CN103311537A - Recycling method of battery positive material, positive pole piece and preparation method thereof - Google Patents
Recycling method of battery positive material, positive pole piece and preparation method thereof Download PDFInfo
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- CN103311537A CN103311537A CN2012100726921A CN201210072692A CN103311537A CN 103311537 A CN103311537 A CN 103311537A CN 2012100726921 A CN2012100726921 A CN 2012100726921A CN 201210072692 A CN201210072692 A CN 201210072692A CN 103311537 A CN103311537 A CN 103311537A
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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
- 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
Abstract
The invention discloses a recycling method of a positive material in positive leftovers of a lithium-ion battery. The method comprises the following steps of: placing the positive leftovers into a solvent, ultrasonically vibrating the positive leftovers until the positive material is stripped from a substrate, collecting the positive material and drying. The recycling method is simple to operate, high in recycling rate and low in cost. The invention also discloses a lithium-ion battery positive pole piece and a preparation method thereof. The preparation method is simple in process, and the resource and the energy can be greatly saved.
Description
Technical field
The present invention relates to the recovery method of positive electrode in a kind of lithium ion cell positive leftover bits and pieces, a kind of anode pole piece and preparation method thereof.
Background technology
Human productive life needs ample resources to do backing, and in modern process, electronic product brings great convenience for people's productive life, and portable electronics is more and more universal in daily life.Lithium ion battery has the advantages such as high voltage, large capacity and high power because of it, since nineteen ninety comes out, obtained extensively popularizing.At present, the annual production of whole world lithium ion battery surpasses 5,000,000,000, and the annual production of China is also above 1,000,000,000.In the case, people are to just quite large as the demand of the cobalt of anode material for lithium-ion batteries acid lithium.Because cobalt is scarce resource, a large amount of consumption of cobalt ore cause global cobalt valency to sharp rise.Because China's cobalt resource is limited, often needs from the overseas market import, this need to consume a large amount of foreign exchanges on the one hand, has also aggravated on the other hand the degree of dependence of China to foreign resources.
In addition, if the old and useless battery that a large amount of uses of lithium ion battery produce do not recycled, can be to environment.For this reason, how research is saved cobalt resource and how to be recycled cobalt and become the emphasis that researchers are studied.At present, for waste and old lithium ion battery, people have developed such as technology such as hydrometallurgy, solution extraction and pyrogenic processes to recycle cobalt wherein.Can realize recovery of Co on these theoretical methods, but in specific implementation process, all need use a large amount of solvents, not only increased the cost that reclaims, also bring the discharging of waste water, waste gas simultaneously, tend to environment is caused secondary pollution.
For reducing cost recovery, more effectively reclaim useful metal, someone explores the reclaiming method of lithium ion cell anode material lithium cobaltate and (sees patent: utilize waste and old lithium ion battery to reclaim the method for preparing the sour lithium of cobalt: application number 200910093727.8) once from the failure mechanism of waste and old lithium ion battery.Its key step comprises: obtain waste and old cobalt acid lithium from lithium ion battery; Component to waste and old cobalt acid lithium is revised; And the waste and old cobalt acid of after baking lithium.The advantage of the method is the regeneration of waste and old cobalt acid lithium is re-used, and has saved the conversion process of cobalt salt.
Said method relatively is suitable for the recycling to old and useless battery, but in the preparation process of lithium ion battery, tends to produce a large amount of pole piece or batteries scrapped off quality, also can produce a considerable amount of leftover bits and pieces in electrode cutting process.If adopt said method to reclaim this part cobalt acid lithium, can cause the waste of financial resources and material resources, recycle this part cobalt acid lithium but there is no at present suitable method.
Summary of the invention
Technical problem to be solved by this invention is to have overcome a large amount of leftover bits and pieces that produce in preparation process for lithium ion battery in the prior art, the defective that lacks suitable recovery method, and provide the recovery method of positive electrode in a kind of lithium ion cell positive leftover bits and pieces, the method is easy and simple to handle, the rate of recovery is high, and cost is low, and a kind of anode slice of lithium ion battery and preparation method thereof also is provided, the positive electrode that this anode pole piece utilization is reclaimed is made, and has greatly saved resource and the energy.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides the recovery method of positive electrode in a kind of lithium ion cell positive leftover bits and pieces, it comprises the steps: anodal leftover bits and pieces is placed solvent, and ultrasonic vibration to positive electrode is peeled off from base material, collects described positive electrode, dry getting final product.
