CN105576312A - Method for recovering positive electrode and negative electrode mixture of waste lithium ion battery - Google Patents
Method for recovering positive electrode and negative electrode mixture of waste lithium ion battery Download PDFInfo
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- CN105576312A CN105576312A CN201410522975.0A CN201410522975A CN105576312A CN 105576312 A CN105576312 A CN 105576312A CN 201410522975 A CN201410522975 A CN 201410522975A CN 105576312 A CN105576312 A CN 105576312A
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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 present invention relates to a method for recovering the positive electrode and negative electrode mixture of a waste lithium ion battery. The method comprises that a positive electrode and a negative electrode are separated through a jigging ore separation method or a magnetic fluid sorting method, the separated positive electrode or negative electrode is respectively placed into a high temperature liquid to make the electrode material be separated from the electrode current collector and enter the high temperature liquid, water is added to the high temperature liquid, and dissolving filtration is performed to obtain the filter cake only containing the electrode current collector and the mixed filtrate containing the high temperature liquid and the electrode material, or filtration is performed to obtain the mixture filter cake containing the electrode material and the electrode current collector and the filtrate containing the high temperature liquid, wherein the temperature of the high temperature liquid is not less than the separation or decomposition temperature of a binder for adhering and fixing the electrode material. According to the present invention, the method has advantages of high separation efficiency, simple process, environmental protection, low cost and the like, and can solve the waste lithium ion battery pollution and resource problem.
Description
Technical field
The present invention relates to the recovery method of old and useless battery, specifically, relate to the method for the both positive and negative polarity mixture reclaiming waste and old lithium ion battery.
Background technology
Now because scrapping of electronic product is more and more, the learies for the lithium ion battery of electronic product is also increasing, and it is also more and more important how lithium ion battery is reclaimed in resource environmental protection.The key reclaiming lithium ion battery is the positive pole reclaimed wherein, negative pole, the existing relevant recovery technology about lithium ion battery in prior art, as: Chinese patent application CN01130735.8, a kind of recovery method is disclosed in the invention that denomination of invention is 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, be not suitable for scale and reclaim requirement! therefore, research and develop the resource environmental protection recycling method about lithium ion battery that a kind of efficiency is high, pollution-free, cost is low, by the pollution and resource problem that solve waste lithium ion, there is important value and social effect.
Summary of the invention
The object of the invention is to the defect overcoming prior art, the method for the both positive and negative polarity mixture of the recovery waste and old lithium ion battery that a kind of efficiency is high, pollution-free, cost is low is provided, to solve pollution and the resource problem of waste lithium ion.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method reclaiming the both positive and negative polarity mixture of waste and old lithium ion battery, by after lithium ion battery fragmentation for the existing mature technology of employing, therefrom isolated both positive and negative polarity mixture, described both positive and negative polarity mixture comprises positive pole and negative pole, described positive pole comprises positive electrode and plus plate current-collecting body, and described negative pole comprises negative material and negative current collector; Described recovery method comprises the steps:
1. by jigging or magnetic fluid separating method, positive pole and negative pole are separated: because the proportion of positive pole and negative pole has larger difference, therefore by jigging or magnetic fluid separating method, positive pole and negative pole are separated;
2. put into high-temp liquid by being separated the positive pole obtained, by the heat effect of high-temp liquid, positive electrode is separated from plus plate current-collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain only containing the filter cake of plus plate current-collecting body and containing the mixing filtrate of high-temp liquid and positive electrode; Cleaning, drying is carried out to the filter cake obtained, namely obtains plus plate current-collecting body; Secondary filter is carried out to the mixing filtrate containing high-temp liquid and positive electrode, namely obtains the filter cake containing positive electrode 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 positive electrode that is adhesively fixed or decomposition temperature;
3. put into high-temp liquid by being separated the negative pole obtained, by the heat effect of high-temp liquid, negative material is separated from negative current collector, then in high-temp liquid, water is added, carry out dissolution filter, obtain only containing the filter cake of negative current collector and containing the mixing filtrate of high-temp liquid and negative material; Cleaning, drying is carried out to the filter cake obtained, namely obtains negative current collector; Secondary filter is carried out to the mixing filtrate containing high-temp liquid and negative material, namely obtains the filter cake containing negative 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 negative material that is adhesively fixed or decomposition temperature.
