CN116832805B - A waste lithium battery graphite-supported manganese dioxide catalyst and its preparation method and application - Google Patents
A waste lithium battery graphite-supported manganese dioxide catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a graphite-loaded manganese dioxide catalyst for waste lithium batteries, and a preparation method and application thereof; the waste lithium battery graphite supported manganese dioxide catalyst is prepared by performing wet ball milling on waste graphite powder, dispersing the obtained activated graphite into a mixed solution of KMnO 4 and MnSO 4, and performing hydrothermal reaction at 120-180 ℃ for 8-20 hours, wherein the catalyst enhances the catalytic activity of formaldehyde at room temperature, nonmetallic and metal doping atoms contained in the waste lithium battery graphite not only provide a large number of defect sites for anchoring the manganese dioxide and generate highly-dispersed and active manganese dioxide active sites with enhanced activity for improving the catalytic performance of formaldehyde, but also promote the stripping of the graphite in the formation process, further enlarge the surface area of the waste lithium battery graphite, and reversely influence the final growth morphology of the manganese dioxide, so that the active area is greatly improved, and the enhancement of the catalytic activity of formaldehyde is realized.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a graphite-supported manganese dioxide catalyst for waste lithium batteries, a preparation method thereof and application thereof in enhancing catalytic oxidation of formaldehyde.
Background
Formaldehyde (HCHO) is a colorless and readily soluble, irritating gas that has been identified by the international agency for research on cancer (IARC) as a class of carcinogens. Acute poisoning of formaldehyde is manifested by irritation to skin and mucous membrane. The long-term exposure to formaldehyde can reduce the respiratory function of the organism, the information integration function of the nervous system and influence the immune response of the organism, and has toxic effects on cardiovascular system, endocrine system, digestive system, reproductive system and kidney. When the formaldehyde concentration reaches 0.1mg/m 3, the throat is uncomfortable, and when the formaldehyde concentration reaches 0.5mg/m 3, eyes are stimulated, and lacrimation is caused. When reaching 0.6mg/m 3, severe cases such as throat pain, nausea, vomiting, pulmonary edema and the like are caused. When 30mg/m 3 is reached, death of the person may result.
The main source of formaldehyde is glue for gluing artificial boards (melamine is also used as glue and MDI glue, formaldehyde is not contained but is expensive, and not popularized), and is generally urea-formaldehyde resin which takes formaldehyde as a main component, and along with decoration, the artificial boards enter families, and formaldehyde is released into the families. Secondly, the formaldehyde is released from coating, paint, textile and other fabric soft packages, wallpaper, wall cloth, artificial leather products and the like. Residual formaldehyde and unreacted formaldehyde in the plate can be gradually released to the surrounding environment, and the formaldehyde is a main body for forming indoor formaldehyde pollution. The release period of formaldehyde is as long as 3-15 years, and if the formaldehyde is not treated effectively, the formaldehyde can cause great harm to human health.
The current methods for removing indoor formaldehyde are mainly divided into three categories, namely a ventilation method, an adsorption method and a chemical method. Limitations of ventilation facilities, outdoor environments, etc. make increasing ventilation a method for effectively controlling indoor formaldehyde concentration for a long period of time. The adsorption method has the problem of adsorption saturation, formaldehyde can be released into a room after saturation, and formaldehyde can not be removed for a long time. The chemical method is commonly a photocatalysis method and a catalytic oxidation method, wherein the photocatalysis method cannot be widely popularized due to excessive dependence on ultraviolet light, and the catalytic oxidation method can completely oxidize and decompose formaldehyde into CO 2 and H 2 O and has stronger oxidizing property. Transition metal oxides are a type of catalyst for chemical catalytic oxidation of formaldehyde, but the slow catalytic reaction rate in a high-temperature catalytic environment is still a problem to be solved.
