CN116314652A - Biomass-based carbon@ferric oxide composite material and preparation method and application thereof - Google Patents

Biomass-based carbon@ferric oxide composite material and preparation method and application thereof Download PDF

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CN116314652A
CN116314652A CN202310013475.3A CN202310013475A CN116314652A CN 116314652 A CN116314652 A CN 116314652A CN 202310013475 A CN202310013475 A CN 202310013475A CN 116314652 A CN116314652 A CN 116314652A
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biomass
composite material
oxide composite
ferric oxide
based carbon
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杨宏训
吴帅霆
靳艳春
王梓
刘坤
邹旭飞
李雷
陈莺莺
孙志华
�田�浩
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Jiangsu University of Science and Technology
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a biomass-based carbon@ferric oxide composite material, a preparation method and application thereof, wherein the biomass-based carbon@ferric oxide composite material is prepared from biomass, ferric salt and ultrapure water through hydrothermal and calcination treatment; the biomass-based carbon@ferric oxide composite material is of a sheet-shaped structure, wherein ferric oxide particles are riveted on a carbon matrix, the diameters of the ferric oxide particles are 16-28 nm, and the BET specific surface area is 35.67-103.81 m 2 g ‑1 . The biomass-based carbon@ferric oxide composite material provided by the invention is applied to a lithium ion battery, and has long cycle lifeThe advantages of high specific capacity, wide sources of raw materials, convenient mass production, low price, safe operation, easy recovery of byproducts and environment-friendly pollution-free production.

Description

Biomass-based carbon@ferric oxide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy materials and preparation, in particular relates to a lithium ion battery anode material and a preparation method and application thereof, and particularly relates to a biomass-based carbon@ferric oxide composite material and a preparation method and application thereof.
Background
With the rapid worldwide development of electric vehicles and energy storage power stations as well as renewable energy sources, there is a higher demand for energy storage devices, and energy storage technology has become critical. Among various secondary batteries, lithium ion batteries are considered as the most important energy storage and conversion technology, have the outstanding advantages of high energy and high power density, and are also considered as one of the most effective energy storage modes at present. Therefore, further improvement of energy density and cycle performance thereof is also a difficulty and a hot spot of current research.
The metal oxide has high specific capacity as a lithium ion battery cathode material, however, most of the metal oxides have the problem of rapid capacity attenuation when being used as lithium ion battery electrodes, which also limits the development and practical application of the metal oxide as the lithium ion battery cathode material. The carbon material has unique excellent performance, good stability and conductivity, is suitable for being used as a carrier of good metal oxide, and enhances the cycle performance of the metal oxide by buffering the volume change stress of the metal oxide in the charge and discharge process of the lithium ion battery. Biomass, on the other hand, is a rich agricultural waste with high levels of hemicellulose, lignin and cellulose making it a suitable carbon source for carbon electrodes for high performance energy storage systems. In recent years, many scientists have been devoted to the preparation of novel biomass-based nanocarbon materials and the research of their potential applications. The method for applying the composite anode material with the combination of the high-performance cheap carbon material and the iron oxide to the high-performance anode of the lithium ion battery has important significance for solving the current energy crisis and environmental pollution problems. Chinese patent CN108975306a discloses a method for preparing an iron oxide doped biomass porous carbon material, which comprises immersing decolorized enteromorpha in ferric nitrate solution, and calcining and carbonizing under inert gas atmosphere to obtain the iron oxide doped biomass porous carbon material. The method uses a decoloring agent, and iron oxide particles obtained by combining an impregnation method with calcination treatment are large and difficult to control. Chinese patent CN106732358A discloses a method for preparing biomass carbonized microsphere loaded with ferric oxide; firstly, adding an iron salt solution into a hot surfactant solution; cooling, adding crushed coconut shells, stirring, fully mixing and drying; then adding the mixture into zinc acetate solution for hydrothermal reaction, cleaning the product after cooling, and drying the product to obtain the biomass carbonized microsphere loaded with ferric oxide. The method needs to use a surfactant and zinc acetate, and zinc acetate is added to easily introduce zinc-containing impurities into the final product, so that the purity of the material is low and the cost is high. Chinese patent CN108933251a discloses a biomass carbon/iron oxide composite material and a preparation method thereof, wherein biomass carbon is prepared by using an activator KOH at a high temperature, and then prepared iron oxide particles are further loaded on the biomass carbon by a hydrothermal method; the biomass is carbonized at high temperature (800-950 ℃), the energy consumption is high, and the use of the strong base activator is unfavorable for environmental protection. It can be seen that although the existing carbon-based composite materials have porous structures and disordered properties, most reports currently involve complex production processes and high cost of the materials, and are not attractive along with environmental pollution.
