CN114843650B - A high-value recycling method for lithium battery graphite negative electrode waste - Google Patents
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Abstract
本发明公开了一种石墨负极废料高附加值化利用的方法，属于固体废弃物回收的技术领域。主要包括高温酸浸、高温煅烧、湿料球磨、喷雾干燥以及二次煅烧等工艺。石墨废料首先经过硫酸浸出以及高温煅烧获得高纯度的再生石墨；接着分别添加一定比例的硅粉、PVP粉末、酒精试剂和NMP试剂进行两次球磨得到浆料。随后将浆料通过喷雾—热解干燥工艺先得到硅碳材料前驱体，最终经过二次煅烧后得到球型硅碳材料产品。此外，浆料中的NMP和酒精试剂也可以进行回收，实现了整个流程的闭路循环。本工艺得到再生石墨的纯度高；并且后续制备得到大小均一，球形度高的硅碳材料产品，展现出优异的电化学性能。整个工艺流程具有绿色环保的特点，满足清洁生产的要求。
The invention discloses a method for high value-added utilization of graphite negative electrode waste, and belongs to the technical field of solid waste recycling. It mainly includes processes such as high-temperature acid leaching, high-temperature calcination, wet material ball milling, spray drying and secondary calcination. The graphite waste is first subjected to sulfuric acid leaching and high-temperature calcination to obtain high-purity regenerated graphite; then a certain proportion of silicon powder, PVP powder, alcohol reagent and NMP reagent are added respectively for two times of ball milling to obtain slurry. Subsequently, the slurry is subjected to a spray-pyrolysis drying process to first obtain a silicon-carbon material precursor, and finally a spherical silicon-carbon material product is obtained after secondary calcination. In addition, the NMP and alcohol reagent in the slurry can also be recycled, realizing a closed-loop cycle of the entire process. The regenerated graphite obtained by this process has high purity; and the silicon-carbon material product with uniform size and high sphericity is subsequently prepared, showing excellent electrochemical properties. The entire process flow is green and environmentally friendly, and meets the requirements of clean production.
Description
Technical Field
The invention belongs to the technical field related to solid waste treatment in the battery industry, and particularly relates to a high-value recovery technology for graphite negative electrode waste of waste lithium batteries.
Background
According to the latest data, the average annual scrappage of the failed lithium batteries in China exceeds 50 ten thousand tons by 2020, and serious environmental pollution and resource waste are caused. Of all lithium battery anode materials, graphite is most commonly used. As the charge and discharge times of lithium ion batteries are increased, the interlayer spacing is enlarged or even peeled off due to intercalation and deintercalation of lithium ions in graphite, resulting in gradual attenuation of the capacity of the battery material until failure.
There are many ways to recycle the waste lithium ion anode material, the most predominant recycling way being to recycle to secondary electrode material. However, the negative graphite is difficult to meet the requirements of the high energy density negative electrode material due to the relatively low capacity (372 mAh/g), and thus limits its further development. However, silicon has a very high theoretical capacity (4200 mAh/g) and is considered as a promising anode material for the next generation. Therefore, the cheap regenerated graphite, asphalt, nano silicon powder and dispersing agent PVP are mixed to prepare the silicon-carbon composite material product, so that the capacity of the silicon-carbon composite material product can be greatly improved, and the high-value utilization of graphite negative electrode waste is realized.