Another kind provided by the present invention reclaims the method for the both positive and negative polarity mixture of waste and old lithium ion battery, also be by after lithium ion battery fragmentation for the existing mature technology of employing, therefrom isolated both positive and negative polarity mixture, described both positive and negative polarity mixture comprises positive pole and negative pole, described positive pole comprises positive electrode and plus plate current-collecting body, and described negative pole comprises negative material and negative current collector; Described recovery method comprises the steps:
1. by jigging or magnetic fluid separating method, positive pole and negative pole are separated: because the proportion of positive pole and negative pole has larger difference, therefore by jigging or magnetic fluid separating method, positive pole and negative pole are separated;
2. put into high-temp liquid by being separated the positive pole obtained, by the heat effect of high-temp liquid, positive electrode is separated from plus plate current-collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain the mixture filter cake containing positive electrode and plus plate current-collecting body and the filtrate containing high-temp liquid; Carry out separating treatment (as: screening or selection by winnowing process) after cleaning, drying is carried out to the mixture filter cake obtained again, namely obtain positive electrode and the plus plate current-collecting body of separation; The temperature of described high-temp liquid is not less than separation for the bonding agent of the positive electrode that is adhesively fixed or decomposition temperature;
3. put into high-temp liquid by being separated the negative pole obtained, by the heat effect of high-temp liquid, negative material is separated from negative current collector, then in high-temp liquid, water is added, carry out dissolution filter, obtain the mixture filter cake containing negative material and negative current collector and the filtrate containing high-temp liquid; Carry out separating treatment (as: screening or selection by winnowing process) after cleaning, drying is carried out to the mixture filter cake obtained again, namely obtain negative material and the negative current collector of separation; The temperature of described high-temp liquid is not less than separation for the bonding agent of the negative material that is adhesively fixed or decomposition temperature.
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.
The method of the both positive and negative polarity mixture of recovery waste and old lithium ion battery of the present invention also has following improvement project:
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 by separation net and only allow pulverous electrode material to pass through, separation net being taken out from container and directly can obtain the separated electrode current collecting body got off, to 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, described high-temp liquid and positive electrode and plus plate current-collecting body or chemical reaction does not occur with negative material and negative current collector, to ensure reclaimed product purity and recycle value.
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 the method flow diagram of a kind of positive pole reclaimed in the both positive and negative polarity mixture of waste and old lithium ion battery that embodiment 1 provides.
Fig. 2 is the method flow diagram of a kind of negative pole reclaimed in the both positive and negative polarity mixture of waste and old lithium ion battery that embodiment 2 provides.
Fig. 3 is the method flow diagram of the positive pole in the both positive and negative polarity mixture of the another kind recovery waste and old lithium ion battery that embodiment 3 provides.
Fig. 4 is the method flow diagram of the negative pole in the both positive and negative polarity mixture of the another kind recovery waste and old lithium ion battery that embodiment 4 provides.