Wherein, described ultrasonic frequency range preferably is 20-30kHz.
Wherein, the described ultrasonic time peels off fully from base material with described positive electrode and is as the criterion.
Wherein, described positive electrode is the conventional positive electrode that uses in this area, preferably is lithium cobaltate cathode material.
Wherein, described base material is the conventional base material in this area, is generally the aluminium foil material.
Wherein, described preferred solvents ground is polar organic solvent, more preferably is acetone and/or ethanol.
Wherein, the consumption of described solvent is as the criterion with the described leftover bits and pieces of complete submergence.
The condition of described drying and method are condition and the method for this area routine.Preferably, the temperature of described drying is 60-110 ℃.
The present invention also provides a kind of preparation method of anode slice of lithium ion battery, and it comprises the steps: that described positive electrode and the 1-METHYLPYRROLIDONE that will be obtained by above-mentioned recovery method are mixed to get electrode slurry, coats on the base material, gets final product.
Wherein, described base material is the conventional base material in this area, is generally the aluminium foil material.
Wherein, described positive electrode and 1-METHYLPYRROLIDONE proportioning can be the conventional proportioning in the preparation anode material for lithium-ion batteries field.The mass ratio of described positive electrode and 1-METHYLPYRROLIDONE preferably is 1: 0.5-1: 0.8.
The present invention also provides a kind of anode slice of lithium ion battery that is made by above-mentioned preparation method.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but combination in any namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is: the recovery method of positive electrode is easy and simple to handle in the lithium ion cell positive leftover bits and pieces of the present invention, the rate of recovery is high, cost is low, the positive electrode that anode slice of lithium ion battery utilization of the present invention is reclaimed is made, and technique simply and has greatly been saved resource and the energy.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited.
Used raw material or reagent is except specifying among the embodiment, all commercially available getting.
Embodiment 1
Lithium cobaltate cathode pole piece leftover bits and pieces (cobalt acid lithium content 90%) remaining when getting an amount of preparation lithium ion cell positive in a beaker, is poured acetone into, and acetone is advisable can cover leftover bits and pieces; Beaker is placed on and ultrasonicly in the ultrasonic device that frequency is 20kHz separates fully with aluminium foil to positive electrode; Then sort out aluminium foil and directly reclaim, with the method for toppling over a large amount of acetone solvents are reclaimed simultaneously; At last positive electrode is placed 60 ℃ of oven dry of baking oven to get final product.The rate of recovery that records cobalt acid lithium reaches 99.5%.
The positive electrode and the 1-METHYLPYRROLIDONE that reclaim are made anode sizing agent according to mass ratio at 3: 2, again are coated on and make anode pole piece on the aluminium foil.The specific capacity of test recovery positive electrode is 145mAh/g in button cell.The specific capacity (143mAh/g) of the positive pole that makes with the fresh cobalt of direct employing acid lithium is compared, and the cobalt acid lithium of recovery has embodied similar specific capacity, prove that the positive electrode of recovery can be used for being processed into positive pole fully again.
Embodiment 2
Lithium cobaltate cathode pole piece leftover bits and pieces (cobalt acid lithium content 90%) remaining when getting an amount of preparation lithium ion cell positive in a beaker, is poured ethanol into, and ethanol is advisable can cover leftover bits and pieces; Beaker is placed on and ultrasonicly in the ultrasonic device that frequency is 25kHz separates fully with aluminium foil to positive electrode; Then sort out aluminium foil and directly reclaim, with the method for toppling over a large amount of alcohol solvents are reclaimed simultaneously; At last positive electrode is placed 90 ℃ of oven dry of baking oven to get final product.The rate of recovery that records cobalt acid lithium reaches 99.7%.
The positive electrode and the 1-METHYLPYRROLIDONE that reclaim are made anode sizing agent according to mass ratio at 5: 4, again are coated on and make anode pole piece on the aluminium foil.The specific capacity of test recovery positive electrode is 144mAh/g in button cell.The specific capacity (143mAh/g) of the positive pole that makes with the fresh cobalt of direct employing acid lithium is compared, and the cobalt acid lithium of recovery has embodied similar specific capacity, prove that the positive electrode of recovery can be used for being processed into positive pole fully again.
