CN113651307A - Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof - Google Patents
Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sodium ion battery carbon negative electrode material prepared based on waste wood chips and a preparation method thereof. The invention utilizes the waste wood chips as biomass raw materials, can fully utilize a large amount of chips generated in the production process of wood products, and has the advantages of environmental protection, low cost and the like; the method of low-carbonization heating rate pyrolysis has the effects of reducing the defect concentration, increasing the interlayer spacing and improving the graphitization degree, so that the electrochemical performance of the material is effectively improved; the hard carbon negative electrode material prepared by the method has higher first coulombic efficiency and reversible specific capacity, shows excellent cycle stability and rate capability, and is an ideal sodium ion battery negative electrode material.
Description
Technical Field
The invention belongs to the field of preparation of sodium ion battery electrode materials, and particularly relates to a method for preparing a high-efficiency sodium ion battery carbon negative electrode material based on waste wood dust, and the sodium ion battery carbon negative electrode material obtained by the preparation method.
Background
With the rapid development of human society and the consumption of traditional fossil energy, the problems of energy crisis and environmental pollution continue to be aggravated, and therefore, it is important to develop efficient energy conversion methods and clean energy systems. At present, lithium ion batteries have become competitive novel energy systems due to their advantages of high power and energy density, long cycle life, good safety, and the like, and are widely applied to daily lives of smart phones, notebook computers, electric vehicles, and the like. However, since the development of large-scale energy storage devices is urgently needed and the reserves of lithium resources are limited, the development of alternatives to lithium ion batteries is required to meet the needs of future development. Sodium is an element widely distributed in nature that is more abundant, more readily available than lithium in the earth's crust, and similar in physical and chemical properties to the lithium element. Sodium Ion Batteries (SIBs) have attracted considerable attention from researchers and are considered to be a promising alternative to LIBs.
In the research of Sodium Ion Batteries (SIBs), it is important to search for high-performance electrode materials. There is a lack of suitable negative electrode materials for SIBs, which is a factor that limits the development thereof. In previous studies, carbon materials have been widely used in electrochemical energy systems due to their excellent conductivity, abundant storage and low cost, and are considered as the most promising electrode materials. Graphite, a conventional carbon material, has found widespread use in lithium ion batteries due to its excellent electrochemical properties. However, the graphite cathode material has poor sodium storage performance due to large radius of sodium ions and high ionization potential. Hard carbon is carbon that is difficult to graphitize at temperatures above 2500 ℃, is composed of randomly oriented, defective discrete pieces of graphite, and has a structure called a "card house" model. Compared to graphite, hard carbon has larger interlayer spacing and more defects, showing the advantages of low potential (-0.1) and high capacity.
Biomass material, as one of the precursors for the production of hard carbon, is considered a reliable large-scale carbon source due to its low cost, renewable and environmentally friendly advantages. Biomass carbon materials such as rice hulls, pomelo peels, bagasse, banana peels, corncobs and the like have proved to have good sodium storage performance. The first coulombic efficiency (ICE) determines the available energy density of the anode material in practical application, and is one of the important factors for realizing industrial application of hard carbon in SIBs. Most hard carbons exhibit lower ICE due to irreversible sodium storage sites, side reactions, and the formation of Solid Electrolyte Interphase (SEI). In order to improve the ICE of the hard carbon cathode material, the Zhu of Tianjin university and the like adopt pyrolysis and H2The hard carbon material is prepared by a reduction combined method. In the study, H2The reduction treatment obviously reduces the oxygen content in the hard carbon, reduces the defects of the material and the occurrence of unnecessary side reactions, further improves the sodium storage performance of the material, and effectively improves the ICE of the hard carbon. Researchers find that the first coulombic efficiency of the hard carbon material is low due to irreversible intercalation of sodium ions in the first discharge process, the specific surface area, the defect concentration, the heteroatom content and the like are main factors influencing the hard carbon material, and the research and development of the high-first-efficiency biomass hard carbon material have important significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-efficiency first-effect sodium-ion battery carbon negative electrode material prepared based on waste wood chips and a preparation method thereof. The prepared hard carbon material has low defect concentration, proper interlayer spacing and high graphitization degree, and the special structure is favorable for the intercalation and deintercalation of sodium ions, thereby effectively improving the first coulomb efficiency of the material.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided a method for preparing a carbon negative electrode material for a sodium ion battery based on waste wood chips, comprising:
the method comprises the following steps: carrying out ultrasonic washing pretreatment on the waste wood chip biomass raw material to remove surface dust impurities, and drying to obtain a biomass precursor;
step two: transferring the treated biomass precursor into a muffle furnace to carry out pre-carbonization in the atmosphere of air, wherein the temperature rise rate of the pre-carbonization is 1-20 ℃/min, the pyrolysis temperature is 200-400 ℃, and the heat preservation time is 1-5 hours; naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
step three: transferring the pre-carbonized product into a high-temperature tube furnace for high-temperature carbonization under the protection of inert gas, wherein the heating rate of the high-temperature carbonization is 0.25-1 ℃/min, the pyrolysis temperature is 1200-2+95% Ar) for 1-10 hours; naturally cooling, grinding and sieving;
step four: and washing the treated hard carbon material with an acid solution to remove metal heteroatoms, centrifugally washing the hard carbon material with deionized water and ethanol to be neutral, and drying the hard carbon material to obtain the hard carbon material.