Under the important policy guide of environmental management and sustainable development of society, the recycling of waste lithium batteries attracts great importance. The negative electrode of the lithium battery is composed of a copper foil coated with a graphite-based anode material, wherein graphite occupies about 12-21wt%. The waste graphite cathode contains hetero atoms such as sulfur, nitrogen and the like, and also contains metal atoms such as nickel, cobalt, iron, manganese, lithium, copper and the like, so that a large number of defect sites can be provided for being used as a regenerated catalyst. Therefore, the waste lithium battery graphite is compounded with the oxide of the chemical catalytic formaldehyde, so that the catalytic activity of the formaldehyde is improved at room temperature.
Disclosure of Invention
Aiming at the defects and the problems to be solved in the prior art, the invention provides a graphite-loaded manganese dioxide catalyst for waste lithium batteries, a preparation method thereof and application thereof in enhancing formaldehyde catalytic oxidation. The catalyst can improve the catalytic activity of formaldehyde at room temperature.
The technical scheme of the invention is as follows:
A preparation method of a graphite-loaded manganese dioxide catalyst for a waste lithium battery comprises the following steps:
(1) Pretreating, namely placing the waste graphite powder into a ball mill for wet ball milling to obtain activated graphite;
The waste graphite powder is derived from black powder in a dry process flow in a waste lithium ion battery recovery process, is subjected to discharge, crushing, incineration and screening, and can be directly used as a raw material due to complete separation from other substances in the dry process, and further impurity removal is not needed;
putting waste graphite powder into a ball milling tank, pouring deionized water, uniformly stirring, performing wet ball milling, filtering after ball milling is finished, and drying to obtain activated graphite;
Preferably, the mass volume ratio of the waste graphite powder to the deionized water is 50:800, g/mL;
The ball milling rotation speed is 200-1000 rpm, preferably 500-800 rpm; the ball milling time is 2-10 hours, preferably 2-4 hours;
(2) Dispersing the activated graphite obtained in the step (1) into a mixed solution of KMnO 4 and MnSO 4, uniformly stirring, heating to 120-180 ℃ after sealing for hydrothermal reaction for 8-20 hours, cooling to room temperature, filtering, washing and drying to obtain the graphite-loaded manganese dioxide catalyst of the waste lithium battery;
Preferably, the mass volume ratio of the activated graphite to the mixed solution of KMnO 4 and MnSO 4 is 3-8:150, g/mL, preferably 5:150, g/mL;
Preferably, the temperature of the hydrothermal reaction is 150 ℃ and the time is 12 hours;
The mole ratio of KMnO 4 to MnSO 4 is (1-10): 1, preferably 3:1;
The total amount of KMnO 4 and MnSO 4 can indirectly regulate and control the MnO 2 load, and the MnO 2 load is 1% -30%, preferably 17%;
The total amount of KMnO 4 and MnSO 4 is determined according to MnO 2 load, waste graphite powder consumption and formula (a);
2KMnO4+3MnSO4+2H2O＝5MnO2+2H2SO4(a)。
The invention relates to a graphite-supported manganese dioxide catalyst for waste lithium batteries, which is prepared by the method, wherein manganese dioxide is of a birnessite type structure.
