CN111977646A - Method for preparing expanded graphite/silicon carbon material from graphite cathode of waste battery - Google Patents
Method for preparing expanded graphite/silicon carbon material from graphite cathode of waste battery Download PDFInfo
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- CN111977646A CN111977646A CN202010698688.0A CN202010698688A CN111977646A CN 111977646 A CN111977646 A CN 111977646A CN 202010698688 A CN202010698688 A CN 202010698688A CN 111977646 A CN111977646 A CN 111977646A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
A method for preparing an expanded graphite/silicon carbon material by using a graphite cathode of a waste battery. The invention comprises the following steps: (1) pickling, filtering and drying the waste graphite negative electrode sheet to obtain a graphite material; (2) mixing the graphite material obtained in the step (1) with an intercalation agent and an oxidizing agent for reaction, and then washing, filtering and drying to obtain expandable graphite; (3) placing the expandable graphite in a muffle furnace to be roasted for a period of time to obtain the expandable graphite; (4) and ball-milling the obtained expanded graphite and a silicon-carbon material to obtain the expanded graphite/silicon-carbon composite material. According to the method provided by the invention, the pollution generated by the waste lithium ion battery is effectively reduced, and the waste graphite material of the negative electrode can be recycled to be regenerated into the expanded graphite/silicon carbon composite negative electrode material. The regenerated material has excellent mechanical strength and toughness, good cycle performance, large reversible capacity and high capacity retention rate.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a method for preparing an expanded graphite/silicon carbon material by using a graphite cathode of a waste battery
Background
Since the commercialization of lithium ion batteries in 1990, lithium ion batteries have been widely used in portable electronic devices such as mobile phones, notebook computers, and digital cameras because of their advantages of high capacity, light weight, good cycle performance, and little pollution. However, since the rise of lithium ion batteries, a large amount of graphite materials are used as battery electrodes, and a reasonable recycling method is lacked, so that a large amount of graphite materials are wasted.
The current commercialized negative electrode material is mainly graphite (MCMB), the theoretical specific capacity of the negative electrode material is only 372mAh/g, and compared with the traditional graphite negative electrode material, silicon has extremely high specific mass capacity (4200mAh/g) which is more than ten times that of natural graphite. Compared with a carbon material, the silicon has higher lithium-releasing and-inserting potential, can effectively avoid the precipitation of lithium in the process of high-rate charge and discharge, and can improve the safety of the battery. However, since the silicon has a volume expansion effect in the charging and discharging processes, the structure of the silicon is damaged, the active material falls off from the current collector, and an irreversible electrolyte membrane is continuously formed, so that the reversible capacity, the cycling stability and the rate capability of the silicon negative electrode material are poor. Silicon carbon composite nanostructures are a very effective way to suppress volume expansion. This is mainly because the carbon material has good electrical conductivity and small volume change. The coated silicon material can enhance the conductivity of the material, and avoid agglomeration among silicon nano particles and expansion of the material, thereby prolonging the cycle life and improving the rate capability.
Researches show that the expanded graphite has excellent electrical and mechanical properties and high theoretical specific surface area, the characteristics determine the huge application potential of the expanded graphite in the field of lithium ion batteries, and a plurality of researchers have developed researches for improving the electrochemical properties of the cathode material by compounding the expanded graphite. In particular, the lithium ion battery cathode material prepared from the expanded graphite/silicon carbon material by using the waste graphite has good economic benefit and wide market prospect.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing an expanded graphite/silicon carbon material by using a graphite cathode of a waste battery, the method has simple preparation process, effectively utilizes the waste graphite material, and the regenerated material has the characteristics of large reversible capacity, designable capacity, good cycle performance and large-current discharge capacity and high tap density.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing expanded graphite/silicon carbon material by using graphite cathode of waste battery comprises the following steps:
(1) acid washing, filtering and drying the negative plate of the waste lithium battery to obtain a graphite material;
(2) placing the obtained regenerated graphite material in a mixed solution of an oxidant and an intercalating agent for reaction, and after the reaction is finished, washing, filtering and drying to obtain expandable graphite;
(3) placing the prepared expandable graphite in a muffle furnace for roasting for a certain time, and cooling to obtain the expandable graphite after the reaction is finished;
(4) and ball-milling the obtained expanded graphite and a silicon-carbon material to obtain the expanded graphite/silicon-carbon composite material.