Disclosure of Invention
The invention aims to overcome the problems and the defects of the prior art and provides a biomass-based carbon@ferric oxide composite material as well as a preparation method and application thereof.
The biomass carbon sheet is prepared by mixing biomass powder with ferric salt solution, performing hydrothermal treatment and utilizing the catalysis of ferric ions; then adding more ferric salt into the biomass carbon sheet, and under the hydrothermal condition, loading the generated ferric oxide nano particles on the carbon sheet, thereby obtaining the biomass-based carbon@ferric oxide composite material.
The composite material provided by the invention has the advantages of simple preparation process, low production cost, good adsorption performance, high thermal and acid stability, no secondary pollution and capability of realizing high-value utilization of biomass resources. The prepared material is applied to a lithium ion battery anode material, and has high capacity and excellent cycle performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a biomass-based carbon@ferric oxide composite material is prepared from biomass, ferric salt and ultrapure water through hydrothermal and calcining treatment; the biomass-based carbon@ferric oxide composite material is of a sheet structure, wherein ferric oxide particles are riveted on a carbon matrix, the diameters of the ferric oxide particles are 16-28 nm, and the BET specific surface area is 35.67-103.81 m 2 g -1 。
In order to achieve the above purpose, the invention adopts another technical scheme that:
a preparation method of a biomass-based carbon@ferric oxide composite material comprises the following steps:
(1) Cleaning biomass with ultrapure water, drying in an oven, polishing to powder, and sequentially mixing the biomass powder, ferric salt and ultrapure water according to a mass-volume ratio of 1: (0.2-0.6): (50-100) g/mL, mixing and stirring for 0.5-1.5 h, transferring into an autoclave, carrying out hydrothermal treatment at 150-200 ℃ for 5-12 h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) According to the mass-to-volume ratio, the obtained product A, ferric salt and ultrapure water are sequentially 1: (0.5-2): (50-100) g/mL, mixing and stirring for 0.5-1.5 h, transferring into an autoclave, carrying out hydrothermal treatment at 150-200 ℃ for 5-12 h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) Spreading the product B obtained in the step 2 in a porcelain boat, placing the porcelain boat in a tube furnace in inert atmosphere, heating at a rate of 0.5-2 ℃/min to 500-600 ℃ and keeping for 1-3 h, and naturally cooling to room temperature to obtain the biomass-based carbon@ferric oxide composite material.
Further preferably, the biomass is one or more of peanut shell, bagasse, coconut shell, corn leaf, reed and the like in any mass ratio.
Further preferably, the ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulfate in any mass ratio.
Further preferably, the temperature range of the freeze-drying in the step 2 is-40 to-80 ℃.
Further preferably, the inert atmosphere in the step 3 is nitrogen, argon or a mixed gas of nitrogen and argon in any proportion.
In order to achieve the above purpose, a third technical scheme adopted by the invention is as follows:
the specific method for applying the biomass-based carbon@ferric oxide composite material to the lithium ion battery as a negative electrode material comprises the following steps of:
(a) Uniformly mixing biomass-based carbon@ferric oxide composite material, polyvinylidene fluoride and ketjen black according to the mass ratio of (7-8) (1-2) (1) to obtain a solid mixture;
(b) Mixing the solid mixture obtained in the step (a) with N-methyl pyrrolidone according to the mass ratio of (10-20) (80-90), and uniformly stirring to obtain slurry;
(c) Coating the slurry obtained in the step (b) on a copper foil, and drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 10-25 mu m;
(d) Taking the electrode plate of the lithium ion battery obtained in the step (c) as an electrode negative plate, taking the lithium plate as an electrode positive plate, taking a microporous polypropylene film as a diaphragm, and taking 1mol/L LiPF (lithium ion battery power factor) 6 And the solvent is electrolyte, and is filled withAnd assembling the CR2032 button lithium ion battery in the glove box filled with argon.