The method comprises the steps of firstly carrying out acid leaching treatment on waste graphite by sulfuric acid treatment to obtain purified graphite, wherein the concentration of the sulfuric acid is 2mol/L, the liquid-solid ratio is 50:3, the acid leaching time is 60 min, the acid leaching temperature is 40 ℃, then adding the graphite into a mixed solution of an oxidant and an intercalating agent for reaction, filtering, washing with water, drying to obtain expandable graphite, and placing the expandable graphite in a muffle furnace for calcination for a period of time to obtain the expanded graphite, wherein the oxidant is KMnO 4, and the intercalating agent is concentrated nitric acid. The mass ratio of the oxidant to the graphite material is 1:2, the liquid-solid ratio of the intercalating agent to the graphite material is 15:1, the reaction time is 8 h, the subsequent calcination temperature is 900 ℃ and the time is 30 s, finally, the silicon-carbon material is added, and the expanded graphite/silicon-carbon composite material is prepared by ball milling, wherein the mass ratio of the expanded graphite to the silicon-carbon material is 3:7, the ball milling rotating speed is 450 r/min, the ball material ratio in ball milling is 20:1, and the ball milling time is 7 h. The resulting expanded graphite/silicon carbon composite exhibited a specific discharge capacity of 1400 mAh/g at a magnification of 0.1C.
In view of the defects of high reagent consumption and high silicon-carbon material consumption in the preparation of spherical silicon-carbon materials by using waste graphite. The invention aims to develop a new technology, namely, adopting the processes of high-temperature acid leaching, high-temperature calcination, wet material ball milling, spray drying, secondary calcination and the like, namely adopting the wet ball milling and spray drying combined high-temperature calcination process to prepare the spherical silicon-carbon material product with high sphericity and good uniformity, and showing excellent electrochemical performance. In addition, the ethanol and NMP in the organic solvent can be recycled, so that the closed cycle of the whole process is realized.
Disclosure of Invention
Aiming at the problem of low added value of the regenerated graphite of the lithium ion battery, the invention provides a high-temperature acid leaching, high-temperature calcination, wet material ball milling, spray drying and secondary calcination process, so as to prepare spherical silicon-carbon material particles, and the spherical silicon-carbon material particles have excellent electrochemical performance, thereby realizing the recycling regeneration and high-value utilization of the lithium ion battery.
The invention is realized by the following technical scheme:
The recovery method of the graphite cathode material of the lithium battery is characterized by comprising the following steps of high-temperature acid leaching, high-temperature calcination, wet ball milling, spray drying, secondary calcination and the like, and the specific steps are as follows:
(1) Sulfuric acid leaching is carried out on the graphite cathode of the waste lithium ion battery, stirring is added in the leaching process, water bath heat preservation treatment is added, leaching slag is obtained, and then high-temperature roasting is carried out, so that the regenerated graphite is obtained.
(2) Adding nano silicon powder, PVP powder and alcohol solution into the regenerated graphite obtained in the step (1), and performing first ball milling in a ball mill to obtain slurry.
(3) And (3) adding the asphalt/NMP solution into the mixed slurry obtained in the step (2) for secondary ball milling to obtain secondary slurry.
(4) And (3) performing spray drying on the secondary slurry obtained in the step (3) to obtain a silicon-carbon material precursor.
(5) And (3) performing secondary calcination on the precursor obtained in the step (4) to obtain a spherical silicon-carbon material product.
Further, the acid leaching process in the step (1) uses sulfuric acid as a reagent, the concentration is 50-500 g/L, the leaching temperature is 50-100 ℃, the liquid-solid ratio is 5:1-15:1, the leaching time is 2-12 h, the temperature in the roasting process is 500-1500 ℃, and the heat preservation time is 1-6 h. And (3) introducing protective gas in the roasting process, wherein the protective gas is N 2 or Ar, and the flow is 60-120 mL/min.
Further, the nano silicon powder in the step (2) accounts for 5% -30% of the mass of graphite, the PVP dispersing agent accounts for 5% -20% of the mass of silicon powder, and the liquid-solid ratio of alcohol to the total material is 3:1-5:1. The ball milling speed is 200-500 rpm, and the ball milling time is 1-6 h.
Further, the mass of the added asphalt in the step (3) is 5-30% of the mass of the graphite and the silicon powder, and the liquid-solid ratio of the added NMP to the asphalt is 3:1-15:1. The ball milling speed is 200-500 rpm, and the ball milling time is 1-6 h.