Preferably, the acid used in the acid washing in step (1) is one or more selected from nitric acid, sulfuric acid and trifluoroacetic acid.
Preferably, in the step (1), the solid-to-liquid ratio of the negative electrode plate to the acid is 1: 10-100 g/L, and more preferably, the solid-to-liquid ratio of the negative electrode plate to the acid is 60 g/L.
Preferably, in the step (1), the mass concentration of the pickling acid is 0-5 mol/L, and more preferably, the mass concentration of the pickling acid is 2 mol/L.
Preferably, in the step (1), the time for pickling is 10-120 min, and more preferably, the time for pickling is 30 min.
Preferably, in the step (1), the temperature is 20-60 ℃, and more preferably, the pickling temperature is 40 ℃.
Preferably, in the step (2), the oxidizing agent is selected from one or more of potassium permanganate, potassium dichromate, perchloric acid and hydrogen peroxide.
Preferably, in step (2), the intercalation agent is selected from one or more of concentrated nitric acid, concentrated sulfuric acid, glacial acetic acid and concentrated phosphoric acid.
Preferably, in the step (2), the solid-to-liquid ratio of the graphite material to the intercalation agent is 1: 10-50 g/mL, and more preferably, the solid-to-liquid ratio of the graphite material to the intercalation agent is 1:15 g/mL.
Preferably, in the step (2), the mass ratio of the graphite material to the oxidant is 1: 0.3-1, and more preferably, the mass ratio of the graphite material to the oxidant is 2: 1.
Preferably, in the step (2), the reaction time is 10-120 min. More preferably, the reaction time is 60 min.
Preferably, in step (2), the water is washed until the pH is neutral.
Preferably, in the step (3), the roasting temperature is 600-1000 ℃, and more preferably, the roasting temperature is 900 ℃.
Preferably, in the step (3), the roasting time is 10s to 5min, and more preferably, the roasting time is 30 s.
Preferably, in the step (4), the mass ratio of the expanded graphite to the silicon-carbon material is 1: 1-9, and more preferably, the mass ratio of the expanded graphite to the silicon-carbon material is 3: 7.
Preferably, in the step (4), the rotation speed of the ball mill is 450 r/min.
Preferably, in the step (4), the mass ratio of the ball milling beads is 20: 1.
Preferably, in the step (4), the ball milling time is 3-15 h, and more preferably 7 h.
The invention has the beneficial effects that:
(1) the invention adopts the acid cleaning method to completely separate the copper foil from the negative active material (graphite), simultaneously removes the compound on the surface of the pole piece, and retains the typical sp of the graphite2Obtaining a high-purity graphite material by using the planar structure characteristics and the layered morphology;
(3) the prepared expanded graphite is subjected to ball milling to obtain the expanded graphite/silicon-carbon composite material which has good mechanical strength and toughness and effectively reduces the falling of an active material caused by the volume expansion of silicon.
(4) The method has the advantages of simple process flow, high efficiency and environment-friendly recovery process, and the prepared expanded graphite/silicon carbon composite material is suitable for large-scale industrial recovery.
Drawings
FIG. 1 is an abstract drawing of the present invention;
FIG. 2 is an SEM image of an expanded graphite/silicon carbon composite material prepared in example 1 of the present invention;
fig. 3 is an electrochemical cycle diagram of the expanded graphite/silicon carbon composite material prepared in example 1 of the present invention.
