CN113292070A - Biomass-based battery negative electrode material and preparation method thereof - Google Patents
Biomass-based battery negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a biomass-based battery negative electrode material and a preparation method thereof, wherein biomass is cleaned, dried and crushed into powder, and then the powder is subjected to acid treatment and heating carbonization treatment to obtain a porous carbonized product; then adding manganese acetate into the urea aqueous solution, uniformly stirring, adding the porous carbonized product, performing ultrasonic oscillation, performing suction filtration, and drying to obtain a precursor; adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into a sodium hydroxide solution, uniformly stirring and mixing, and performing heat treatment to obtain a surface-modified porous carbonized product; and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, and heating to release hydrogen to obtain the carbon dioxide-modified porous carbon material. The battery cathode material takes biomass as a main raw material, is green and environment-friendly, has good rate performance and high cycle stability, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a biomass-based battery negative electrode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high voltage, high energy density, small self-discharge, long cycle life, no pollution, no memory effect and the like, and is widely applied to the fields of electronic equipment such as mobile phones, computers and the like, automobiles, aerospace and the like.
In recent years, lithium ion batteries have been unable to meet the increase of demand for high-energy power supplies, and generally, the total specific capacity of the lithium ion batteries is determined by the components composing the batteries, and the negative electrode material is used as a main body of lithium storage to realize the insertion and extraction of lithium ions in the charging and discharging process, which is the key to improve the relevant performances of the lithium ion batteries, such as the total specific capacity, the cyclicity, and the charging and discharging.
The negative electrode material of the lithium ion battery in the current market is graphite, which has the advantages of low cost, good conductivity, stable physical and chemical properties, long cycle life and the like, but the graphite has low ion diffusion coefficient, an SEI film is easily formed on the surface of an electrode, and the three-dimensional crystal structure can be damaged in the charging and discharging process, so that the multiplying power performance and the cycle stability are not high, and the graphite negative electrode has the defects of low reversible cycle capacity, difficult rapid charging and discharging, poor overcharge and overdischarge capacity and the like in the lithium ion battery. Other materials capable of being used as the negative electrode, such as tin-based materials, transition metal oxides and the like, have the problems of low reaction potential, large volume change and the like, so that the rate performance and the cycle life of the full-cell are influenced.
The biomass carbon is a carbon material with reaction activity obtained by carbonizing and activating biomass, and has an excellent popularization value if being applied to preparation of battery materials due to wide biomass sources and low cost. However, single biomass carbon is similar to graphite, the rate capability and the circulation stability are poor, and the commercial popularization significance is not great.
Disclosure of Invention
In view of the above, the invention aims to provide a biomass-based battery negative electrode material and a preparation method thereof, which have good rate performance and high cycle stability.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) cleaning, drying and crushing biomass into powder of 50-80 meshes, and then performing acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) adding manganese acetate into a urea aqueous solution with the mass concentration of 20-30%, uniformly stirring, adding a porous carbonized product, carrying out ultrasonic oscillation at 300-500W for 4-6 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 8-10 mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
Preferably, in step (1), the biomass is selected from any one of corn stover, wood chips or peanut shells.
Preferably, in the step (1), the acid treatment is specifically performed by: adding the powder into a nitric acid solution with the mass concentration of 20-30% and the weight of 5-8 times of that of the powder, stirring at 70-80 ℃ for 3-4 hours, filtering, and drying to obtain an acid treatment product.
Preferably, in the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1 part of the acid treatment product and 7-9 parts of potassium carbonate into 15-18 parts of water, carrying out ultrasonic oscillation treatment at 300-500W for 3-4 hours, filtering, drying, and carrying out heat treatment at 1000-1200 ℃ for 2-3 hours to obtain the porous carbonized product.
Preferably, in the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 25-30: 15 to 20.
Preferably, in the step (3), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into the sodium hydroxide solution, the mixture is uniformly dispersed by ultrasonic waves, and then the precursor, the nano silicon powder and the nano titanium dioxide are sequentially added while stirring, and the mixture is uniformly stirred.