The invention has the advantages and beneficial effects that:
(1) The method is not applicable to surfactants and other transition metal salts in the preparation process, biomass carbon is not treated at high temperature, and the composite anode material based on biomass carbon@ferric oxide is successfully prepared and used for the anode of the lithium ion battery, so that the production cost of hard carbon materials is reduced, and a thought is provided for industrialization of the biomass carbon anode material.
(2) In the biomass-based carbon@ferric oxide composite material, ferric oxide nano particles are 16-28 nm and uniformly distributed in a carbon material.
(3) The components and the microstructure of the composite material prepared by the hydrothermal synthesis and calcination method endow the electrode with a larger contact area between the material and the electrolyte, so that the lithium ion battery has a more suitable diffusion path in the active material transportation process, has lower electron transfer resistance, can improve the conductivity of the material, and effectively relieves the volume expansion of the material, thereby improving the cycle performance and the rate capability of the battery, meeting the requirements of more high-capacity electronic equipment and leading the application range of the lithium ion battery to be wider. The biomass-based carbon@ferric oxide composite material disclosed by the invention is used as a lithium ion battery anode material, and the cycle performance of the biomass-based carbon@ferric oxide composite material is obviously superior to that of Chinese patent CN108933251A (see figure 6).
Drawings
FIG. 1 is an XRD pattern of a peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 of the invention.
Fig. 2 is a scanning electron microscope image of the peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 of the invention.
FIG. 3 is a transmission electron microscope image of the peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 of the invention.
Fig. 4 is a raman spectrum of the peanut shell-based porous carbon@iron oxide composite material prepared in example 1 of the invention.
Fig. 5 is a nitrogen adsorption and desorption isothermal graph of the peanut shell-based porous carbon@iron oxide composite material prepared in example 1 of the invention.
FIG. 6 shows a peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 of the invention as a lithium ion battery anode material at 200mA g -1 Constant current charge-discharge curve graph of the next 2 nd turn.
FIG. 7 shows that the peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 of the invention is used as a negative electrode material of a lithium ion battery at 200mAg -1 The following cycle performance graph.
Detailed Description
In order that those skilled in the art will more fully appreciate the present invention, a more particular and complete description of the technical aspects of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. The preparation method of the biomass-based carbon@ferric oxide composite material specifically comprises the following steps:
(1) Cleaning peanut shells by using ultrapure water, placing the peanut shells in an oven for drying and polishing to obtain powder, taking 1g of peanut shell powder and 0.4 ferric nitrate, adding 70mL of ultrapure water, stirring for 1h, transferring the mixture into a 100mL autoclave, carrying out hydrothermal treatment at 200 ℃ for 12h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) Adding 1g of ferric salt and 80mL of ultrapure water into the product A respectively, stirring for 0.5h, transferring into a 100mL autoclave, carrying out hydrothermal treatment at 200 ℃ for 12h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) And (3) spreading the product B obtained in the step (2) in a porcelain boat, placing in a tube furnace in an inert atmosphere, keeping the temperature at 500 ℃ at a heating rate of 2 ℃/min for 3 hours, and naturally cooling to room temperature to obtain the peanut shell-based porous carbon@ferric oxide composite material.
2. Application of biomass-based carbon@ferric oxide composite material in CR2032 button lithium ion battery, and the specific method comprises the following steps:
(a) Uniformly mixing peanut shell-based porous carbon@ferric oxide composite material, polyvinylidene fluoride and ketjen black according to a mass ratio of 8:1:1 to obtain a solid mixture;
(b) Mixing the solid mixture obtained in the step (a) with N-methyl pyrrolidone according to the mass ratio of 20:80, and uniformly stirring to obtain slurry;
(c) Coating the slurry obtained in the step (b) on a copper foil, and drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 10-25 mu m;
(d) Taking the electrode plate of the lithium ion battery obtained in the step (c) as an electrode negative plate, taking the lithium plate as an electrode positive plate, taking a microporous polypropylene film as a diaphragm, and taking 1mol/L LiPF (lithium ion battery power factor) 6 And the solvent is electrolyte, and the CR2032 button lithium ion battery is assembled in a glove box filled with argon.
3. Performance test of CR2032 button lithium ion battery: the lithium ion battery assembled in the step (d) is controlled to be 100mA g within the voltage range of 0.01-3V -1 The current density of (2) is used for the first three times of charge-discharge activation. After activation, the voltage is in the range of 0.01-3V, and 200mAg -1 Is subjected to charge-discharge cycle test.
