CN112072089A - Biomass lithium ion battery negative electrode material and preparation method thereof - Google Patents
Biomass lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly discloses a biomass lithium ion battery cathode material and a preparation method thereof. The raw materials of the invention are rich in sources and renewable, and the lithium ion battery cathode material has good specific capacity, cycling stability and rate capability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a biomass lithium ion battery cathode material and a preparation method thereof, and particularly relates to a graphene/biomass porous carbon nano composite cathode material for a lithium ion battery and a preparation method thereof.
Background
Due to the rapid development of economy, people have an increasing demand for energy, and the current commercialized negative electrode material of the lithium ion battery mainly is graphite derived from natural ore, coal tar and the like. On one hand, the increasing shortage of fossil energy can not meet the gradually expanded lithium battery market; on the other hand, the graphite negative electrode material has lower theoretical specific capacity (372 mAhg)-1) And the actual specific capacity is lower (about 330 mAhg)-1) The lithium ion battery has poor rate capability, poor cycle performance and low discharge voltage, which easily causes lithium deposition to cause safety problems, and cannot meet the requirements of high-energy lithium ion batteries, so that the development of renewable and excellent-performance cathode materials is urgent.
The natural biomass material has wide source, low cost and environmental protection, and has the characteristic of carbon structure after carbonization, thus being a cathode material with great potential. Graphene is an allotrope of carbon, is a planar film with a honeycomb-type layered structure with hexagonal rings, is only one carbon atom layer thick, and when the graphene is used as a lithium ion battery cathode material, the electrochemical energy storage performance of the graphene is superior to that of graphite, the charging speed is ten times faster than that of graphite, and the load capacity of the lithium ion battery can be improved. In addition, nitrogen doping modification is also a method for effectively improving the electrochemical performance of the carbon material, and nitrogen atoms can improve the charge transfer efficiency of the carbon material and improve the conductivity of the carbon material; the nitrogen doping increases the pore structure of the carbon material, exposes more active sites, is beneficial to improving the reaction activity of the material, and has very important application value.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a biomass porous carbon material with excellent electrochemical performance, wherein the biomass porous carbon material has the advantages of low cost, large specific surface area, reasonable pore size distribution, excellent performance and the like.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a biomass lithium ion battery negative electrode material comprises the following steps:
(1) extracting cellulose from agricultural and forestry waste biomass;
(2) preparing an electrostatic spinning solution: the electrostatic spinning solution comprises a cellulose spinning solution and a chitosan spinning solution, and cellulose and chitosan powder are respectively dissolved in an ionic liquid at normal temperature;
(3) preparing a cellulose/chitosan core-shell porous composite nanofiber membrane: carrying out coaxial spinning on cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle head, wherein the cellulose is a shell, and the chitosan is a core, so that the improvement of the electrochemical performance of the finally prepared cathode material by doping nitrogen element in a composite system of the chitosan and the maximum retention of the nitrogen element in the carbonization process are effectively exerted, a receiving plate is a copper foil, the receiving distance is 3-20cm, the voltage is 12-15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane is obtained;
(4) preparing a porous carbon nano composite fiber membrane: placing the obtained cellulose/chitosan core-shell porous composite nanofiber membrane in a tubular furnace or a high-temperature carbonization furnace under the protection of inert atmosphere at the heating rate of 1-10 DEG C
Performing carbonization at the temperature of 600-1500 ℃ to obtain the porous carbon nano composite fiber membrane;
(5) activation of the porous carbon nano composite fiber membrane: oxidizing the porous carbon nano composite fiber membrane in 0.5-5% nitric acid for 1-3h, filtering and washing, then putting the porous carbon nano composite fiber membrane into a thionyl chloride solution taking dimethyl formamide as a solvent, and then adding an amino compound to obtain an activated porous carbon nano composite fiber membrane;
(6) obtaining a biomass-based lithium ion battery negative electrode material: and immersing the activated porous carbon nano composite fiber membrane into the graphene dispersion liquid for 1-3h, taking out and drying to obtain the biomass lithium ion battery cathode material.