Preferably, in the step (3), the mass ratio of the precursor, the nano silicon powder, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and the sodium hydroxide solution is 10: 0.8-1.2: 0.1-0.2: 0.03-0.05: 30-40.
Preferably, in the step (3), the heat treatment process conditions are as follows: heating to 500-600 ℃ at a heating rate of 10-15 ℃/min, preserving heat for 1-2 hours, then heating to 800-900 ℃ at a heating rate of 5-7 ℃/min, and preserving heat for 5-6 hours.
Preferably, in the step (3), after the heat treatment, filtering to obtain a solid, washing with water to be neutral, and drying to obtain the surface-modified porous carbonized product.
Preferably, in the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.1 to 0.2.
Preferably, in the step (4), the ball-to-material ratio of the mixing ball milling is 60-70: 1, the ball milling speed is 300-500 r/min, and the ball milling time is 6-7 hours.
Preferably, in the step (4), the process conditions of heating and hydrogen releasing are as follows: heating to 420-480 ℃ at a heating rate of 10-12 ℃/min, preserving heat for 4-6 hours, and controlling the hydrogen partial pressure to be below 0.0001MPa in the heat preservation process.
The biomass-based battery negative electrode material is prepared by the preparation method.
The invention has the beneficial effects that:
the method comprises the steps of cleaning, drying and crushing biomass into powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product; then adding manganese acetate into the urea aqueous solution, uniformly stirring, adding the porous carbonized product, performing ultrasonic oscillation, performing suction filtration, and drying to obtain a precursor; adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into a sodium hydroxide solution, uniformly stirring and mixing, and performing heat treatment to obtain a surface-modified porous carbonized product; and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material. The battery cathode material takes biomass as a main raw material, is green and environment-friendly, has good rate performance and high cycle stability, and has a good application prospect.
The invention carries out acid treatment on the powder prepared from the biomass, degrades components such as lignin in the biomass, and generates a porous carbonized product with rich pores by virtue of the chemical activation of potassium carbonate in the subsequent heating and carbonizing treatment process. The pore structure provides a good basis for the electrical properties of the product.
And adding the porous carbonized product into a urea aqueous solution containing manganese acetate, so that manganese acetate and the like are embedded into pores to obtain a precursor. Adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazol bis (trifluoromethanesulfonyl) imide salt into a sodium hydroxide solution, carrying out heat treatment, in the process, converting the nano titanium dioxide into sodium titanate, partially converting manganese ions into sodium manganate, compounding the nano silicon powder, the residual manganese ions, the sodium titanate and the like on the surface of the porous carbonized product, and carrying out surface modification on the porous carbonized product, thereby greatly increasing the specific surface area of the product, increasing active sites, being beneficial to rapid implementation of electrochemical reaction and improving electrical properties. The invention also adds a small amount of 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt which is an ionic liquid, wherein amino and imidazole have certain coordination effect on metal ions, and imidazole has conductivity, thereby accelerating electron conduction on the one hand, playing a stabilizing role on the other hand and improving the circulation stability.
In the invention, the surface modified porous carbonized product and lithium hydride are mixed and ball-milled in the atmosphere of carbon dioxide, and then hydrogen is discharged by heating, so that lithium is embedded into the surface modified porous carbonized product, and a protective layer is formed on the surface of the porous carbonized product, thereby further improving the electrical properties of the product.
Drawings
Fig. 1 is a TEM image of the battery anode material obtained in example 1.
Detailed Description
The preferred embodiments of the present invention will be described in detail below.
Example 1:
a preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) firstly, cleaning, drying and crushing corn straws into 50-mesh powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) then adding manganese acetate into a urea aqueous solution with the mass concentration of 30%, uniformly stirring, adding a porous carbonized product, carrying out 300W ultrasonic oscillation for 6 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 8mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material (shown in figure 1).
