CN114335785B - Method for efficiently regenerating graphite cathode - Google Patents
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- CN114335785B CN114335785B CN202210005682.XA CN202210005682A CN114335785B CN 114335785 B CN114335785 B CN 114335785B CN 202210005682 A CN202210005682 A CN 202210005682A CN 114335785 B CN114335785 B CN 114335785B
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Abstract
The invention belongs to the technical field of battery material recycling and discloses a method for efficiently regenerating a graphite cathode, which comprises the following steps: under inert atmosphere, the graphite negative electrode sheet of the waste lithium ion battery is placed on a carbon-based substrate, the graphite negative electrode sheet is rapidly heated to high temperature by adopting a high-temperature short-time heating method, high-temperature heat treatment is carried out for a short time, and then the high-efficiency regeneration of the graphite negative electrode is realized by rapid cooling. The method can realize the direct regeneration of the graphite cathode plate in a short time (second level), obviously improve the time and energy efficiency, and avoid the problems of long period, complexity, high energy consumption and the like of the traditional graphite regeneration process.
Description
Technical Field
The invention belongs to the technical field of battery material recycling, and particularly relates to a method for efficiently regenerating a graphite cathode.
Background
Over the past decade, driven by the shortage of fossil energy supplies and the "dual carbon" goal, the Lithium Ion Battery (LIB) market demand has increased dramatically. Currently, there are approximately 71.9 billion mobile phones in use worldwide, approaching 10 billion notebook computers and several billion tablet computers. The demand for lithium ion batteries in the field of consumer electronics is not only kept high, but is further increased due to the deep popularity of various consumer electronics. In actual life, the replacement time of the mobile phone battery is 12-18 months, the recovery rate of the mobile phone is lower than 5%, and even when various policies encourage and people's environmental awareness is continuously improved, the recovery rate is still lower than 10%. By 2025, the global lithium ion battery market will reach $ 950 billion, with an estimated annual growth rate of about 16% and 10700 tons of wasted/used LIB in 2012. It is expected that about 1100 million tons of spent lithium ion batteries will be produced by 2030.
The negative electrode in the lithium ion battery accounts for about 10% of the battery cost, so that the negative electrode material gradually gets attention in the industrial field and the scientific research field. The negative electrode material contained a large amount of copper, carbon and a small amount of lithium metal (31 mg g) -1 ) Therefore, the method has important significance for recycling the whole negative electrode. At present, the recovery of the negative electrode is mainly carried out by the following methods, such as heat treatment, leaching, grinding flotation, electrolysis, ultrasonic hydrolysis and the like. Populus et al used a two-step calcination of graphite followed by 1.5mol L -1 Leaching lithium with HCl, removing Cu and Al, and adding Na 2 CO 3 Separating out lithium, the purity of the obtained lithium carbonate is higher than 99%, and simultaneously the waste graphite passes through air gasRegeneration was achieved by heat treatment at 500 ℃ for 1 hour under an atmosphere. Gao et al performed sulfuric acid cure-acid leach experiments and continued calcination at 1500 ℃ for graphite regeneration. The purity of the regenerated graphite can reach 99.6%. Zhou et al utilized crushing, vibratory screening and gas separation to separate and recover copper and carbon powder from the negative electrode, and copper and graphite of different particle sizes achieved different recoveries and purities. The grinding flotation is used for separating and recovering graphite from the waste lithium ion battery, and the graphite flotation rate can reach 73.56%. Zhang et al also used flotation technology to separate graphite from LiCoO 2 Then, the decomposed organic binder was removed by pyrolysis at 500 c, and the remaining pyrolysis product was removed by ultrasonic cleaning. Zhang et al realized direct regeneration of graphite by electrolysis, and simultaneously peeled the negative electrode material from the current collector, and the first discharge capacity reached 427.81mAh g at 0.1C -1 (ii) a Zhang et al realize the preparation of few-layer graphene and the recovery of metallic lithium element by a direct ultrasonic hydrolysis method, and realize better economic benefit. However, these methods have the disadvantages of large energy consumption, large amount of sewage generation, complicated process, low efficiency, etc., so a method with low energy consumption, simple process, high efficiency, and environmental friendliness is urgently needed to realize direct regeneration of the graphite cathode.