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 method for a kind of positive pole reclaimed in the both positive and negative polarity mixture of waste and old lithium ion battery that the present embodiment provides is as follows: lithium ion battery is carried out broken apart rear obtained both positive and negative polarity mixture and by jigging or magnetic fluid separating method, positive pole and negative pole are separated.Put in high-temp liquid by being separated the positive pole obtained, the temperature general control of high-temp liquid is between 450 DEG C ~ 700 DEG C, the bonding agent of bonding positive electrode can be made at these temperatures to decompose, the positive electrode sticked on positive pole is separated from plus plate current-collecting body 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 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 the positive electrode fine powder of separation; Heated oxide process is carried out to positive pole fine material powder and can improve its content, obtain positive electrode 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 method for a kind of negative pole reclaimed in the both positive and negative polarity mixture of waste and old lithium ion battery that the present embodiment provides is as follows: lithium ion battery is carried out broken apart rear obtained both positive and negative polarity mixture and by jigging or magnetic fluid separating method, positive pole and negative pole are separated.Put in high-temp liquid by being separated the negative pole obtained, the temperature of described high-temp liquid is greater than decomposition or the separation temperature of bonding agent; By the heat effect of high-temp liquid, the negative material sticked to above negative current collector enters in high-temp liquid as graphite powder will separate; In high-temp liquid, add water, form the aqueous solution by the dissolving of water, filter, obtain filter cake and filtrate.Cleaning, drying is carried out to filter cake, then sieves, namely obtain negative material if graphite powder and negative collector electrode material are as Copper Foil.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 method for a kind of positive pole reclaimed in the both positive and negative polarity mixture of waste and old lithium ion battery that the present embodiment provides is as follows: lithium ion battery is carried out broken apart rear obtained both positive and negative polarity mixture and make positive pole and negative pole separate by jigging or magnetic fluid separating method.Put in high-temp liquid by being separated the positive pole obtained, the temperature general control of high-temp liquid is between 450 DEG C ~ 700 DEG C, the bonding agent of bonding positive electrode can be made at these temperatures to decompose, cause the positive electrode sticked on plus plate current-collecting body 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 plus plate current-collecting body and the mixing filtrate containing positive electrode and high-temp liquid, so-called once filtration is exactly allow positive electrode filters by the size of controlled filter mesh and plus plate current-collecting body can not filter; After filter cake containing plus plate current-collecting body is carried out cleaning, drying, namely obtain plus plate current-collecting body, as: aluminium block; Mixing filtrate is carried out secondary filter, namely obtains the filter cake containing positive electrode and the filtrate containing high-temp liquid; Cleaning, drying is carried out to filter cake, namely obtains positive electrode, heated oxide process is carried out to the filter cake after cleaning, drying and can improve its content, obtain positive electrode 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 method that the another kind that the present embodiment provides reclaims the negative pole in the both positive and negative polarity mixture of waste and old lithium ion battery is as follows: lithium ion battery is carried out broken apart rear obtained both positive and negative polarity mixture and make positive pole and negative pole separate by jigging or magnetic fluid separating method.Putting in high-temp liquid by being separated the negative pole obtained, by the heat effect of high-temp liquid, causing the negative material sticked to above negative current collector to enter in high-temp liquid as graphite powder separates; Water is added in high-temp liquid, the aqueous solution is formed by the dissolving of water, 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; 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 (10)
1. reclaim a method for the both positive and negative polarity mixture of waste and old lithium ion battery, described both positive and negative polarity mixture comprises positive pole and negative pole, and described positive pole comprises positive electrode and plus plate current-collecting body, and described negative pole comprises negative material and negative current collector; It is characterized in that, described method comprises the steps:
11) by jigging or magnetic fluid separating method, positive pole and negative pole are separated;
12) high-temp liquid is put into by being separated the positive pole obtained, by the heat effect of high-temp liquid, positive electrode is separated from plus plate current-collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain only containing the filter cake of plus plate current-collecting body and containing the mixing filtrate of high-temp liquid and positive electrode; Cleaning, drying is carried out to the filter cake obtained, namely obtains plus plate current-collecting body; Secondary filter is carried out to the mixing filtrate containing high-temp liquid and positive electrode, namely obtains the filter cake containing positive electrode and the filtrate containing high-temp liquid;
13) high-temp liquid is put into by being separated the negative pole obtained, by the heat effect of high-temp liquid, negative material is separated from negative current collector, then in high-temp liquid, water is added, carry out dissolution filter, obtain only containing the filter cake of negative current collector and containing the mixing filtrate of high-temp liquid and negative material; Cleaning, drying is carried out to the filter cake obtained, namely obtains negative current collector; Secondary filter is carried out to the mixing filtrate containing high-temp liquid and negative material, namely obtains the filter cake containing negative material and the filtrate containing high-temp liquid.