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 20% and the weight of 8 times of that of the powder, stirring and treating for 3 hours at the temperature of 80 ℃, filtering and drying to obtain an acid treatment product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 9kg of potassium carbonate into 15kg of water, carrying out 500W ultrasonic oscillation treatment for 3 hours, filtering, drying, and carrying out heat treatment at 1200 ℃ for 2 hours to obtain the porous carbonized product.
In the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 30: 15.
in the step (3), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a sodium hydroxide solution, the mixture is uniformly dispersed by ultrasonic waves, and then the precursor, the nano silicon powder and the nano titanium dioxide are sequentially added while stirring, and the mixture is uniformly stirred.
In the step (3), the mass ratio of the precursor, the nano silicon powder, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and the sodium hydroxide solution is 10: 1.2: 0.1: 0.05: 30.
in the step (3), the heat treatment process conditions are as follows: heating to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 2 hours, then heating to 900 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours.
And (3) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
In the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.2.
in the step (4), the ball-material ratio of the mixing ball mill is 60: 1, the ball milling speed is 500 r/min, and the ball milling time is 6 hours.
In the step (4), the process conditions of heating and hydrogen releasing are as follows: heating to 420 ℃ at the heating rate of 12 ℃/min, and keeping the temperature for 6 hours, wherein the hydrogen partial pressure is controlled to be below 0.0001MPa in the heat preservation process.
Example 2:
a preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) cleaning, drying and crushing poplar sawdust into 80-mesh powder, and then performing acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) then adding manganese acetate into a urea aqueous solution with the mass concentration of 20%, uniformly stirring, adding a porous carbonized product, carrying out 500W ultrasonic oscillation for 4 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 10mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 30% and the weight of 5 times of that of the powder, stirring and treating for 4 hours at 70 ℃, filtering and drying to obtain an acid treated product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 7kg of potassium carbonate into 18kg of water, carrying out ultrasonic oscillation treatment for 4 hours at 300W, filtering, drying, and carrying out heat treatment for 3 hours at 1000 ℃ to obtain the porous carbonized product.
In the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 25: 20.
in the step (3), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a sodium hydroxide solution, the mixture is uniformly dispersed by ultrasonic waves, and then the precursor, the nano silicon powder and the nano titanium dioxide are sequentially added while stirring, and the mixture is uniformly stirred.
In the step (3), the mass ratio of the precursor, the nano silicon powder, the manganese nitrate, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt to the sodium hydroxide solution is 10: 0.8: 0.2: 0.03: 40.
in the step (3), the heat treatment process conditions are as follows: heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 1 hour, then heating to 800 ℃ at the heating rate of 7 ℃/min, and preserving heat for 6 hours.
And (3) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
In the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.1.
in the step (4), the ball-material ratio of the mixing ball mill is 70: 1, the ball milling speed is 300 r/min, and the ball milling time is 7 hours.
In the step (4), the process conditions of heating and hydrogen releasing are as follows: heating to 480 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 4 hours, wherein the hydrogen partial pressure is controlled to be below 0.0001MPa in the heat preservation process.
Example 3:
a preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) firstly, cleaning, drying and crushing peanut shells into 70-mesh powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) then adding manganese acetate into a urea aqueous solution with the mass concentration of 25%, uniformly stirring, adding a porous carbonized product, carrying out 400W ultrasonic oscillation for 5 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 9mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 25% and the weight of 7 times of that of the powder, stirring and treating for 3.5 hours at 75 ℃, filtering and drying to obtain an acid treated product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 8kg of potassium carbonate into 17kg of water, carrying out 400W ultrasonic oscillation treatment for 3.5 hours, filtering, drying, and carrying out heat treatment at 1100 ℃ for 2.5 hours to obtain the porous carbonized product.
In the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 28: 18.
in the step (3), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a sodium hydroxide solution, the mixture is uniformly dispersed by ultrasonic waves, and then the precursor, the nano silicon powder and the nano titanium dioxide are sequentially added while stirring, and the mixture is uniformly stirred.