Further, the method for extracting cellulose from biomass in the step (1) comprises the following steps: cleaning biomass, drying at 80-100 ℃, crushing, sieving with a 60-100 mesh sieve, weighing a certain amount of powder, extracting for 12h by using an organic solvent, carrying out suction filtration and drying, adding 3-10% sodium hydroxide solution into the dried powder to react for 1-4h, adding glacial acetic acid and 30% hydrogen peroxide after suction filtration and cleaning, reacting for 4-8h at 40-60 ℃, carrying out ultrasonic dispersion for 0.5h, and drying after centrifugation or suction filtration and cleaning to obtain cellulose.
Further, the agricultural and forestry waste biomass is at least one material selected from wood, bamboo brush wood or leftovers, straw, rice straw, hemp stalk, cotton stalk, reed stalk, corn stalk, sorghum stalk, vine, shrub, bagasse, peanut shell, walnut shell, rice husk or rubber seed shell.
Further, the organic solvent is at least one of analytically pure benzene, toluene, methanol, absolute ethanol, diethyl ether, chloroform, acetone or petroleum ether.
Further, the ionic liquid in the step (2) is one of 1-butyl-3-methylimidazole chloride salt, 1-allyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole acetate or 1-ethyl-3-methylimidazole acetate.
Further, the amine compound in the step (5) is a diamine, triamine or tetraamine compound.
Furthermore, the amido compound is one of analytically pure ethylenediamine, o-phenylenediamine, m-phenylenediamine, cyclohexanediamine, diethylenetriamine, triethylenetetramine or triethylenetetramine.
Further, the particle size of the graphene powder in the step (6) is 6-15 μm.
The invention also provides application of the biomass lithium ion battery cathode material prepared by the method in preparation of a lithium battery.
The invention also provides application of the porous carbon nano composite fiber membrane prepared by the preparation method in preparing electrode materials.
The preparation method has the beneficial effects that the prepared biomass lithium ion battery cathode material is wide in raw material source, easy to obtain and renewable, the prepared cathode material has a large number of pores, natural nitrogen is doped, an interpenetrating cross-linked network and graphene are synergistic, the rapid transmission of lithium ions is facilitated, and the performance of the cathode material as the lithium ion battery cathode material can be effectively improved.
Drawings
FIG. 1 is a morphology of cellulose and chitosan electrospun core-shell;
FIG. 2 is a multiplying power performance test chart of the biomass lithium ion battery cathode material prepared by the invention;
fig. 3 is a display diagram showing the cycle stability of the biomass lithium ion battery anode material prepared by the invention.
Detailed Description
The present invention is further described below with reference to specific examples, which are only exemplary and do not limit the scope of the present invention in any way. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials, reagents and the like used in the examples are commercially available unless otherwise specified, and the reagents used therein are analytical grade reagents such as toluene, absolute ethanol and the like, and the concentrations thereof are 99.7% or more.
Example 1
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium acetate ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 2.5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 700 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 Dimethylformamide (DMF)/thionyl chloride (SOCl)2) The solution reacts for 3 hours at 70 ℃, and then o-phenylenediamine with equivalent weight to thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.4 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X1. And (3) forming a half cell by the negative electrode material X1 and the metal lithium to detect the electrochemical performance.
Example 2
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium acetate ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 2.5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1000 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 Dimethylformamide (DMF)/thionyl chloride (SOCl)2) The solution reacts for 3 hours at 70 ℃, and then o-phenylenediamine with equivalent weight to thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.4 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X2. And (3) forming a half cell by the negative electrode material X2 and the metal lithium to detect the electrochemical performance.