Test results: the XRD spectrum of example 1 (as shown in fig. 1), the peanut shell-based porous carbon @ iron oxide composite material exhibited typical diffraction peaks corresponding to the crystal planes of iron oxide, further confirming successful preparation of the material.
Taking the peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 as an example, scanning by an electron microscope, wherein the scanning result is shown in fig. 2, and the structure of the prepared peanut shell-based porous carbon@ferric oxide composite material is a sheet structure as can be seen from fig. 2.
FIG. 3 is a transmission electron microscope image of the peanut shell-based porous carbon@ferric oxide composite material prepared in example 1 of the invention. It can be seen that iron oxide nanoparticles with a size around 20nm are uniformly dispersed in the carbon matrix, which means that the iron oxide composite material is well dispersed.
Fig. 4 is a raman spectrum of the peanut shell-based porous carbon@iron oxide composite material prepared in example 1 of the invention. As can be seen, at-1350 and-1600 cm -1 There are two broad characteristic peaks corresponding to sp respectively 2 Pi-bond delocalized D and G bands. I D /I G A value of about 0.15 indicates that the material contains a large number of defects that can provide more active sites for the reaction, shortening Li + And the transmission path of the material performance is improved.
Fig. 5 is a nitrogen adsorption-desorption isothermal curve of the material. As can be seen, the isotherm is a typical type IV isotherm, with one P/P 0 Hysteresis loops in the range of about 0.45 to 1.0 indicate that the material contains mesoporous structures as well as slit-like pores. The specific surface area of the material is 92.66m 2 g -1 . This highly porous structure can shorten the electron transport path and increase Li + The active sites are stored, thereby enhancing lithium storage of the material.
FIG. 6 is 200mAg -1 Constant current charge and discharge curve of the lower 2 nd turn. As can be seen from the graph, the charge-discharge capacity of the second cycle is about 719.86/854.32mAh g -1 The coulombic efficiency was about 84.26%.
FIG. 7 shows a peanut shell based porous carbon@ferric oxide composite material as a lithium ion battery anode material at 200mA g -1 The following cycle performance graph. After 100 circles of circulation, the charge and discharge capacity is 711.7/716.71mAh g -1 Has excellent cycle performance.
Example 2
1. The preparation method of the biomass-based carbon@ferric oxide composite material specifically comprises the following steps:
(1) Cleaning peanut shells by using ultrapure water, placing the peanut shells in an oven for drying and polishing to obtain powder, taking 1g of peanut shell powder and 0.2 ferric nitrate, adding 70mL of ultrapure water, stirring for 1h, transferring the mixture into a 100mL autoclave, carrying out hydrothermal treatment at 150 ℃ for 12h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) Adding 1.5g of ferric nitrate and 80mL of ultrapure water into the product A respectively, stirring for 0.5h, transferring into a 100mL autoclave, carrying out hydrothermal treatment at 180 ℃ for 12h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) And (3) spreading the product B obtained in the step (2) in a porcelain boat, placing in a tube furnace in an inert atmosphere, keeping the temperature at 550 ℃ at a heating rate of 2 ℃/min for 3 hours, and naturally cooling to room temperature to obtain the peanut shell-based porous carbon@ferric oxide composite material.
2. Application of biomass-based carbon@ferric oxide composite material in CR2032 button lithium ion battery, and specific method and steps are the same as in example 1.
3. The performance test method of the CR2032 button lithium ion battery was the same as in example 1. The lithium electrical properties are shown in table 1.
Example 3
1. The preparation method of the biomass-based carbon@ferric oxide composite material specifically comprises the following steps:
(1) Cleaning peanut shells by using ultrapure water, placing the peanut shells in an oven for drying and polishing to obtain powder, taking 1g of peanut shell powder and 0.6 ferric chloride, adding 70mL of ultrapure water, stirring for 1h, transferring the mixture into a 100mL autoclave, carrying out hydrothermal treatment at 180 ℃ for 12h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) Adding 1g of ferric chloride and 80mL of ultrapure water into the product A respectively, stirring for 0.5h, transferring into a 100mL autoclave, carrying out hydrothermal treatment at 200 ℃ for 12h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) And (3) spreading the product B obtained in the step (2) in a porcelain boat, placing in a tube furnace in an inert atmosphere, keeping the temperature at 600 ℃ at a heating rate of 2 ℃/min for 3 hours, and naturally cooling to room temperature to obtain the peanut shell-based porous carbon@ferric oxide composite material.