In the step (3), the mass ratio of the precursor, the nano silicon powder, the manganese nitrate, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt to the sodium hydroxide solution is 10: 1: 0.15: 0.04: 35.
in the step (3), the heat treatment process conditions are as follows: heating to 550 ℃ at a heating rate of 10-15 ℃/min, preserving heat for 1.5 hours, then heating to 850 ℃ at a heating rate of 6 ℃/min, and preserving heat for 5.5 hours.
And (3) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
In the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.15.
in the step (4), the ball-material ratio of the mixing ball mill is 65: 1, the ball milling speed is 400 r/min, and the ball milling time is 6.5 hours.
In the step (4), the process conditions of heating and hydrogen releasing are as follows: heating to 450 ℃ at the heating rate of 11 ℃/min, and keeping the temperature for 5 hours, wherein the hydrogen partial pressure is controlled to be below 0.0001MPa in the heat preservation process.
Comparative example 1
A preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) firstly, cleaning, drying and crushing corn straws into 50-mesh powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) adding the porous carbonized product, the nano silicon powder, the nano titanium dioxide and the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 8mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(3) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 20% and the weight of 8 times of that of the powder, stirring and treating for 3 hours at the temperature of 80 ℃, filtering and drying to obtain an acid treatment product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 9kg of potassium carbonate into 15kg of water, carrying out 500W ultrasonic oscillation treatment for 3 hours, filtering, drying, and carrying out heat treatment at 1200 ℃ for 2 hours to obtain the porous carbonized product.
In the step (2), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a sodium hydroxide solution, uniformly dispersed by ultrasonic waves, stirred and sequentially added with the porous carbonized product, the nano silicon powder and the nano titanium dioxide, and uniformly stirred.
In the step (2), the mass ratio of the porous carbonized product, the nano silicon powder, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and the sodium hydroxide solution is 10: 1.2: 0.1: 0.05: 30.
in the step (2), the heat treatment process conditions are as follows: heating to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 2 hours, then heating to 900 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours.
And (2) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
In the step (3), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.2.
in the step (3), the ball-material ratio of the mixing ball mill is 60: 1, the ball milling speed is 500 r/min, and the ball milling time is 6 hours.
In the step (3), the process conditions of heating and hydrogen releasing are as follows: heating to 420 ℃ at the heating rate of 12 ℃/min, and keeping the temperature for 6 hours, wherein the hydrogen partial pressure is controlled to be below 0.0001MPa in the heat preservation process.
Comparative example 2
A preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) firstly, cleaning, drying and crushing corn straws into 50-mesh powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) then adding manganese acetate into a urea aqueous solution with the mass concentration of 30%, uniformly stirring, adding a porous carbonized product, carrying out 300W ultrasonic oscillation for 6 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, nano silicon powder and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 8mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 20% and the weight of 8 times of that of the powder, stirring and treating for 3 hours at the temperature of 80 ℃, filtering and drying to obtain an acid treatment product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 9kg of potassium carbonate into 15kg of water, carrying out 500W ultrasonic oscillation treatment for 3 hours, filtering, drying, and carrying out heat treatment at 1200 ℃ for 2 hours to obtain the porous carbonized product.
In the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 30: 15.
in the step (3), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a sodium hydroxide solution, the mixture is uniformly dispersed by ultrasonic waves, and then the precursor and the nano silicon powder are sequentially added while stirring, and the mixture is uniformly stirred.
In the step (3), the mass ratio of the precursor, the nano silicon powder, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and the sodium hydroxide solution is 10: 1.2: 0.05: 30.
in the step (3), the heat treatment process conditions are as follows: heating to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 2 hours, then heating to 900 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours.
And (3) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
In the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.2.
in the step (4), the ball-material ratio of the mixing ball mill is 60: 1, the ball milling speed is 500 r/min, and the ball milling time is 6 hours.
In the step (4), the process conditions of heating and hydrogen releasing are as follows: heating to 420 ℃ at the heating rate of 12 ℃/min, and keeping the temperature for 6 hours, wherein the hydrogen partial pressure is controlled to be below 0.0001MPa in the heat preservation process.
