 | 电子科技大学中山学院 | Method for recovering lithium by adopting waste lithium iron phosphate batteries |
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