The graphite-loaded manganese dioxide catalyst for the waste lithium battery can be used for removing formaldehyde by room-temperature catalytic oxidation, and comprises the following specific steps:
(1) The pretreatment of formaldehyde removal experiment, wherein the formaldehyde purification experiment is carried out in a closed experiment cabin with the volume of 100L, the closed cabin consists of a cabin body, a cover body and a sealing clamp, the inner wall of the experiment cabin is wiped by distilled water before the experiment, the experiment cabin is cleaned, the cabin body is closed after the inner wall of the experiment cabin is dried to measure the air in the cabin, a British PPM HTV-M formaldehyde analyzer is adopted to measure the formaldehyde concentration, and the experiment can be carried out after the formaldehyde concentration is measured to be lower than 0.08 PPM;
(2) Weighing graphite-loaded manganese dioxide catalyst of waste lithium batteries, placing the catalyst into a small fan, uniformly spreading the catalyst, placing the catalyst into a formaldehyde test cabin together with a formaldehyde tester, immediately covering a cover, sealing the cover, and performing corresponding experiments at room temperature;
the amount of the graphite-supported manganese dioxide catalyst of the waste lithium battery is 1-5 g, preferably 1.5g;
the initial concentration of formaldehyde gas is 0.2 to 1ppm, preferably 0.5ppm.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, waste lithium battery graphite and manganese dioxide are compounded by an in-situ synthesis method, and the waste lithium battery graphite and manganese dioxide supplement each other in a hydrothermal process, so that a large number of defect sites are provided for anchoring the manganese dioxide by nonmetal and metal doping atoms contained in the waste lithium battery graphite, high-dispersion and activity-enhanced manganese dioxide active sites are generated for improving formaldehyde catalytic performance, and meanwhile, the stripping of graphite is promoted by the manganese dioxide in the forming process, the surface area of the waste lithium battery graphite is further enlarged, the final growth morphology of the manganese dioxide is adversely affected, the active area is greatly increased, and the improved formaldehyde catalytic activity is realized.
Drawings
FIG. 1 SEM images (a) of C@17% MnO 2 in example 1 and SEM images (b) of AG@17% MnO 2 in example 4 of the present invention.
FIG. 2 is a graph showing the efficiency of efficiently oxidizing and removing formaldehyde at room temperature of the graphite-supported manganese dioxide catalyst for waste lithium batteries prepared in the embodiment 1 of the invention.
FIG. 3 is a graph showing the efficiency of efficiently oxidizing and removing formaldehyde at room temperature of the graphite-supported manganese dioxide catalyst for waste lithium batteries prepared in the embodiment 4 of the invention.
FIG. 4 is a graph showing N 2 adsorption-desorption characteristics of C@17% MnO 2 in example 1, AG@17% MnO 2 in example 4, waste graphite powder C and activated waste graphite powder AG according to the present invention.
FIG. 5 pore size distribution diagrams of C@17% MnO 2 in example 1, AG@17% MnO 2 in example 4, waste graphite powder C and activated waste graphite powder AG of the present invention.
FIG. 6 is a graph of the efficiency of the efficient oxidation of formaldehyde removal at room temperature for the catalyst of example 1 C@17% MnO 2, example 4 AG@17% MnO 2, and example 5 AC@17% MnO 2 according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the scope of the present invention is not limited thereto.
The waste graphite powder used in the following examples was from Zhejiang Tianneng New Material Co., ltd, and its metal content is shown in Table 1:
TABLE 1 Metal content Meter for waste graphite
The specific surface area, pore volume and average pore diameter data of the relevant materials involved in the examples are shown in Table 2:
TABLE 2 specific surface area, pore volume, average pore size data for waste graphite loaded MnO 2 before and after ball milling
Example 1
The method is characterized in that waste graphite powder which is not pretreated is used as a carrier, and a waste lithium battery graphite-loaded manganese dioxide catalyst is prepared by changing manganese dioxide loading, and is specifically realized through the following synthesis steps:
5g of waste graphite powder which is not pretreated is dispersed into a KMnO 4：MnSO4 solution (150 mL) with the molar ratio of 3:1, the total amount of KMnO 4 and MnSO 4 is regulated to control the loading amount of manganese dioxide to be 0%, 1%, 7%, 13%, 17% and 25%, the mixture is stirred for 5min at 25 ℃ in a constant-temperature heating magnetic stirrer, then the mixture is poured into a 200mL hydrothermal kettle, and the mixture is reacted for 12h at 150 ℃ after being sealed. After the reaction is finished, cooling the hydrothermal kettle to room temperature, filtering the precipitate, flushing with deionized water, and then putting the filtered solid into an oven for drying at 70 ℃ to obtain the waste lithium battery graphite-supported manganese dioxide catalyst with different manganese dioxide loadings (sequentially marked as C, C@1% MnO 2、C@7％MnO2、C@13％MnO2、C@17％MnO2 and C@25% MnO 2).