Comparative example 3
A preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) firstly, cleaning, drying and crushing corn straws into 50-mesh powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) then adding manganese acetate into a urea aqueous solution with the mass concentration of 30%, uniformly stirring, adding a porous carbonized product, carrying out 300W ultrasonic oscillation for 6 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, the nano silicon powder and the nano titanium dioxide into 8mol/L sodium hydroxide solution, stirring and uniformly mixing, and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 20% and the weight of 8 times of that of the powder, stirring and treating for 3 hours at the temperature of 80 ℃, filtering and drying to obtain an acid treatment product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 9kg of potassium carbonate into 15kg of water, carrying out 500W ultrasonic oscillation treatment for 3 hours, filtering, drying, and carrying out heat treatment at 1200 ℃ for 2 hours to obtain the porous carbonized product.
In the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 30: 15.
and (3) adding the precursor, the nano silicon powder and the nano titanium dioxide into the sodium hydroxide solution while stirring, and uniformly stirring.
In the step (3), the mass ratio of the precursor, the nano silicon powder, the nano titanium dioxide and the sodium hydroxide solution is 10: 1.2: 0.1: 30.
in the step (3), the heat treatment process conditions are as follows: heating to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 2 hours, then heating to 900 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours.
And (3) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
In the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.2.
in the step (4), the ball-material ratio of the mixing ball mill is 60: 1, the ball milling speed is 500 r/min, and the ball milling time is 6 hours.
In the step (4), the process conditions of heating and hydrogen releasing are as follows: heating to 420 ℃ at the heating rate of 12 ℃/min, and keeping the temperature for 6 hours, wherein the hydrogen partial pressure is controlled to be below 0.0001MPa in the heat preservation process.
Comparative example 4
A preparation method of a biomass-based battery negative electrode material comprises the following specific steps:
(1) firstly, cleaning, drying and crushing corn straws into 50-mesh powder, and then carrying out acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) then adding manganese acetate into a urea aqueous solution with the mass concentration of 30%, uniformly stirring, adding a porous carbonized product, carrying out 300W ultrasonic oscillation for 6 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) and adding the precursor, the nano silicon powder, the nano titanium dioxide and the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 8mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain the battery cathode material.
In the step (1), the specific method of acid treatment is as follows: adding the powder into a nitric acid solution with the mass concentration of 20% and the weight of 8 times of that of the powder, stirring and treating for 3 hours at the temperature of 80 ℃, filtering and drying to obtain an acid treatment product.
In the step (1), the specific method of the heating carbonization treatment comprises the following steps: adding 1kg of acid-treated product and 9kg of potassium carbonate into 15kg of water, carrying out 500W ultrasonic oscillation treatment for 3 hours, filtering, drying, and carrying out heat treatment at 1200 ℃ for 2 hours to obtain the porous carbonized product.
In the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 30: 15.
in the step (3), 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a sodium hydroxide solution, the mixture is uniformly dispersed by ultrasonic waves, and then the precursor, the nano silicon powder and the nano titanium dioxide are sequentially added while stirring, and the mixture is uniformly stirred.
In the step (3), the mass ratio of the precursor, the nano silicon powder, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and the sodium hydroxide solution is 10: 1.2: 0.1: 0.05: 30.
in the step (3), the heat treatment process conditions are as follows: heating to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 2 hours, then heating to 900 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours.
And (3) filtering to obtain a solid after heat treatment, washing to be neutral, and drying to obtain the surface-modified porous carbonized product.
Test examples
Application tests were carried out on the negative electrode materials obtained in examples 1 to 3 and comparative examples 1 to 4.
Mixing the negative electrode material with acetylene black and a polyvinylidene fluoride membrane according to a mass ratio of 93: 3: 4, mixing, using N-methyl pyrrolidone for size mixing, uniformly coating on the surface of the copper foil, and drying to prepare a negative plate; lithium sheet as counter electrode, Celgard, USA as separator, 1mol/L LiPF6/EC + DMC [ V (EC): v (dmc) ═ 1:1] was used as an electrolyte and assembled into a button cell in a stainless steel glove box filled with argon gas. Constant-current and constant-voltage charge and discharge tests are carried out on a Land-BTL10 (blue electricity) full-automatic battery program-controlled tester, and all electrical performance indexes are shown in Table 1.