Example 3
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium acetate ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 2.5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1500 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 Dimethylformamide (DMF)/thionyl chloride (SOCl)2) Reacting the solution at 70 ℃ for 3h, and then adding o-phenylenediamine-carbon nano composite fibers with equivalent weight to thionyl chlorideThe membrane is activated.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.4 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X3. And (3) forming a half cell by the negative electrode material X3 and the metal lithium to detect the electrochemical performance.
Example 4
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium chloride ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 2.5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1000 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
The obtained porous carbon nano composite fiber membrane is added into 1.5 percent of nitreOxidizing in acid for 2h, filtering and washing, and then putting into a reactor with a volume ratio of 1: 500 Dimethylformamide (DMF)/thionyl chloride (SOCl)2) The solution reacts for 3 hours at 70 ℃, and then o-phenylenediamine with equivalent weight to thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.4 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X4. And (3) forming a half cell by the negative electrode material X4 and the metal lithium to detect the electrochemical performance.
Example 5
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium chloride ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 2.5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1000 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 of Dimethylformamide (DMF)/thionyl chloride (SOCl2) solution is reacted for 3 hours at 70 ℃, and then o-phenylenediamine with equivalent weight to that of thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.8 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X5. And (3) forming a half cell by the negative electrode material X5 and the metal lithium to detect the electrochemical performance.
Example 6
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium chloride ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 2.5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1000 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 of Dimethylformamide (DMF)/thionyl chloride (SOCl2) solution is reacted for 3 hours at 70 ℃, and then triethylenetetramine with equivalent weight to the thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.8 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X6. And (3) forming a half cell by the negative electrode material X6 and the metal lithium to detect the electrochemical performance.
Example 7
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium acetate ionic liquid, and stirring at normal temperature for 12 hours to prepare 5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1000 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 of Dimethylformamide (DMF)/thionyl chloride (SOCl2) solution is reacted for 3 hours at 70 ℃, and then triethylenetetramine with equivalent weight to the thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.8 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X7. And (3) forming a half cell by the negative electrode material X7 and the metal lithium to detect the electrochemical performance.
Example 8
The embodiment provides a preparation method of a biomass lithium ion battery cathode material, which comprises the following steps:
(1) cellulose extraction
Cleaning and drying the wood powder at 100 ℃, sieving the wood powder with a 60-100 mesh sieve after crushing, weighing 10g of wood powder, extracting the wood powder for 12 hours by adopting benzene/absolute ethyl alcohol, and then carrying out suction filtration and drying. Adding the dried powder into 3% sodium hydroxide solution for reaction for 3h, performing suction filtration and cleaning, adding glacial acetic acid and 30% hydrogen peroxide for reaction for 4h at 60 ℃, performing ultrasonic dispersion for 30min, and performing centrifugation or suction filtration and cleaning, and drying to obtain the cellulose.
(2) Electrospinning solution preparation
Dissolving the obtained cellulose in 1-ethyl-3-methylimidazolium acetate ionic liquid, and stirring at normal temperature for 12 hours to prepare 2.5 wt% cellulose spinning solution; dissolving a certain amount of chitosan powder in the same ionic liquid, and stirring for 12 hours to prepare 5 wt% of chitosan spinning solution.
(3) Preparation of cellulose/chitosan core-shell porous composite nanofiber membrane
And (2) carrying out coaxial spinning on the cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle, wherein the receiving distance is 15cm, the voltage is 15kV, and the cellulose/chitosan core-shell porous composite nanofiber membrane with the cellulose as the shell and the chitosan as the core is obtained.
(4) Porous composite nanofiber membrane carbonization
And placing the porous nano fiber membrane in a tubular furnace under the protection of nitrogen, and carbonizing at 1000 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain the porous carbon nano composite fiber membrane.
(5) Porous carbon nanocomposite fiber membrane activation
Oxidizing the obtained porous carbon nano composite fiber membrane in 1.5% nitric acid for 2h, filtering and washing, and then putting into a container with a volume ratio of 1: 500 of Dimethylformamide (DMF)/thionyl chloride (SOCl2) solution is reacted for 3 hours at 70 ℃, and then triethylenetetramine with equivalent weight to the thionyl chloride is added to activate the carbon nano composite fiber membrane.