In FIG. 1, an SEM image of a waste lithium battery graphite (without pretreatment) supported manganese dioxide catalyst prepared at 17% manganese dioxide loading is shown, which is mainly composed of regular-shape nano-sheets. The lamellar structure will expose more active sites than the block structure.
The application of the graphite-loaded manganese dioxide catalyst for waste lithium batteries with different manganese dioxide loadings in efficiently oxidizing and removing formaldehyde at room temperature is realized by the following steps:
1.5g of graphite-loaded manganese dioxide catalyst of the waste lithium battery is weighed and placed in a small fan, and is put into a formaldehyde test cabin together with a formaldehyde tester after being evenly paved, and is immediately covered with a cover to seal, and corresponding experiments are carried out at room temperature. And (3) injecting quantitative formaldehyde solution into the heating plate from the plug opening by using the needle cylinder, and plugging the plug opening. When the indication in the formaldehyde tester is stabilized at 0.5ppm, the fan is started, and the formaldehyde concentration is recorded at intervals of 10 minutes.
The test results show that the formaldehyde removal rate is optimal when the MnO 2 loading is 17 percent, and the formaldehyde removal rate is 80.04 percent within 1h (see figure 2). In the hydrothermal reaction process, when the manganese dioxide load is increased to a certain value, waste graphite reacts with KMnO 4 to generate corresponding MnO 2, the MnO 2 morphology with the best formaldehyde removal performance is wanted to be obtained in the one-step hydrothermal method, the pH value of the solution is important in the reaction, when the waste graphite participates in the reaction, the pH value of the solution can be changed differently, the morphology of the generated MnO 2 can be different, and therefore, the difference of the raw material proportion is demonstrated, and the MnO 2 with different morphologies can appear. Meanwhile, metal atoms (see table 1) such as nickel, cobalt, iron, manganese, lithium, copper and the like in the waste graphite can also participate in the reaction in the hydrothermal process, so that more active sites are formed on the surface of the material.
Example 2
The method is characterized in that waste graphite powder which is not pretreated is used as a carrier, and a waste lithium battery graphite-loaded manganese dioxide catalyst is prepared by changing the ratio of KMnO 4 to MnSO 4, and is specifically realized by the following synthesis steps:
5g of unpretreated waste graphite powder is dispersed into KMnO 4：MnSO4 solution with the molar ratio of 1:1, 2:1, 3:1 and 4:1, the loading amount of MnO 2 is 17 percent, and the mixture is stirred for 5 minutes at 25 ℃ in a constant-temperature heating magnetic stirrer, then poured into a 200mL hydrothermal kettle, and reacted for 12 hours at 150 ℃ after sealing. And after the reaction is finished, cooling the hydrothermal kettle to room temperature, filtering the precipitate, flushing with deionized water, and then putting the filtered solid into an oven for drying at 70 ℃ to prepare the waste graphite-loaded manganese dioxide.
The method for testing the waste lithium battery graphite-loaded manganese dioxide catalyst by using the KMnO 4 and MnSO 4 in the ratio of 4:1 is similar to that of example 1.
The test results show that the formaldehyde removal rate in 1h is 79.60% when the ratio of KMnO 4 to MnSO 4 is 4:1.
Example 3
The method is characterized in that pretreated waste graphite powder is used as a carrier, and a waste lithium battery graphite-loaded manganese dioxide catalyst is prepared by changing the rotating speed of a ball mill, and is specifically realized through the following synthesis steps:
(1) And (3) putting 50g of waste graphite powder into a ball milling tank, pouring 800mL of deionized water into the tank, uniformly stirring the waste graphite powder and the deionized water, and respectively obtaining activated graphite under different ball milling conditions, wherein the rotation speed of a ball mill is 200rpm, 400rpm, 600rpm and 800rpm, and the ball milling time is 2 hours.