2. reclaim a method for the both positive and negative polarity mixture of waste and old lithium ion battery, described both positive and negative polarity mixture comprises positive pole and negative pole, and described positive pole comprises positive electrode and plus plate current-collecting body, and described negative pole comprises negative material and negative current collector; It is characterized in that, described method comprises the steps:
21) by jigging or magnetic fluid separating method, positive pole and negative pole are separated;
22) high-temp liquid is put into by being separated the positive pole obtained, by the heat effect of high-temp liquid, positive electrode is separated from plus plate current-collecting body, then in high-temp liquid, water is added, carry out dissolution filter, obtain the mixture filter cake containing positive electrode and plus plate current-collecting body and the filtrate containing high-temp liquid; Carry out separating treatment again after cleaning, drying is carried out to the mixture filter cake obtained, namely obtain positive electrode and the plus plate current-collecting body of separation;
23) high-temp liquid is put into by being separated the negative pole obtained, by the heat effect of high-temp liquid, negative material is separated from negative current collector, then in high-temp liquid, water is added, carry out dissolution filter, obtain the mixture filter cake containing negative material and negative current collector and the filtrate containing high-temp liquid; Carry out separating treatment again after cleaning, drying is carried out to the mixture filter cake obtained, namely obtain negative material and the negative current collector of separation.
3. method as claimed in claim 1 or 2, is characterized in that: the temperature of described high-temp liquid is not less than decomposition for the bonding agent of be adhesively fixed positive electrode or negative material or separation temperature.
4. method as claimed in claim 1 or 2, is characterized in that: in the container holding high-temp liquid, be provided with separation net.
5. method as claimed in claim 1 or 2, is characterized in that: described high-temp liquid is fuse salt.
6. method as claimed in claim 5, is characterized in that: described fuse salt is the salt-mixture of chlorate or chlorate.
7. method as claimed in claim 1 or 2, is characterized in that: described high-temp liquid and positive electrode and plus plate current-collecting body or chemical reaction does not occur with negative material and negative current collector.
8. method as claimed in claim 1 or 2, is characterized in that: make the bonding agent wherein remained decompose removing to the positive electrode obtained by heated oxide.
9. method as claimed in claim 1 or 2, is characterized in that: when the plus plate current-collecting body obtained is aluminium foil, and the temperature of described high-temp liquid is higher than the fusing point of aluminium.
10. 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 |
|---|---|---|---|
| CN201410522975.0A CN105576312B (en) | 2014-10-06 | 2014-10-06 | The method for recycling the positive and negative anodes mixture of waste and old lithium ion battery |
| 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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| CN201410522975.0A CN105576312B (en) | 2014-10-06 | 2014-10-06 | The method for recycling the positive and negative anodes mixture of waste and old lithium ion battery |
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| CN105576312A true CN105576312A (en) | 2016-05-11 |
| CN105576312B CN105576312B (en) | 2019-03-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233305A (en) * | 2019-06-28 | 2019-09-13 | 武汉大学 | A kind of fused salt regeneration activating method of waste and old lithium ion battery tertiary cathode material |
| CN111430831A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering waste lithium ion battery negative electrode material |
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| US4058396A (en) * | 1976-11-26 | 1977-11-15 | Electric Power Research Institute, Inc. | Recovery of lead from batteries |
| US20050100793A1 (en) * | 2003-11-10 | 2005-05-12 | Polyplus Battery Company | Active metal electrolyzer |
| CN101205104A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Recovery method of lithium ion battery anode material waste slurry |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4058396A (en) * | 1976-11-26 | 1977-11-15 | Electric Power Research Institute, Inc. | Recovery of lead from batteries |
| US20050100793A1 (en) * | 2003-11-10 | 2005-05-12 | Polyplus Battery Company | Active metal electrolyzer |
| CN101205104A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Recovery method of lithium ion battery anode material waste slurry |
| 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 |
|---|---|---|---|---|
| CN110233305A (en) * | 2019-06-28 | 2019-09-13 | 武汉大学 | A kind of fused salt regeneration activating method of waste and old lithium ion battery tertiary cathode material |
| CN111430831A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering waste lithium ion battery negative electrode material |
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Effective date of registration: 20210420 Address after: 200051 room 271, 2 / F, building 6, 2453 Wanhangdu Road, Changning District, Shanghai Patentee after: Shanghai Peijun Technology Co.,Ltd. Address before: 201600, A-208, No. 1558 West Hui song Road, Shanghai, Songjiang District Patentee before: SHANGHAI QIMOU ENERGY TECHNOLOGY DEVELOPMENT Co.,Ltd. |