Disclosure of Invention
Aiming at the existing complicated technical route for recycling waste graphite and lower recycling efficiency, the invention aims to provide a method for realizing a regenerated graphite cathode, which is quick, efficient, convenient, low in energy consumption and environment-friendly.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for efficiently regenerating a graphite cathode comprises the steps of treating a graphite cathode electrode piece of a waste battery by adopting a high-temperature short-time heating method in an inert atmosphere, and then rapidly cooling to realize efficient regeneration of the graphite cathode.
Preferably, the waste battery is completely discharged to be lower than 2.0V, the graphite negative electrode plate is washed by a solvent to remove electrolyte remaining on the surface and is naturally dried, wherein the washing solvent is preferably dimethyl carbonate.
Preferably, the battery products using the graphite negative electrode are various lithium ion batteries.
Preferably, the temperature of the high-temperature short-time treatment is 1000-2000 ℃.
Preferably, the short time of the high-temperature short-time treatment is 10ms to 1s.
Preferably, the heating method of the high-temperature short-time treatment is a pulse heating method, and is preferably realized by a method of direct joule heat heating, heat conduction heating or laser light source radiation heating.
Preferably, the joule heating and thermal conduction heating method can be implemented by placing the graphite cathode electrode sheet on a carbon-based substrate and electrifying the carbon-based substrate, wherein the carbon-based material is one of carbon cloth, a carbon plate and carbon paper.
Preferably, the temperature rise rate of the rapid temperature rise is 10 to 10 5 ℃/s。
Preferably, the rapid cooling mode is natural cooling or air cooling, metal roller cooling and the like.
Preferably, the cooling rate of the rapid cooling is 10-10 3 ℃/s。
Preferably, the inert gas is one or more selected from argon or nitrogen.
Preferably, the high-temperature short-time method is used for treating the graphite negative electrode sheet once to many times.
In addition, the invention also claims the application of the method in the regeneration of the graphite negative electrode plate of the waste lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method can realize the direct regeneration of the graphite cathode plate in a short time (second level), obviously improve the time and energy efficiency, and avoid the problems of long period, complexity, high energy consumption and the like of the traditional graphite regeneration process.
(2) The method can realize the battery performance regeneration (specific energy density) of the graphite, and simultaneously, because the treatment time is short, the method well preserves the existing Solid Electrolyte Interface (SEI) layer of the graphite in the waste battery, and obviously improves the first coulombic efficiency of the graphite.
(3) According to the invention, dead lithium or a lithium compound existing in the waste graphite is used as a lithium source, and lithium can be pre-supplemented in the regeneration process, so that the first coulomb efficiency of the graphite is obviously improved.
(4) The method can realize direct regeneration of graphite without stripping graphite, and avoids the complex processes of crushing, grinding and sieving or calcining, grinding, sieving and the like adopted in the traditional graphite stripping treatment process.
(5) The preparation process only needs short-time current heating, so the method is environment-friendly and low in cost, and avoids the generation of a large amount of toxic and harmful gases, solid waste residues, a large amount of waste liquid and waste water in the traditional regeneration process (high-temperature calcination, acid-base recovery and the like).
Drawings
FIG. 1 is a graph comparing the time ranges for graphite regeneration according to the present invention and conventional heating methods for graphite electrode recovery or regeneration;
fig. 2 is a first-turn charge-discharge curve diagram of the button cell assembled by the high-efficiency regenerated graphite negative electrode and the waste graphite group and the commercial graphite prepared in example 1 of the invention at 0.01-3V and 0.1C; it can be seen that the capacity of the waste graphite is seriously lost, which is mainly caused by the destruction of the graphite laminated structure and the existence of a large amount of dead lithium between layers; the regenerated graphite processed by the method can realize retention of SEI, restoration of a layered structure and lithium pre-supplement, and the capacity and the efficiency are remarkably improved.