(2) 5G of pretreated waste graphite powder is dispersed into KMnO 4：MnSO4 solution with the molar ratio of 3:1, the loading amount of MnO 2 is 17%, the mixture is stirred for 5min at 25 ℃ in a constant-temperature heating magnetic stirrer, then the mixture is poured into a 200mL hydrothermal kettle, and the mixture is sealed and then reacted for 12h at 150 ℃ in an oven. And after the reaction is finished, cooling the hydrothermal kettle to room temperature, filtering the precipitate, flushing with deionized water, and then placing the filtered solid into a vacuum oven for drying at 70 ℃ to obtain the graphite-loaded manganese dioxide catalyst material of the waste lithium battery.
The method for testing the graphite-loaded manganese dioxide catalyst of the waste lithium battery, which is prepared at different ball milling speeds, is applied to efficiently oxidizing and removing formaldehyde at room temperature, and is the same as that of example 1.
The test result shows that the formaldehyde removal rate in 1h is 84.31% when the rotating speed of the ball mill is 400 rmp.
Example 4
The method is characterized in that pretreated waste graphite powder is used as a carrier, and a waste lithium battery graphite-loaded manganese dioxide catalyst is prepared by changing the ball milling time of a ball mill, and is specifically realized through the following synthesis steps:
(1) 50g of waste graphite powder is placed in a ball milling tank, 800mL of deionized water is poured into the tank, the waste graphite powder and the deionized water are uniformly stirred, 5g of waste graphite powder is placed in a ball mill for carrying out, the rotation speed of the ball mill is 600rpm, the ball milling time is 2h (the obtained material is marked as AG@17% MnO 2), 4h, 6h and 8h, and activated graphite under different ball milling conditions is prepared.
(2) 5G of pretreated waste graphite powder is dispersed into KMnO 4：MnSO4 solution with the molar ratio of 3:1, the loading amount of MnO 2 is 17%, the mixture is stirred for 5min at 25 ℃ in a constant-temperature heating magnetic stirrer, then the mixture is poured into a 200mL hydrothermal kettle, and the mixture is sealed and then reacted for 12h at 150 ℃ in an oven. And after the reaction is finished, cooling the hydrothermal kettle to room temperature, filtering the precipitate, flushing with deionized water, and then placing the filtered solid into a vacuum oven for drying at 70 ℃ to obtain the graphite-loaded manganese dioxide catalyst material of the waste lithium battery.
In FIG. 1b is an SEM image of a spent lithium battery graphite (pretreated) supported manganese dioxide catalyst prepared at a ball milling time of 2h, which is seen to be a typical birnessite layered structure. It is clear from the characterization of specific surface area and pore size distribution (see fig. 4, 5 and table 2) that the porous material has a large specific surface area (27.62 m 2/g) and a rich mesoporous structure, which is very helpful for absorption and diffusion of formaldehyde gas molecules.
The method for testing the graphite-loaded manganese dioxide catalyst of the waste lithium battery, which is prepared during different ball milling times, is applied to efficiently oxidizing and removing formaldehyde at room temperature, and the testing method is the same as that of example 1.
The test results show that the formaldehyde removal rate in 1h is 97.58% when the ball milling time of the ball mill is 2h (see figure 3).
Example 5
The preparation of the supported manganese dioxide catalyst using commercial activated carbon (from grapefruit Activity Co.) as a support is accomplished by the following synthesis steps:
(1) 50g of commercial activated carbon was placed in a ball milling pot, 800mL of deionized water was poured into the pot, the commercial activated carbon and deionized water were stirred uniformly, the rotation speed of the ball mill was 600rpm, and the ball milling time was 2 hours, to prepare Activated Carbon (AC).