(6) Obtaining the final product
And (3) immersing the activated carbon nano composite fiber membrane into 0.8 wt% of graphene dispersion liquid for 1h, taking out and drying to obtain a negative electrode material X8. And (3) forming a half cell by the negative electrode material X8 and the metal lithium to detect the electrochemical performance. The electrochemical performance indexes of the batteries obtained in the above examples are compared as shown in the following table:
table 1: performance index of the product of each example
The above description is given for the purpose of illustrating the invention in more detail, and it is not to be taken by way of limitation, since numerous changes and modifications may be made therein by those skilled in the art without departing from the spirit of the invention, and it is intended to cover in the appended claims all such changes and modifications as fall within the true spirit and scope of the invention.
Claims (10)
1. A preparation method of a biomass lithium ion battery cathode material is characterized by comprising the following steps:
(1) extracting cellulose from agricultural and forestry waste biomass;
(2) preparing an electrostatic spinning solution: the electrostatic spinning solution comprises a cellulose spinning solution and a chitosan spinning solution, and cellulose and chitosan powder are respectively dissolved in an ionic liquid at normal temperature;
(3) preparing a cellulose/chitosan core-shell porous composite nanofiber membrane: coaxially spinning cellulose and chitosan spinning solution by adopting a high-voltage electrostatic spinning device provided with a coaxial needle head, wherein the cellulose is a shell, the chitosan is a core, a receiving plate is a copper foil, the receiving distance is 3-20cm, and the voltage is 12-15kV, so that the cellulose/chitosan core-shell porous composite nanofiber membrane is obtained;
(4) preparing a porous carbon nano composite fiber membrane: placing the obtained cellulose/chitosan core-shell porous composite nanofiber membrane in a tubular furnace or a high-temperature carbonization furnace under the protection of inert gas, and carbonizing at the temperature of 600-1500 ℃ at the heating rate of 1-10 ℃/min to obtain a porous carbon nanocomposite fiber membrane;
(5) activation of the porous carbon nano composite fiber membrane: oxidizing the porous carbon nano composite fiber membrane in 0.5-5% nitric acid for 1-3h, filtering and washing, then putting the porous carbon nano composite fiber membrane into a thionyl chloride solution taking dimethyl formamide as a solvent, and then adding an amino compound to obtain an activated porous carbon nano composite fiber membrane;
(6) obtaining a biomass-based lithium ion battery negative electrode material: and immersing the activated porous carbon nano composite fiber membrane into the graphene dispersion liquid for 1-3h, taking out and drying to obtain the biomass lithium ion battery cathode material.
2. The preparation method of the biomass lithium ion battery anode material according to claim 1, wherein the step (1) of extracting cellulose from biomass comprises the following steps: cleaning biomass, drying at 80-100 ℃, crushing, sieving with a 60-100 mesh sieve, weighing a certain amount of powder, extracting for 12h by using an organic solvent, carrying out suction filtration and drying, adding 3-10% sodium hydroxide solution into the dried powder to react for 1-4h, adding glacial acetic acid and 30% hydrogen peroxide after suction filtration and cleaning, reacting for 4-8h at 40-60 ℃, carrying out ultrasonic dispersion for 0.5h, and drying after centrifugation or suction filtration and cleaning to obtain cellulose.
3. The preparation method of any one biomass lithium ion battery anode material according to claim 1 or 2, characterized in that the agriculture and forestry waste biomass is at least one material selected from wood, bamboo twigs or leftovers, straws, rice straws, hemp stalks, cotton stalks, reed stalks, corn stalks, sorghum stalks, vines, shrubs, bagasse, peanut shells, walnut shells, rice husks or rubber seed husks.