FIG. 3 is a schematic view of the present invention showing direct regeneration without peeling;
FIG. 4 is a schematic representation of the steps of the regeneration process of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Of course, the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Although the steps in the present invention are arranged by using reference numbers, the order of the steps is not limited, and the relative order of the steps can be adjusted unless the order of the steps is explicitly stated or other steps are required for the execution of a certain step. It is to be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
Example 1
A method for efficiently regenerating a graphite negative electrode comprises the following steps: discharging the waste lithium ion battery to 2.0V, washing a graphite negative plate of the waste lithium ion battery for three times by using dimethyl carbonate under an inert atmosphere to remove electrolyte remained on the surface, and then placing the negative plate for 6h for naturally airing; and then placing the graphite negative plate on the upper part of the carbon cloth, connecting positive and negative leads to the two ends of the carbon cloth, setting the constant current power supply parameter as current 8A, detecting the temperature of the carbon cloth in real time by a thermal radiation thermodetector so that the temperature of the graphite negative plate is raised to 1200 ℃ and kept for 500ms, and then quickly cooling to realize the high-efficiency regeneration of the graphite negative electrode.
Example 2
A method for efficiently regenerating a graphite cathode comprises the following steps: discharging the waste lithium ion battery to 2.0V, washing a graphite negative plate of the waste lithium ion battery for three times by using dimethyl carbonate under an inert atmosphere to remove electrolyte remained on the surface, and then placing the negative plate for 12h for natural airing; and then placing the graphite negative plate on the upper part of the carbon plate, connecting positive and negative wires to two ends of the carbon plate, setting constant current power supply parameters as current 20A, detecting the temperature of the carbon plate in real time by a thermal radiation thermodetector to enable the temperature of the graphite negative plate to rise to 2000 ℃ and keep the temperature for 40ms, and then rapidly cooling to realize the high-efficiency regeneration of the graphite negative electrode.
Example 3
A method for efficiently regenerating a graphite negative electrode comprises the following steps: discharging the waste lithium ion battery to 2.0V, washing a graphite negative plate of the waste lithium ion battery for three times by using dimethyl carbonate under an inert atmosphere to remove electrolyte remained on the surface, and then placing the negative plate for 6h for naturally airing; and then placing the graphite negative plate on the upper part of the carbon plate, connecting positive and negative leads to the two ends of the carbon plate, setting the constant current power supply parameter as current 10A, detecting the temperature of the carbon plate in real time by a thermal radiation thermodetector, raising the temperature of the graphite negative plate to 1800 ℃ and keeping the temperature for 50ms, and then quickly cooling to realize the efficient regeneration of the graphite negative electrode.
Example 4
A method for efficiently regenerating a graphite negative electrode comprises the following steps: discharging the waste lithium ion battery to 2.0V, washing a graphite negative plate of the waste lithium ion battery for three times by using dimethyl carbonate under an inert atmosphere to remove electrolyte remained on the surface, and then placing the negative plate for 8h for naturally airing; and then placing the graphite negative plate on the upper part of the carbon plate, connecting positive and negative leads to the two ends of the carbon plate, setting the constant current power supply parameter as current 20A, detecting the temperature of the carbon plate in real time by a thermal radiation thermodetector so that the temperature of the graphite negative plate is raised to 1500 ℃ and kept for 80ms, and then quickly cooling to realize the high-efficiency regeneration of the graphite negative electrode.
Before and after regeneration of the graphite cathode of the waste lithium ion battery in example 1 and commercial graphite were subjected to performance evaluation, according to the following graphite: SP: PVDF =90:5:5, homogenizing to prepare a pole piece, using a lithium piece as a counter electrode and an electrolyte of 1.0M LiPF6 in EC, DEC =1, and performing a performance test, wherein the results are as follows:
the waste lithium ion battery is a waste notebook computer battery, the battery capacity is 60% of the nominal capacity, the positive electrode is lithium cobaltate, the negative electrode is waste graphite, and the battery type is a soft package wound battery; commercial graphite is commercially available beiibri graphite.