Further, the inlet temperature of the spray drying equipment in the step (4) is 140-200 ℃, the outlet temperature is 60-100 ℃, the atomization pressure is 0.05-0.3 MPa, and the feeding speed is 20-500 mL/min.
Further, the calcining temperature in the step (5) is 1000-1600 ℃ under the normal pressure condition, the calcining time is 1-8 h, the pressure is controlled at 1 atm, the calcining process needs to be conducted with protective gas, the protective gas is N 2 or Ar, and the flow is 100-500 mL/min.
The invention has the technical key points that:
(1) The invention has the characteristic of small acid consumption. The method is characterized in that compared with a comparison file, the method adopts acid with the concentration of 0-4.0 mol/L and the solid-liquid ratio of 1:0-15 g/L, and the acid concentration in the comparison file is 0-5 mol/L and the solid-liquid ratio is 1:0-100 g/L.
(2) The silicon-carbon material prepared by the invention has the characteristics of low silicon content and high electrochemical performance. The silicon-carbon material synthesized by the application has the silicon content of 5-30% of the mass of graphite compared with a comparison document. More preferably, when the silicon content is 30%, the first-time capacity of the silicon-carbon material is 1136 mAh/g, the first-time efficiency is 88.2%, the silicon capacity is silicon content=3788:1, and the first-time efficiency is 84.4% and the ratio 2328:1 of the silicon capacity to the content is far higher than that in the comparison document.
(3) The silicon-carbon material prepared by the invention has the characteristics of green and environment-friendly. In particular, the alcohol and NMP used in this application are recovered by evaporation-condensation-fractionation, as compared with comparative document 1. And the recovery rate of the organic reagent is more than 90 percent.
The technical scheme disclosed in the comparison document is that a method for preparing an expanded graphite/silicon carbon material by using a graphite cathode of a waste battery is characterized by comprising the following steps:
Washing, filtering, washing and drying the waste battery graphite negative electrode plate to obtain a graphite carbon material falling off from the negative copper foil;
Adding mixed solution of concentrated sulfuric acid, potassium permanganate and hydrogen peroxide into the graphite carbon material for reaction, and then washing, filtering and drying to obtain expandable graphite;
Placing the expandable graphite into a muffle furnace for roasting treatment to obtain expanded graphite;
ball-milling and mixing the expanded graphite with a silicon-carbon material to obtain an expanded graphite/silicon-carbon material;
After the expanded graphite is subjected to ball milling and mixing to obtain the expanded graphite/silicon carbon material, the method further comprises the steps of grinding the obtained expanded graphite/silicon carbon material, and sieving the ground expanded graphite/silicon carbon material powder to obtain the recyclable expanded graphite/silicon carbon material powder.
The technical scheme of the application has the following distinguishing technical characteristics with the comparison file:
(1) The application discloses a high-value recovery method of graphite negative electrode waste of a lithium battery, which comprises the processes of high-temperature acid leaching, high-temperature calcination, wet ball milling, spray drying, secondary calcination and the like, and spherical silicon-carbon material particles are prepared;
The comparison document discloses a method for preparing expanded graphite/silicon carbon material by using a graphite cathode of a waste battery, which comprises the steps of carrying out acid leaching, washing and drying on a cathode copper foil of a lithium battery to obtain recovered graphite, adding mixed solution of concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and the like into the recovered graphite, carrying out washing, drying and high-temperature roasting treatment to obtain expanded graphite, and carrying out ball milling and mixing on the expanded graphite added with the silicon carbon material to obtain expanded graphite/silicon carbon material powder.
Therefore, the treatment process in the comparison document is different from the treatment process in the application, not only the wet ball milling and spray drying technology which is not provided by the application is needed, but also the treatment mode of the intermediate first calcined graphite powder is different from the treatment mode of the intermediate first calcined graphite powder on the graphite slag, the two are different for objects, and the physicochemical properties of the different objects are also different, so that the subsequent treatment process has no combined technical foundation.