TABLE 1 comparison of electrical Properties
As shown in Table 1, the negative electrode materials obtained in examples 1 to 3 have excellent electrical properties, good rate capability and high cycle stability.
Comparative example 1 omits the step (2), comparative example 2 omits the nano titanium dioxide in the step (3), comparative example 3 omits the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt in the step (3), comparative example 4 omits the step (4), the electrical properties of the obtained negative electrode material are obviously deteriorated, and the synergistic effect of manganese intercalation, titanium, 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and lithium surface modification is illustrated, so that the electrical properties of the product are improved.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a biomass-based battery negative electrode material is characterized by comprising the following specific steps:
(1) cleaning, drying and crushing biomass into powder of 50-80 meshes, and then performing acid treatment and heating carbonization treatment on the powder to obtain a porous carbonized product;
(2) adding manganese acetate into a urea aqueous solution with the mass concentration of 20-30%, uniformly stirring, adding a porous carbonized product, carrying out ultrasonic oscillation at 300-500W for 4-6 hours, carrying out suction filtration, and drying to obtain a precursor;
(3) adding the precursor, nano silicon powder, nano titanium dioxide and 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into 8-10 mol/L sodium hydroxide solution, uniformly stirring and carrying out heat treatment to obtain a surface-modified porous carbonized product;
(4) and finally, mixing the surface-modified porous carbonized product with lithium hydride in a carbon dioxide atmosphere, ball-milling, heating and releasing hydrogen to obtain the battery cathode material.
2. The method according to claim 1, wherein in the step (1), the acid treatment is carried out by the following specific method: adding the powder into a nitric acid solution with the mass concentration of 20-30% and the weight of 5-8 times of that of the powder, stirring at 70-80 ℃ for 3-4 hours, filtering, and drying to obtain an acid treatment product.
3. The preparation method according to claim 1, wherein in the step (1), the specific method of the heating carbonization treatment comprises the following steps in parts by weight: adding 1 part of the acid treatment product and 7-9 parts of potassium carbonate into 15-18 parts of water, carrying out ultrasonic oscillation treatment at 300-500W for 3-4 hours, filtering, drying, and carrying out heat treatment at 1000-1200 ℃ for 2-3 hours to obtain the porous carbonized product.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the manganese acetate to the urea aqueous solution to the porous carbonized product is 1: 25-30: 15 to 20.
5. The preparation method according to claim 1, wherein in the step (3), the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into the sodium hydroxide solution, uniformly dispersed by ultrasonic waves, and then the precursor, the nano silicon powder and the nano titanium dioxide are sequentially added while stirring, and uniformly stirred.
6. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the precursor, the nano silicon powder, the nano titanium dioxide, the 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and the sodium hydroxide solution is 10: 0.8-1.2: 0.1-0.2: 0.03-0.05: 30-40.
7. The method according to claim 1, wherein in the step (3), the heat treatment is performed under the following process conditions: heating to 500-600 ℃ at a heating rate of 10-15 ℃/min, preserving heat for 1-2 hours, then heating to 800-900 ℃ at a heating rate of 5-7 ℃/min, and preserving heat for 5-6 hours.
8. The preparation method according to claim 1, wherein in the step (4), the mass ratio of the surface-modified porous carbonized product to the lithium hydride is 10: 0.1 to 0.2.
9. The preparation method according to claim 1, wherein in the step (4), the process conditions for heating and hydrogen releasing are as follows: heating to 420-480 ℃ at a heating rate of 10-12 ℃/min, preserving heat for 4-6 hours, and controlling the hydrogen partial pressure to be below 0.0001MPa in the heat preservation process.
10. A biomass-based battery negative electrode material obtained by the preparation method of any one of claims 1 to 9.
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