Further, in the first step, the waste wood chips are one of the following wood chips of arbors: camphor wood chips, walnut tree wood chips, elm wood chips and chinaberry wood chips.
Further, in the first step, the liquid selected for washing the biomass raw material is one or more of deionized water, absolute ethyl alcohol and acetone, the ultrasonic washing time is 6-12 hours, and the temperature of the liquid for washing is 30-80 ℃.
Further, in the second step, the temperature rise rate of the pre-carbonization is 3 ℃/min, the pyrolysis temperature is 300 ℃, and the heat preservation time is 2 hours.
Further, in the third step, the heating rate of high-temperature carbonization is 0.25 ℃/min, the pyrolysis temperature is 1300 ℃, and the heat preservation time is 2 hours. In the third step, the flow rate of the inert gas is 10-100 CC/min. The cooling rate was maintained at 5 deg.C/min.
Further, in the fourth step, the acid solution is selected from one of hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid and sulfuric acid, the concentration of the acid solution is 1-5M, and the soaking and washing time is 1-24 hours.
According to another aspect of the present invention, there is provided a carbon negative electrode material for sodium ion batteries, characterized in that: prepared by the method described above.
According to another aspect of the invention, the hard carbon material electrode plate is prepared by uniformly grinding the carbon negative electrode material of the sodium ion battery, acetylene black, sodium carboxymethylcellulose and polyacrylic acid in proportion, adding deionized water, magnetically stirring to obtain uniformly mixed electrode slurry, uniformly coating the battery slurry on a copper foil by using a coating machine, placing the copper foil in a vacuum drying oven, drying the copper foil in vacuum for hours, and preparing the copper foil into a wafer electrode by using a sheet punching machine.
Further, the mass ratio of the acetylene black to the sodium carboxymethyl cellulose to the polyacrylic acid is 8:1:0.5: 0.5.
According to another aspect of the present invention, there is provided a sodium ion battery comprising the hard carbon material electrode sheet described above.
Arbor trees refer to trees with tall and big trunk, are mainly distributed in fertile land and warm areas, are widely distributed, and are generally used for landscaping, building and furniture manufacturing and the like. However, in practice, a large amount of waste wood chips is usually produced, and thus, the value of the waste wood chips is low. The invention takes the waste wood dust as the raw material, has the advantages of simple preparation process flow, environmental protection, low cost and the like, and is convenient for large-scale mass production.
The invention relates to a method combining pre-carbonization and low-heating-rate pyrolysis, wherein the pre-carbonization method enables a biomass organic carbon chain to initially form a ring structure, and an oxygen-based functional group is introduced; the method of low temperature rise rate pyrolysis can effectively reduce the defect concentration of the hard carbon material, the closure of partial micropores on the surface of the hard carbon material and the reduction of the specific surface area can effectively reduce the irreversible capacity loss of the hard carbon material, the prepared hard carbon material has proper interlayer spacing and higher graphitization degree, is beneficial to the embedding and the separation of sodium ions, has high first coulombic efficiency and reversible specific capacity, has a platform charging curve and higher platform capacity ratio, has excellent cycle stability and rate capability, and is an ideal sodium ion battery cathode material.
Drawings
Fig. 1 is an XRD pattern of the anode materials prepared in examples 1,2,4 of the present invention and comparative examples 1, 2;
FIG. 2 is a Raman diagram of negative electrode materials prepared according to examples 1,2,4 of the present invention and comparative examples 1, 2;
FIG. 3 is a charge and discharge graph of the negative electrode material prepared in comparative example 1 of the present invention;
FIG. 4 is a charge-discharge curve diagram of the negative electrode material prepared in example 4 of the present invention;
fig. 5 is a graph of cycle performance of the anode materials prepared in examples 1,2,4 of the present invention and comparative examples 1, 2;
fig. 6 is a graph of rate performance of the anode materials prepared in example 4 of the present invention and comparative example 1;
fig. 7 is an SEM image of the anode material prepared in example 4 of the present invention;
fig. 8 is an HRTEM of a negative electrode material prepared in example 4 of the present invention.