Specifically, the treatment mode of adding concentrated sulfuric acid, potassium permanganate and hydrogen peroxide mixed solution into graphite powder in a comparison file is different from the treatment mode of carrying out sulfuric acid leaching and high-temperature roasting on graphite slag in the application, the concentrated sulfuric acid in the comparison file can negatively affect the subsequent drying and roasting of the graphite powder, sulfur dioxide toxic gas is easy to generate, and a large amount of reagent is consumed, and unlike the method for the file, pure graphite powder can be obtained only by simple acid leaching and roasting, and the graphite powder obtained by the comparison file is not completely pure.
The concentration of ions (Li, al, cu, fe) in the graphite treated by the method can be reduced to below 100 ppm, and ash content (weight percent) is less than 0.2 percent, in other words, the purity of the graphite is not less than 99.8 percent. The first capacity and the first efficiency of the regenerated graphite at the multiplying power of 0.1C are 91.4% and 346.3 mAh/g respectively, and the capacity retention rate after 100 circles is 93.2%. Then ball milling, spray drying and high temperature calcining are carried out to form spherical silicon-carbon material products, and the electrochemical performance of the silicon-carbon material is greatly improved. When the silicon content was 30%, the first capacity and the first efficiency at a magnification of 0.1C were 1136 mAh/g and 88.4%, and the capacity retention after 100 cycles was 84.6%. In addition, in the process of preparing the silicon-carbon material, the solvents ethanol and NMP in the slurry can be continuously recycled, so that the closed cycle of the whole flow is realized.
Drawings
Figure 1 SEM pictures of spherical silicon carbon particles at different magnifications,
Figure 2 cycle performance of spherical silicon carbon material.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be made with reference to specific embodiments.
The invention provides a high-value recovery method of graphite negative electrode waste of a lithium battery, which mainly comprises the processes of high-temperature acid leaching, high-temperature calcination, wet ball milling, spray drying, secondary calcination and the like, and is described by a specific embodiment.
Example 1
(1) Carrying out sulfuric acid leaching on 20g negative electrode graphite (containing Li 1460 ppm, cu 713 ppm, fe 4592 ppm, al 379 ppm and C97.9%) with sulfuric acid concentration of 200 g/L, liquid-solid ratio of 10:1, water bath temperature of 80 ℃ and leaching time of 4 h, then carrying out high-temperature roasting with roasting temperature of 1000 ℃ and heat preservation time of 1 h, wherein protective gas is required to be introduced in the calcining process, the protective gas is N 2 or Ar, the flow is 60 mL/min, and the regenerated graphite (containing Li 34.8 ppm, cu 164.4 ppm, fe 35.4 ppm, al 102.8 ppm and C99.86%).
(2) Adding the regenerated graphite obtained in the step (1) into nano silicon powder, a dispersing agent PVP and alcohol for ball milling to form slurry. The mass ratio of the regenerated graphite to the nanometer silicon powder to the PVP is 1:0.3:0.03, the liquid-solid ratio of the alcohol to the total materials is 5:1, the ball milling speed is 300 rpm, and the ball milling time is 3 h.
(3) Adding asphalt/NMP solution into the slurry obtained in the step (2) for secondary ball milling to form secondary slurry, wherein the mass of asphalt is 10% of the sum of the mass of graphite and the mass of silica powder, the liquid-solid ratio of the added NMP to the asphalt is 5:1, the secondary ball milling speed is 300 rpm, and the secondary ball milling time is 2 h.
(4) And (3) performing spray granulation on the secondary slurry obtained in the step (3) by spray drying equipment, wherein the inlet temperature is 160 ℃, the outlet temperature is 80 ℃, the materialization pressure is 0.1 Mpa, and the feeding speed is 100 mL/min.