2. Application of biomass-based carbon@ferric oxide composite material in CR2032 button lithium ion battery, and specific method and steps are the same as in example 1.
3. The performance test method of the CR2032 button lithium ion battery was the same as in example 1. The lithium electrical properties are shown in table 1.
Example 4
1. The preparation method of the biomass-based carbon@ferric oxide composite material specifically comprises the following steps:
(1) Cleaning peanut shells by using ultrapure water, placing the peanut shells in an oven for drying and polishing to obtain powder, taking 1g of peanut shell powder and 0.5 ferric nitrate, adding 70mL of ultrapure water, stirring for 1h, transferring the mixture into a 100mL autoclave, carrying out hydrothermal treatment at 200 ℃ for 12h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) Adding 2g of ferric nitrate and 80mL of ultrapure water into the product A respectively, stirring for 0.5h, transferring into a 100mL autoclave, carrying out hydrothermal treatment at 200 ℃ for 12h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) And (3) spreading the product B obtained in the step (2) in a porcelain boat, placing the porcelain boat in a tube furnace with inert atmosphere, heating at a rate of 1.5 ℃/min to 500 ℃ and keeping for 3 hours, and naturally cooling to room temperature to obtain the peanut shell-based porous carbon@ferric oxide composite material.
2. Application of biomass-based carbon@ferric oxide composite material in CR2032 button lithium ion battery, and specific method and steps are the same as in example 1.
3. The performance test method of the CR2032 button lithium ion battery was the same as in example 1. The lithium electrical properties are shown in table 1.
Example 5
1. The preparation method of the biomass-based carbon@ferric oxide composite material specifically comprises the following steps:
(1) Cleaning coconut shells by using ultrapure water, placing the coconut shells in an oven for drying and polishing to obtain powder, taking 1g of peanut shell powder and 0.2 ferric nitrate, adding 70mL of ultrapure water, stirring for 1h, transferring the mixture into a 100mL autoclave, carrying out hydrothermal treatment at 150 ℃ for 12h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) Adding 1.5g of ferric nitrate and 80mL of ultrapure water into the product A respectively, stirring for 0.5h, transferring into a 100mL autoclave, carrying out hydrothermal treatment at 180 ℃ for 12h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) And (3) spreading the product B obtained in the step (2) in a porcelain boat, placing in a tube furnace in an inert atmosphere, keeping the temperature at 550 ℃ at a heating rate of 2 ℃/min for 3 hours, and naturally cooling to room temperature to obtain the coconut shell-based porous carbon@ferric oxide composite material.
2. Application of biomass-based carbon@ferric oxide composite material in CR2032 button lithium ion battery, and specific method and steps are the same as in example 1.
3. The performance test method of the CR2032 button lithium ion battery was the same as in example 1. The lithium electrical properties are shown in table 1.
Example 6
1. The preparation method of the biomass-based carbon@ferric oxide composite material specifically comprises the following steps:
(1) Cleaning bagasse by using ultrapure water, placing the bagasse in an oven for drying and grinding into powder, taking 1g of peanut shell powder and 0.2 ferric nitrate, adding 70mL of ultrapure water, stirring for 1h, transferring the mixture into a 100mL autoclave, carrying out hydrothermal treatment at 150 ℃ for 12h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) Adding 1.5g of ferric nitrate and 80mL of ultrapure water into the product A respectively, stirring for 0.5h, transferring into a 100mL autoclave, carrying out hydrothermal treatment at 180 ℃ for 12h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) And (3) spreading the product B obtained in the step (2) in a porcelain boat, placing in a tube furnace in an inert atmosphere, keeping the temperature at 600 ℃ at a heating rate of 2 ℃/min for 3 hours, and naturally cooling to room temperature to obtain the bagasse-based porous carbon@ferric oxide composite material.
2. Application of biomass-based carbon@ferric oxide composite material in CR2032 button lithium ion battery, and specific method and steps are the same as in example 1.
3. The performance test method of the CR2032 button lithium ion battery was the same as in example 1. The lithium electrical properties are shown in table 1.