Detailed Description
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the temperature from 25 ℃ to 1300 ℃ at the heating rate of 1 ℃/min under the protection of inert gas argon, preserving the temperature for 2 hours, cooling the product to the room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 2
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the room temperature from 25 ℃ to 1300 ℃ at the heating rate of 0.5 ℃/min under the protection of inert gas argon, preserving the heat for 2 hours, cooling the product to the room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 3
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tubular furnace, heating the temperature from 25 ℃ to 1200 ℃ at the heating rate of 0.25 ℃/min under the protection of inert gas argon, preserving the temperature for 2 hours, cooling the product to the room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 4
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the room temperature from 25 ℃ to 1300 ℃ at the heating rate of 0.25 ℃/min under the protection of inert gas argon, preserving the heat for 2 hours, cooling the product to the room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 5
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tubular furnace, heating the temperature from 25 ℃ to 1400 ℃ at the heating rate of 0.25 ℃/min under the protection of inert gas argon, preserving the temperature for 2 hours, cooling the product to room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 6
The method comprises the following steps: ultrasonically washing biomass juglans mandshurica wood chips for 12 hours by using absolute ethyl alcohol, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at the temperature of 30 ℃, and removing moisture;
step two: transferring the dried wood chips of the juglans mandshurica maxim into a muffle furnace, heating to 200 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving the heat for 1 hour, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the room temperature from 25 ℃ to 1300 ℃ at the heating rate of 0.25 ℃/min under the protection of inert gas nitrogen, preserving the heat for 2 hours, cooling the product to the room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 1M dilute nitric acid solution, soaking for 24 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the solution is neutral, drying the obtained product in a forced air drying oven at the temperature of 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 7
The method comprises the following steps: washing biomass walnut wood chips with acetone for 8 hours, removing dust and impurities, drying the obtained product in a forced air drying oven at 80 ℃ for 24 hours, and removing moisture;
step two: transferring the dried walnut wood chips into a muffle furnace, heating to 400 ℃ at a heating rate of 20 ℃/min in the air atmosphere, preserving the temperature for 5 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: the pre-carbonized product was placed in a tube furnace under hydrogen argon (5% H)2+95% Ar), heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 0.25 ℃/min, preserving heat for 2 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 5M acetic acid solution, soaking for 1 hour, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at the temperature of 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 8
The method comprises the following steps: washing biomass elm wood chips with deionized water for 8 hours, removing dust impurities, drying the obtained product in a forced air drying oven at 60 ℃ for 24 hours, and removing moisture;
step two: transferring the dried elm wood chips into a muffle furnace, heating to 350 ℃ at a heating rate of 15 ℃/min in the air atmosphere, preserving the temperature for 5 hours, naturally cooling with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tubular furnace, heating the temperature from 25 ℃ to 1300 ℃ at the heating rate of 0.5 ℃/min under the protection of nitrogen, preserving the heat for 2 hours, cooling the product to room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 1M sulfuric acid solution, soaking for 3 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at the temperature of 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Example 9
The method comprises the following steps: washing biomass chinaberry wood chips with absolute ethyl alcohol for 4 hours, removing dust impurities, drying the obtained product in a forced air drying oven at 80 ℃ for 24 hours, and removing moisture;
step two: transferring the dried wood chips of the melia azedarach into a muffle furnace, heating to 300 ℃ at a heating rate of 10 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the pre-carbonized product from room temperature 25 ℃ to 1300 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving the heat for 2 hours, cooling the pre-carbonized product to the room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out the pre-carbonized product, grinding the pre-carbonized product, and sieving the pre-carbonized product by using a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M nitric acid solution, soaking for 3 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the acid washing solution is neutral, drying the obtained product in a forced air drying oven at the temperature of 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Comparative example 1
Comparative example 4, comparative example 1 provides a method for preparing a hard carbon material having a high temperature-rise rate of 5 c/min.
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the temperature from 25 ℃ to 1300 ℃ at the heating rate of 5 ℃/min under the protection of inert gas argon, preserving the temperature for 2 hours, cooling the product to room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by using a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
Comparative example 2
Comparative example 4, comparative example 2 provides a method for preparing a hard carbon material having a high temperature rise rate of 2 c/min.