As shown in the above table, by comparing the properties of the commercial graphite, the waste graphite and the regenerated graphite realized by the present invention, it can be seen that the regenerated graphite prepared by the present invention has high coulombic efficiency and capacity exertion, and has strong commercial value.
The above description is only a preferred embodiment of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. that are within the spirit and scope of the present invention should be included.
Claims (8)
1. A method for regenerating a graphite cathode is characterized in that under an inert atmosphere, a graphite cathode electrode piece of a waste battery is treated by adopting a high-temperature short-time heating method, and then is rapidly cooled, so that the high-efficiency regeneration of the graphite cathode is realized;
wherein the temperature of the high-temperature short-time heating method is 1000-2000 ℃;
wherein the time of the high-temperature short-time heating method is 10 ms-1 s;
the high-temperature short-time heating method is realized by a heat conduction heating method or a laser light source radiation heating method;
the method for heating by heat conduction is realized by placing a graphite cathode electrode plate on a carbon-based substrate and electrifying the carbon-based substrate, wherein the carbon-based substrate is one of carbon cloth, a carbon plate and carbon paper.
2. The method as claimed in claim 1, wherein the waste battery is completely discharged to less than 2.0V, the graphite negative electrode plate is washed by a solvent to remove electrolyte remaining on the surface and is naturally dried, and the washing solvent is dimethyl carbonate.
3. The battery of claim 2, wherein the battery product using the graphite negative electrode is various types of lithium ion batteries.
4. The method of claim 1, wherein the rapid cooling is performed by natural cooling or air cooling.
5. The method of claim 1, wherein the rapid cooling has a cooling rate of 10 to 10% 3 ℃/s。
6. The method of claim 1, wherein the inert atmosphere is argon.
7. The method according to claim 1, wherein the high-temperature short-time heating method is used for treating the graphite negative electrode sheet once or more than once.
8. Use of the method according to any one of claims 1 to 7 in the regeneration of graphite negative electrode sheets of waste batteries.
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| CN115872394A (en) * | 2022-12-15 | 2023-03-31 | 山东大学 | Carbon negative electrode material, preparation method and application thereof in quick-charging lithium ion battery |
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| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| JP2019130474A (en) * | 2018-01-31 | 2019-08-08 | 宇部興産株式会社 | Regenerated negative electrode active material recovered from discarded lithium ion battery containing lithium titanate and recovery method of the same |
| CN111883869A (en) * | 2020-06-24 | 2020-11-03 | 华南理工大学 | Method for recycling lithium by using graphite cathode of waste power battery and preparing graphene by using lithium |
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| JP2014127417A (en) * | 2012-12-27 | 2014-07-07 | Nissan Motor Co Ltd | Method for collecting and reusing negative electrode active material of lithium ion battery |
| US9484606B1 (en) * | 2013-03-15 | 2016-11-01 | Hulico LLC | Recycling and reconditioning of battery electrode materials |
| CN103346365B (en) * | 2013-07-22 | 2015-06-24 | 田东 | Method for recycling negative material from waste lithium ion battery |
| CN104882638A (en) * | 2015-04-27 | 2015-09-02 | 云南蓝光矩阵科技有限公司 | Graphite carbon fiber battery |
| CN112325475A (en) * | 2020-10-30 | 2021-02-05 | 陆建军 | Heating pipe, preparation method of heating pipe and liquid heater |
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| CN113410534A (en) * | 2021-06-23 | 2021-09-17 | 昆明理工大学 | Method for recovering graphite and copper foil in anode of waste lithium ion battery through microwave radiation |
| CN113594420B (en) * | 2021-09-30 | 2022-02-01 | 中南大学 | Regeneration method of lithium ion battery graphite cathode and regenerated graphite cathode thereof |
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| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| JP2019130474A (en) * | 2018-01-31 | 2019-08-08 | 宇部興産株式会社 | Regenerated negative electrode active material recovered from discarded lithium ion battery containing lithium titanate and recovery method of the same |
| CN111883869A (en) * | 2020-06-24 | 2020-11-03 | 华南理工大学 | Method for recycling lithium by using graphite cathode of waste power battery and preparing graphene by using lithium |
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