FIG. 4 is an SEM image of an expanded graphite/silicon carbon composite material prepared in example 2 of the present invention;
fig. 5 is an electrochemical magnification chart of the expanded graphite/silicon carbon composite material obtained in example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The embodiment comprises the following steps:
(1) placing the graphite cathode of the waste lithium ion battery in sulfuric acid with the mass fraction of 2mol/L for acid washing for 30min at 40 ℃ according to the solid-to-liquid ratio of 1:80g/mL, filtering and drying to obtain a high-purity regenerated graphite material;
(2) placing the obtained regenerated graphite material into a mixed solution of an oxidant and an intercalating agent for reaction, wherein the volume ratio of graphite (g) to the intercalating agent (mL) to the oxidant (g) is 1:10:0.3, the intercalating agent is concentrated nitric acid and concentrated phosphoric acid, the volume ratio of the intercalating agent to the concentrated phosphoric acid is 1:3, the oxidant is potassium permanganate, stirring and reacting for 60min, washing to be neutral after the reaction is finished, filtering and drying to obtain expandable graphite;
(3) placing the obtained expandable graphite in a muffle furnace to be roasted for 1min at 900 ℃ to obtain expanded graphite; and then, ball-milling the expanded graphite and the silicon-carbon material in a ball mill for 9 hours in a mass ratio of 3:7 and a mass ratio of ball milling beads to powder of 20:1 to obtain the expanded graphite/silicon-carbon composite material.
The expanded graphite/silicon carbon composite material prepared in this example was subjected to electron microscope scanning, and the result is shown in fig. 2 (SEM), where it can be seen that the expanded graphite has a loose structure, and the pores in the expanded graphite are filled with silicon nanoparticles; the feasibility of preparing the expanded graphite/silicon-carbon composite material by the experimental scheme is proved. In addition, electrochemical cycle test is carried out on the expanded graphite/silicon carbon composite material, and the result is shown in figure 3, the specific discharge capacity is kept above 950mAh/g after charging and discharging at the multiplying power of 0.2C and 100 cycles of cycle.
Example 2
(1) Placing the graphite cathode of the waste lithium ion battery in 3mol/L trifluoroacetic acid for acid washing for 30min at 40 ℃ according to a solid-to-liquid ratio of 1:80, filtering and drying to obtain a high-purity regenerated graphite material;
(2) placing the obtained regenerated graphite material into a mixed solution of an oxidant and an intercalating agent for reaction, wherein the ratio of graphite (g) to the intercalating agent (mL) to the oxidant (g) is 1:20:5, the intercalating agent is concentrated sulfuric acid and concentrated phosphoric acid, the volume ratio of the intercalating agent is 1:3, the oxidant is potassium permanganate, stirring and reacting for 50min, washing to be neutral after the reaction is finished, filtering and drying to obtain expandable graphite;
(3) placing the obtained expandable graphite in a muffle furnace, and roasting for 30s at 1000 ℃ to obtain expanded graphite; and then, ball-milling the expanded graphite and the silicon-carbon material in a ball mill for 9 hours in a mass ratio of 1:9 and a mass ratio of ball-milling beads to powder of 20:1 to obtain the expanded graphite/silicon-carbon composite material.
The expanded graphite/silicon carbon composite material prepared in this example is subjected to electron microscope scanning, and the result is shown in fig. 4, and similar to fig. 2(SEM image), it can be seen that the expanded graphite has a loose structure, and the pores in the expanded graphite are filled with silicon nanoparticles, which confirms the feasibility of the experimental scheme for preparing the expanded graphite/silicon carbon composite material. And electrochemical performance tests are carried out on the expanded graphite/silicon carbon composite material under different multiplying powers, as shown in figure 5, the expanded graphite/silicon carbon composite material is respectively charged and discharged for 10 circles under multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C and 0.1C, the specific discharge capacity is respectively maintained to be more than 1400mAh/g, 1200mAh/g, 1000mAh/g, 700mAh/g, 400mAh/g and 1250mAh/g, particularly, the expanded graphite/silicon carbon composite material is charged and discharged at 0.1C after multiplying power circulation, and the specific discharge capacity can be recovered to be more than 1250 mAh/g.