(2) 5G of activated carbon after pretreatment is dispersed into KMnO 4：MnSO4 solution with the molar ratio of 3:1, the loading amount of MnO 2 is 17%, the mixture is stirred for 5min at 25 ℃ in a constant-temperature heating magnetic stirrer, then the mixture is poured into a 200mL hydrothermal kettle, and the mixture is sealed and then reacted for 12h at 150 ℃ in an oven. After the reaction is finished, cooling the hydrothermal kettle to room temperature, filtering the precipitate, flushing with deionized water, and then putting the filtered solid into a vacuum oven for drying at 70 ℃ to obtain the commercial activated carbon supported manganese dioxide catalyst material (marked as AC@17% MnO 2).
The experiment uses the activated carbon with the commercial iodine value of 800 for comparison instead of pure graphite, because the activated carbon has better and more common adsorption performance and is more suitable for comparison as a pure adsorbent. The efficiency map of the high-efficiency oxidation of different composite materials at room temperature is shown in fig. 6, and the efficiency of the activated waste lithium battery graphite-loaded manganese dioxide catalyst (AG@17% MnO 2) containing metal elements for removing formaldehyde at room temperature is obviously higher than that of the activated pure activated carbon-loaded manganese dioxide catalyst (AC@17% MnO 2), which also proves that the metal elements naturally existing in the waste graphite have promotion significance for removing formaldehyde at room temperature of the waste lithium battery graphite-loaded manganese dioxide catalyst prepared later.
Claims (7)
1. A preparation method of a graphite-loaded manganese dioxide catalyst for a waste lithium battery comprises the following steps:
(1) Pretreating, namely placing the waste graphite powder into a ball mill for wet ball milling to obtain activated graphite;
(2) And (3) hydrothermal synthesis, namely dispersing the activated graphite obtained in the step (1) into a mixed solution of KMnO 4 and MnSO 4, uniformly stirring, heating to 120-180 ℃ after sealing, carrying out hydrothermal reaction for 8-20 h, cooling to room temperature, filtering, washing and drying to obtain the graphite-loaded manganese dioxide catalyst of the waste lithium battery.
2. The method for preparing the graphite-supported manganese dioxide catalyst of the waste lithium battery, as claimed in claim 1, is characterized in that in the step (1), the wet ball milling operation method comprises the steps of putting waste graphite powder into a ball milling tank, pouring deionized water, uniformly stirring, performing wet ball milling, filtering after ball milling is finished, and drying to obtain activated graphite;
The mass volume ratio of the waste graphite powder to the deionized water is 50:800, g/mL;
The ball milling rotating speed is 200-1000 rpm; the ball milling time is 2-10 h.
3. The method for preparing the graphite-supported manganese dioxide catalyst for the waste lithium battery, as claimed in claim 1, wherein in the step (2), the mass-volume ratio of the activated graphite to the mixed solution of KMnO 4 and MnSO 4 is 3-8:150 g/mL.
4. The method for preparing the graphite-supported manganese dioxide catalyst for the waste lithium battery as claimed in claim 1, wherein in the step (2), the mole ratio of KMnO 4 to MnSO 4 is (1-10): 1.
5. The method for preparing the graphite-supported manganese dioxide catalyst for the waste lithium battery, as claimed in claim 1, is characterized in that the loading of MnO 2 of the graphite-supported manganese dioxide catalyst for the waste lithium battery is 1% -30%.
6. The graphite-supported manganese dioxide catalyst for waste lithium batteries prepared by the preparation method according to any one of claims 1-5.
7. The use of the graphite-supported manganese dioxide catalyst for waste lithium batteries in removing formaldehyde by room-temperature catalytic oxidation according to claim 6.
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Non-Patent Citations (1)
| Title |
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| 室温下废旧石墨负极负载二氧化锰除甲醛性能的研究;陆剑伟 等;《浙江化工》;20230912;第54卷(第8期);33-39 * |
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