4. The preparation method of the biomass lithium ion battery anode material according to claim 2, wherein the organic solvent is at least one of benzene, toluene, methanol, absolute ethanol, diethyl ether, chloroform, acetone or petroleum ether.
5. The method for preparing the biomass lithium ion battery anode material according to claim 1, wherein the ionic liquid in the step (2) is one of 1-butyl-3-methylimidazole chloride salt, 1-allyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole acetate or 1-ethyl-3-methylimidazole acetate.
6. The method for preparing the biomass lithium ion battery anode material according to claim 1, wherein the amine compound in the step (5) is a diamine, triamine or tetraamine compound.
7. The method for preparing the negative electrode material of the biomass lithium ion battery according to claim 6, wherein the amino compound is one of ethylenediamine, o-phenylenediamine, m-phenylenediamine, cyclohexanediamine, diethylenetriamine, triethylenetetramine or triethylenetetramine.
8. The preparation method of the biomass lithium ion battery anode material according to claim 1, wherein the particle size of the graphene powder in the step (6) is 6-15 μm.
9. Use of the biomass lithium ion battery negative electrode material as claimed in any one of claims 1 to 8 in the preparation of a lithium battery.
10. Use of the porous carbon nanocomposite fiber membrane prepared by the preparation method according to claim 1 for preparing an electrode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112652822A (en) * | 2020-12-23 | 2021-04-13 | 深圳市言九电子科技有限公司 | Cylindrical lithium ion accumulator and its manufacturing process |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969123A (en) * | 2010-09-17 | 2011-02-09 | 北京化工大学 | C/C coaxial nano-fiber composite membrane cathode material for lithium battery and preparation method thereof |
| US20110305903A1 (en) * | 2010-06-11 | 2011-12-15 | Rennsselaer Polytechnic Institute | Sheathed nanotube fiber and method of forming same |
| US20120214375A1 (en) * | 2010-01-21 | 2012-08-23 | Hiramatsu Sangyo Co., Ltd. | Carbon fiber nonwoven fabric, carbon fiber, producing method thereof, electrode, battery, and filter |
| JP2014199803A (en) * | 2013-03-14 | 2014-10-23 | Dic株式会社 | Negative electrode active material for nonaqueous lithium secondary battery, negative electrode for nonaqueous lithium secondary battery containing the same, and nonaqueous lithium secondary battery |
| CN104143624A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Positive electrode material for lithium sulfur battery, and lithium sulfur battery positive electrode |
| US20150099186A1 (en) * | 2012-03-02 | 2015-04-09 | Cornell University | Silicon nanocomposite nanofibers |
| CN107180947A (en) * | 2017-05-11 | 2017-09-19 | 苏州大学 | A kind of flexible battery and preparation method that macroscopic fibres are combined based on metal oxide/graphene |
| US20180006297A1 (en) * | 2016-07-04 | 2018-01-04 | Samsung Electronics Co., Ltd. | Composite electrode active material, lithium battery including the same, and method of preparing the composite electrode active material |
| CN107959012A (en) * | 2017-11-17 | 2018-04-24 | 力信（江苏）能源科技有限责任公司 | A kind of individual layer/double-coating Si oxide composite negative pole material and preparation method thereof |
| CN109577001A (en) * | 2017-09-28 | 2019-04-05 | 鄄城永铭地毯有限公司 | A kind of composite conducting material |
| CN109763210A (en) * | 2019-01-15 | 2019-05-17 | 中国科学院过程工程研究所 | The method that ionic liquid prepares cellulose base carbon fiber or carbon film |
| CN110416526A (en) * | 2019-08-14 | 2019-11-05 | 戴嘉 | A kind of lithium cell cathode material and preparation method thereof |