Example 3
(1) Placing the graphite cathode of the waste lithium ion battery in 2mol/L trifluoroacetic acid for acid washing for 30min at 40 ℃ according to a solid-to-liquid ratio of 1:80g/mL, filtering and drying to obtain a high-purity regenerated graphite material;
(2) placing the obtained regenerated graphite material into a mixed solution of an oxidant and an intercalating agent for reaction, wherein the ratio of graphite (g) to the intercalating agent (mL) to the oxidant (g) is 1:10:0.5, the intercalating agent is concentrated sulfuric acid, the oxidant is potassium permanganate, stirring and reacting for 80min, washing the obtained product to be neutral after the reaction is finished, and filtering and drying the product to obtain expandable graphite;
(3) placing the obtained expandable graphite in a muffle furnace, and roasting for 30s at 1000 ℃ to obtain expanded graphite; and then, ball-milling the expanded graphite and the silicon-carbon material in a ball mill for 12 hours according to the mass ratio of 2:8 and the mass ratio of ball-milling bead powder of 20:1 to obtain the expanded graphite/silicon-carbon composite material.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (4)
1. A method for preparing expanded graphite/silicon carbon material by using a graphite cathode of a waste battery is characterized by comprising the following steps:
(1) acid washing, filtering and drying the negative plate of the waste lithium ion battery to obtain a graphite material;
(2) placing the obtained graphite material in a mixed solution of an oxidant and an intercalating agent for reaction, and after the reaction is finished, washing, filtering and drying to obtain expandable graphite;
(3) placing expandable graphite in a muffle furnace to be roasted for a certain time to obtain the expandable graphite;
(4) and ball-milling the obtained expanded graphite and a silicon-carbon material to obtain the expanded graphite/silicon-carbon composite material.
2. The method for preparing the expanded graphite/silicon carbon material by using the graphite cathode of the waste battery as the anode according to claim 1, wherein the acid used in the acid washing in the step (1) is selected from one or more of nitric acid, sulfuric acid and trifluoroacetic acid; the solid-to-liquid ratio of the negative plate to the acid is 1: 0-100 g/L, preferably 60 g/L; the concentration of acid used for acid washing is 0-5 mol/L, preferably 2 mol/L; the pickling time is 10-120 min, preferably 60 min; the pickling temperature is 20-60 ℃, and preferably 40 ℃.
3. A method for preparing expanded graphite/silicon carbon material from graphite negative electrode of waste battery according to claim 1 and 2, characterized in that, in the step (2), the oxidant is selected from one or more of potassium permanganate, potassium dichromate, perchloric acid and hydrogen peroxide; the intercalation agent is selected from one or more of concentrated nitric acid, concentrated sulfuric acid, glacial acetic acid and concentrated phosphoric acid; the solid-liquid ratio of the graphite material to the intercalation agent is 1: 10-20 g/mL, preferably 1:15 g/mL; the mass ratio of the graphite material to the oxidant is 1: 0.3-1, preferably 2: 1; the reaction time is 0.5-12 h, preferably 8 h; (ii) a The roasting temperature is 600-1000 ℃, and preferably 900 ℃; the roasting time is 10 s-5 min, preferably 30 s.
4. According to the claims 1 to 3, the method for preparing the expanded graphite/silicon carbon material by using the graphite cathode of the waste battery is characterized in that in the step (4), the mass ratio of the expanded graphite to the silicon carbon material is 1: 1-9, preferably 3: 7; the ball milling rotating speed is 450 r/min; the mass ratio of the ball milling bead powder is 20: 1; the ball milling time is 3-15 h, preferably 7 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200541A (en) * | 2021-03-29 | 2021-08-03 | 中南大学 | Method for recycling graphite negative electrode of waste battery |
| CN115159520A (en) * | 2022-07-19 | 2022-10-11 | 安徽南都华铂新材料科技有限公司 | Method for preparing expanded graphite by using graphite waste residues of negative electrode of retired lithium battery |
| CN115172726A (en) * | 2022-08-11 | 2022-10-11 | 昆明理工大学 | Silicon/graphite nano composite material and preparation method and application thereof |
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Application publication date: 20201124 |