The lithium electrical properties of examples 1-6 are shown in Table 1.
Table 1 shows the lithium ion batteries of examples 1 to 6 at 200mA g -1 Charge and discharge test at current, 2 nd turnThe capacity obtained at turn 100.
TABLE 1
Figure BDA0004039104160000081
From Table 1, it can be seen that the biomass-based carbon@iron oxide composite material provided by the invention is used as an anode material applied to a lithium ion battery, and is 200mAg in the range of -1 Under the condition that the charge-discharge capacity is 700mAh g after 100 circles of circulation -1 The graphite cathode material has good cycle performance and is far higher than the current commercialized graphite cathode material.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. The biomass-based carbon@ferric oxide composite material is characterized by being prepared from biomass, ferric salt and ultrapure water through hydrothermal and calcination treatment; the biomass-based carbon@ferric oxide composite material is of a sheet structure, wherein ferric oxide particles are riveted on a carbon matrix, the diameters of the ferric oxide particles are 16-28 nm, and the BET specific surface area is 35.67-103.81 m 2 g -1 。
2. The biomass-based carbon @ iron oxide composite material according to claim 1, wherein: the biomass is one or more of peanut shells, bagasse, coconut shells, corn leaves and reed in any mass ratio.
3. The biomass-based carbon @ iron oxide composite material according to claim 1, wherein: the ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulfate in any mass ratio.
4. A method for preparing the biomass-based carbon @ iron oxide composite material according to claim 1, comprising the steps of:
(1) Cleaning biomass with ultrapure water, drying in an oven, polishing to powder, and sequentially mixing the biomass powder, ferric salt and ultrapure water according to a mass-volume ratio of 1: (0.2-0.6): (50-100) g/mL, mixing and stirring for 0.5-1.5 h, transferring into an autoclave, carrying out hydrothermal treatment at 150-200 ℃ for 5-12 h, naturally cooling to room temperature, and carrying out centrifugal separation, washing and drying to obtain a product A;
(2) According to the mass-to-volume ratio, the obtained product A, ferric salt and ultrapure water are sequentially 1: (0.5-2): (50-100) g/mL, mixing and stirring for 0.5-1.5 h, transferring into an autoclave, carrying out hydrothermal treatment at 150-200 ℃ for 5-12 h, naturally cooling to room temperature, carrying out centrifugal separation, washing and freeze-drying to obtain a product B;
(3) Spreading the product B obtained in the step 2 in a porcelain boat, placing the porcelain boat in a tube furnace in inert atmosphere, heating at a rate of 0.5-2 ℃/min to 500-600 ℃ and keeping for 1-3 h, and naturally cooling to room temperature to obtain the biomass-based carbon@ferric oxide composite material.
5. The method for preparing the biomass-based carbon@ferric oxide composite material is characterized by comprising the following steps of: the temperature range of the freeze drying in the step 2 is-40 to-80 ℃.
6. The method for preparing the biomass-based carbon@ferric oxide composite material is characterized by comprising the following steps of: the inert atmosphere in the step 3 is nitrogen, argon or nitrogen-argon mixed gas with any proportion.
7. Use of a biomass based carbon @ iron oxide composite material according to claim 1, wherein: the application of the material as a cathode material in a lithium ion battery.
8. The method for use according to claim 7, wherein: the method specifically comprises the following steps:
(a) Uniformly mixing biomass-based carbon@ferric oxide composite material, polyvinylidene fluoride and ketjen black according to the mass ratio of (7-8) (1-2) (1) to obtain a solid mixture;
(b) Mixing the solid mixture obtained in the step (a) with N-methyl pyrrolidone according to the mass ratio of (10-20) (80-90), and uniformly stirring to obtain slurry;
(c) Coating the slurry obtained in the step (b) on a copper foil, and drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 10-25 mu m;
(d) Taking the electrode plate of the lithium ion battery obtained in the step (c) as an electrode negative plate, taking the lithium plate as an electrode positive plate, taking a microporous polypropylene film as a diaphragm, and taking 1mol/L LiPF (lithium ion battery power factor) 6 And the solvent is electrolyte, and the CR2032 button lithium ion battery is assembled in a glove box filled with argon.
CN202310013475.3A 2023-01-05 2023-01-05 Biomass-based carbon@ferric oxide composite material and preparation method and application thereof Pending CN116314652A (en)

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