Embodiment 3
Lithium cobaltate cathode pole piece leftover bits and pieces (cobalt acid lithium content 90%) remaining when getting an amount of preparation lithium ion cell positive in a beaker, is poured in the mixed solvent of ethanol and acetone, and the consumption of solvent is advisable can cover leftover bits and pieces; Beaker is placed on and ultrasonicly in the ultrasonic device that frequency is 30kHz separates fully with aluminium foil to positive electrode; Then sort out aluminium foil and directly reclaim, with the method for toppling over a large amount of mixed solvents are reclaimed simultaneously; At last positive electrode is placed 110 ℃ of oven dry of baking oven to get final product.The rate of recovery that records cobalt acid lithium is 99.8%.
The positive electrode and the 1-METHYLPYRROLIDONE that reclaim are made anode sizing agent according to mass ratio at 1: 1, again are coated on and make anode pole piece on the aluminium foil.The specific capacity of test recovery positive electrode is 144.5mAh/g in button cell.The specific capacity (143mAh/g) of the positive pole that makes with the fresh cobalt of direct employing acid lithium is compared, and the cobalt acid lithium of recovery has embodied similar specific capacity, prove that the positive electrode of recovery can be used for being processed into positive pole fully again.
Claims (10)
1. the recovery method of positive electrode in the lithium ion cell positive leftover bits and pieces, it comprises the steps: anodal leftover bits and pieces is placed solvent, and ultrasonic vibration to positive electrode is peeled off from base material, collects described positive electrode, dry getting final product.
2. recovery method as claimed in claim 1 is characterized in that, described ultrasonic frequency range is 20-30kHz.
3. recovery method as claimed in claim 1 is characterized in that, described positive electrode is lithium cobaltate cathode material.
4. recovery method as claimed in claim 1 is characterized in that, described base material is the aluminium foil material.
5. recovery method as claimed in claim 1 or 2 is characterized in that, described solvent is polar organic solvent, preferably is acetone and/or ethanol.
6. recovery method as claimed in claim 1 or 2 is characterized in that, the temperature of described drying is 60-110 ℃.
7. the preparation method of an anode slice of lithium ion battery, its comprise the steps: with recovery method as described in claim 1-6 obtain as described in positive electrode and 1-METHYLPYRROLIDONE be mixed to get electrode slurry, coat on the base material, get final product.
8. preparation method as claimed in claim 7 is characterized in that, described base material is the aluminium foil material.
9. preparation method as claimed in claim 7 is characterized in that, the mass ratio of described positive electrode and 1-METHYLPYRROLIDONE is 1: 0.5-1: 0.8.
10. anode slice of lithium ion battery that is made by each described preparation method of claim 7-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2012100726921A CN103311537A (en) | 2012-03-16 | 2012-03-16 | Recycling method of battery positive material, positive pole piece and preparation method thereof |
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| CN2012100726921A CN103311537A (en) | 2012-03-16 | 2012-03-16 | Recycling method of battery positive material, positive pole piece and preparation method thereof |
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| CN103311537A true CN103311537A (en) | 2013-09-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956533A (en) * | 2014-03-28 | 2014-07-30 | 华南师范大学 | Method for preparing cathode material of lithium ion battery |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453897A (en) * | 2003-05-29 | 2003-11-05 | 南开大学 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
| CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
| CN101212074A (en) * | 2006-12-30 | 2008-07-02 | 上海比亚迪有限公司 | Method for recovering positive pole material of Li-ion battery |
-
2012
- 2012-03-16 CN CN2012100726921A patent/CN103311537A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453897A (en) * | 2003-05-29 | 2003-11-05 | 南开大学 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
| CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
| CN101212074A (en) * | 2006-12-30 | 2008-07-02 | 上海比亚迪有限公司 | Method for recovering positive pole material of Li-ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956533A (en) * | 2014-03-28 | 2014-07-30 | 华南师范大学 | Method for preparing cathode material of lithium ion battery |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
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Application publication date: 20130918 |