(5) And (3) performing secondary calcination on the precursor material obtained in the step (4) to form a spherical silicon-carbon material product, wherein the inlet temperature is 1000 ℃, the calcination time is 2h, the calcination process needs to be performed by introducing protective gas, and the flow of N 2 is 100 mL/min. The morphology of the silicon-carbon material product is shown in figure 1, the electrochemical performance is shown in figure 2, the first capacity and the first efficiency of the silicon-carbon material are 1136 mAh/g and 88.4%, and the capacity retention rate after 100 circles is 84.6%.
Example 2
(1) Carrying out sulfuric acid leaching on 20 g negative electrode graphite (containing Li 1168 ppm, cu 666 ppm, fe 4260 ppm, al 308 ppm and C98.3%) with sulfuric acid concentration of 250 g/L, liquid-solid ratio of 7.5:1, water bath temperature of 90 ℃ and leaching time of 3 h, then carrying out high-temperature roasting with roasting temperature of 1200 ℃ and heat preservation time of 3 h, wherein protective gas is required to be introduced in the roasting process, the protective gas is N 2 or Ar, the flow is 100 mL/min, and the regenerated graphite (containing Li 15.2 ppm, cu 112.6 ppm, fe 21.6 ppm, al 83.2 ppm and C99.91%) is obtained.
(2) Adding the regenerated graphite obtained in the step (1) into nano silicon powder, a dispersing agent PVP and alcohol for ball milling to form slurry. According to the mass ratio of the regenerated graphite to the nanometer silicon powder to the PVP of 1:0.2:0.02, the liquid-solid ratio of the alcohol to the total material of 7.5:1, the ball milling speed of 400 rpm and the ball milling time of 2 h.
(3) Adding asphalt/NMP solution into the slurry obtained in the step (2) for secondary ball milling to form secondary slurry, wherein the mass of asphalt is 15% of the sum of the mass of graphite and the mass of silica powder, the liquid-solid ratio of the added NMP to the asphalt is 7.5:1, the secondary ball milling speed is 200 rpm, and the secondary ball milling time is 3 h.
(4) And (3) performing spray granulation on the secondary slurry obtained in the step (3) by spray drying equipment, wherein the inlet temperature is 180 ℃, the outlet temperature is 60 ℃, the materialization pressure is 0.2 Mpa, and the feeding speed is 150 mL/min.
(5) And (3) performing secondary calcination on the precursor material obtained in the step (4) to form a spherical silicon-carbon material product, wherein the inlet temperature is 1200 ℃, the calcination time is 3 h, the calcination process needs to be performed by introducing protective gas, and the flow of N 2 is 200 mL/min.
Example 3
(1) The method comprises the steps of carrying out sulfuric acid leaching on 20 g negative electrode graphite (containing Li 1650 ppm, cu 682 ppm, fe 5120 ppm, al 408 ppm and C97.8%) with sulfuric acid concentration of 300 g/L, liquid-solid ratio of 10:1, water bath temperature of 90 ℃ and leaching time of 3h, then carrying out high-temperature roasting with roasting temperature of 1200 ℃ and heat preservation time of 3h, wherein protective gas is required to be introduced in the roasting process, the protective gas is N 2 or Ar, the flow is 200 mL/min, and the regenerated graphite (containing Li 2.1 ppm, cu 82.3 ppm, fe 12.7 ppm, al 67.5 ppm and C99.94%) is obtained.
(2) Adding nano silicon powder, dispersing agent PVP and alcohol into the regenerated graphite obtained in the step (1) for ball milling to form slurry. According to the mass ratio of the regenerated graphite to the nanometer silicon powder to the PVP of 1:0.1:0.01, the liquid-solid ratio of the alcohol to the total material of 10:1, the ball milling speed of 400 rpm and the ball milling time of 2 h.
(3) Adding asphalt/NMP solution into the slurry obtained in the step (2) for secondary ball milling to form secondary slurry, wherein the mass of asphalt is 10% of the sum of the mass of graphite and the mass of silica powder, the liquid-solid ratio of the added NMP to the asphalt is 7.5:1, the secondary ball milling speed is 400 rpm, and the secondary ball milling time is 4 h.