| CN111384373A (en) * | 2018-12-29 | 2020-07-07 | 安普瑞斯（南京）有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| US20200255980A1 (en) * | 2019-02-13 | 2020-08-13 | Rensselaer Polytechnic Institute | Methods and systems for producing beaded polymeric fibers with advanced thermoregulating properties |
-
2020
- 2020-09-07 CN CN202010929120.5A patent/CN112072089B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120214375A1 (en) * | 2010-01-21 | 2012-08-23 | Hiramatsu Sangyo Co., Ltd. | Carbon fiber nonwoven fabric, carbon fiber, producing method thereof, electrode, battery, and filter |
| US20110305903A1 (en) * | 2010-06-11 | 2011-12-15 | Rennsselaer Polytechnic Institute | Sheathed nanotube fiber and method of forming same |
| CN101969123A (en) * | 2010-09-17 | 2011-02-09 | 北京化工大学 | C/C coaxial nano-fiber composite membrane cathode material for lithium battery and preparation method thereof |
| US20150099186A1 (en) * | 2012-03-02 | 2015-04-09 | Cornell University | Silicon nanocomposite nanofibers |
| JP2014199803A (en) * | 2013-03-14 | 2014-10-23 | Dic株式会社 | Negative electrode active material for nonaqueous lithium secondary battery, negative electrode for nonaqueous lithium secondary battery containing the same, and nonaqueous lithium secondary battery |
| CN104143624A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Positive electrode material for lithium sulfur battery, and lithium sulfur battery positive electrode |
| US20180006297A1 (en) * | 2016-07-04 | 2018-01-04 | Samsung Electronics Co., Ltd. | Composite electrode active material, lithium battery including the same, and method of preparing the composite electrode active material |
| CN107180947A (en) * | 2017-05-11 | 2017-09-19 | 苏州大学 | A kind of flexible battery and preparation method that macroscopic fibres are combined based on metal oxide/graphene |
| CN109577001A (en) * | 2017-09-28 | 2019-04-05 | 鄄城永铭地毯有限公司 | A kind of composite conducting material |
| CN107959012A (en) * | 2017-11-17 | 2018-04-24 | 力信（江苏）能源科技有限责任公司 | A kind of individual layer/double-coating Si oxide composite negative pole material and preparation method thereof |
| CN111384373A (en) * | 2018-12-29 | 2020-07-07 | 安普瑞斯（南京）有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN109763210A (en) * | 2019-01-15 | 2019-05-17 | 中国科学院过程工程研究所 | The method that ionic liquid prepares cellulose base carbon fiber or carbon film |
| US20200255980A1 (en) * | 2019-02-13 | 2020-08-13 | Rensselaer Polytechnic Institute | Methods and systems for producing beaded polymeric fibers with advanced thermoregulating properties |
| CN110416526A (en) * | 2019-08-14 | 2019-11-05 | 戴嘉 | A kind of lithium cell cathode material and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| AYDIN, MERAL等: "Chitosan derived N-doped carbon coated SnO2 nanocomposite anodes for Na-ion batteries", 《SOLID STATE IONICS》 * |
| CAI, JIE等: "High-Performance Supercapacitor Electrode Materials from Cellulose-Derived Carbon Nanofibers", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| JOAO POULO CAMPOS TRIGUEIRO等: "Layer-by-layer assembled films of multi-walled carbon nanotubes with chitosan and cellulose nanocrystals", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| XU, KAIMENG等: "Green sustainable, facile nitrogen self-doped porous carbon derived from chitosan/cellulose nanocrystal biocomposites as a potential anode material for lithium-ion batteries", 《JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS》 * |
| 张玲莉: "静电纺丝法制备PBS/CNC复合纳米纤维多孔材料及其结构性能研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
| 王智辉等: "LiCl/DMAc溶剂中活化处理对不同类型纤维素静电纺丝效果的影响", 《林业工程学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112652822A (en) * | 2020-12-23 | 2021-04-13 | 深圳市言九电子科技有限公司 | Cylindrical lithium ion accumulator and its manufacturing process |
| CN112652822B (en) * | 2020-12-23 | 2021-11-19 | 深圳市言九电子科技有限公司 | Cylindrical lithium ion accumulator and its manufacturing process |
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