(4) And (3) performing spray granulation on the secondary slurry obtained in the step (3) by spray drying equipment, wherein the inlet temperature is 200 ℃, the outlet temperature is 100 ℃, the materialization pressure is 0.3 Mpa, and the feeding speed is 300 mL/min.
(5) And (3) performing secondary calcination on the silicon-carbon material precursor obtained in the step (4) to form a spherical silicon-carbon material product, wherein the inlet temperature is 1500 ℃, the calcination time is 3 h, the calcination process needs to be performed by introducing protective gas, and the flow rate of N 2 is 300 mL/min.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A high-value recovery method for graphite negative electrode waste of a lithium battery is characterized by comprising the steps of carrying out sulfuric acid leaching on the graphite negative electrode waste of the lithium battery to remove impurities in the waste, carrying out high-temperature calcination to remove organic matters and repair internal structures, adding nano silicon powder, PVP powder and an alcohol solution into regenerated graphite, carrying out primary ball milling in a ball mill to obtain slurry, adding an asphalt/NMP solution into the slurry, carrying out secondary ball milling to obtain secondary slurry, carrying out spray drying on the secondary slurry to obtain spherical silicon-carbon material precursor, and carrying out fractional distillation to recover pure alcohol and NMP reagent after alcohol/NMP gas is generated at an outlet in the spray drying process;
The concentration of sulfuric acid in the acid leaching process is 50-400 g/L, the leaching temperature is 50-100 ℃, the liquid-solid ratio is 5:1-15:1, the leaching time is 2-12 h, the high-temperature calcination temperature of graphite is 500-1500 ℃, the heat preservation time is 1-6 h, protective gas is required to be introduced in the calcination process, the protective gas is N 2 or Ar, and the flow is 60-120 mL/min.
2. The method for recycling the graphite negative electrode waste of the lithium battery, which is characterized in that the mass ratio of graphite to nanometer silicon powder to PVP is 1:0.05-0.4:0.005-0.04, the liquid-solid ratio of alcohol to total materials is 2.5:1-7.5:1, the ball milling speed is 200-500 rpm, and the ball milling time is 1-6 h.
3. The method for recycling the lithium battery graphite negative electrode waste with high value is characterized in that the mass of added asphalt is 5-20% of the sum of the mass of graphite and the mass of silicon powder, the liquid-solid ratio of added NMP to the asphalt is 3:1-15:1, the secondary ball milling speed is 200-500 rpm, and the secondary ball milling time is 1-6 h.
4. The method for recycling graphite negative electrode waste of lithium battery according to claim 1, wherein the inlet temperature of the spray drying process equipment is 120-200 ℃, the outlet temperature is 60-100 ℃, the atomization pressure is 0.05-0.3 MPa, and the feeding speed is 20-500 mL/min.
5. The method for recycling the graphite negative electrode waste of the lithium battery, as set forth in claim 1, is characterized in that the secondary calcination temperature is 1000-1600 ℃, the calcination time is 1-8 hours, the calcination process requires to introduce protective gas, the protective gas is N 2 or Ar, and the flow is 100-500 mL/min.
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| CN108172812A (en) * | 2018-01-30 | 2018-06-15 | 郑州中科新兴产业技术研究院 | A kind of silicon carbon negative electrode material that can be used for power battery and preparation method thereof |
| CN110600684A (en) * | 2018-09-12 | 2019-12-20 | 湖北万润新能源科技发展有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
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| CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN108736007A (en) * | 2018-08-20 | 2018-11-02 | 赣州市瑞富特科技有限公司 | A kind of preparation method of high compacted density lithium ion battery silicon-carbon cathode material |
| CN114335495A (en) * | 2021-12-28 | 2022-04-12 | 南昌航空大学 | Method for preparing silicon-carbon negative electrode material by using waste graphite of lithium ion battery |
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