The method comprises the following steps: ultrasonically washing biomass camphorwood chips for 6 hours by using deionized water, removing dust and impurities, drying the obtained product in a forced air drying oven for 24 hours at 60 ℃, and removing moisture;
step two: transferring the dried camphor wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use;
step three: putting the pre-carbonized product into a tube furnace, heating the temperature from 25 ℃ to 1300 ℃ at the heating rate of 2 ℃/min under the protection of inert gas argon, preserving the temperature for 2 hours, cooling the product to room temperature along with the furnace at the cooling rate of 5 ℃/min, taking out the product, grinding the product, and sieving the product by using a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly carrying out centrifugal washing with deionized water and ethanol until the obtained product is neutral, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon negative electrode material.
The invention provides a typical embodiment of a hard carbon material electrode plate, which is prepared by uniformly grinding the camphor wood chip hard carbon sodium ion battery cathode material obtained in each example and comparative example, acetylene black, sodium carboxymethylcellulose (CMC) and polyacrylic acid (PAA) according to the mass ratio of 8:1:0.5:0.5, adding a proper amount of deionized water, magnetically stirring for 12 hours to obtain uniformly mixed electrode slurry, uniformly coating the electrode slurry on a copper foil by using a coating machine, placing the copper foil in a vacuum drying oven for vacuum drying at 80 ℃ for 12 hours, and preparing the electrode slurry into a wafer electrode with the diameter of 12mm by using a sheet punching machine to obtain the hard carbon material electrode plate.
This example provides a half-cell of a sodium ion battery, where the electrode sheet obtained above is used as a negative electrode, the hard carbon electrode sheet is cut to obtain a 12mm diameter circular sheet, the circular sheet is compacted by a tablet press, the battery is assembled in a glove box filled with high purity argon according to the structure of a CR2016 standard button cell, where a 19 mm diameter glass fiber (Whitman, GF/a) circular sheet is used as a diaphragm, a 12mm diameter sodium metal sheet with a thickness of 0.2 mm is used as a counter electrode and a reference electrode, a 1 mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution is used as an electrolyte, and after standing for 12 h, the battery is subjected to a charge and discharge test with a current density of 20mA/g on a blue cell test platform.
TABLE 1 main parameters and sodium storage Properties of examples 1-5 and comparative examples 1-2
The XRD pattern shown in fig. 1 shows that five samples of examples 1,2,4 and comparative examples 1,2 each show 2 weak and broad diffraction peaks at 24 ° and 43 ° (2 θ), corresponding to diffraction of (002) and (100) planes, respectively, and as the temperature increase rate decreases, the (002) peak shifts to a lower diffraction angle and the 2 θ shifts from 24.42 ° to 23.48 °, and the average interlayer spacings d002 are calculated to be 0.364, 0.367, 0.371, 0.374 and 0.378 nm, respectively, wherein the hard carbon material prepared in example 4 has a larger interlayer spacing, which facilitates intercalation and deintercalation of sodium ions.
The Raman spectrum shown in FIG. 2 shows that the five samples of examples 1,2 and 4 and comparative examples 1 and 2 are respectively at about 1340 cm-11590 sumcm-1Two broad peaks are shown, representing the D peak and the G peak respectively, and the integrated area intensity ratio of the D peak and the G peak is generally used for characterizing the graphitization degree of the carbon material. With decreasing rate of temperature rise, ID / IGThe value decreases continuously from 1.63 to 1.48, where the hard carbon material prepared in example 4 has a higher degree of graphitization.
As can be seen from the charge and discharge curve shown in FIG. 3, the material of comparative example 1 has a current density of 20mA/g and a voltage interval of 0-2V, which shows a first coulombic efficiency of 67.5% and an initial specific capacity of 242.6mAh/g, and has an obvious charge and discharge platform.
As can be seen from the charge-discharge curve shown in FIG. 4, the material of example 4 has a high first coulombic efficiency (82.8%) and an initial specific capacity (324.6 mAh/g) at a current density of 20mA/g and a voltage interval of 0-2V, and has a high platform capacity ratio.
As can be seen from the cycle performance graph shown in fig. 5, the five hard carbon materials of examples 1,2,4 and comparative examples 1,2 all showed good cycle stability, wherein the hard carbon material prepared in example 5 had the highest reversible specific capacity and still had a high capacity retention rate of 98.4% after being cycled 50 times at a current density of 20 mA/g.
As can be seen from the SEM image shown in fig. 6, the hard carbon material of example 4 shows a layered porous structure, which facilitates intercalation and deintercalation of sodium ions, and the surface thereof shows less micropores, which can reduce the loss of irreversible capacity.
The HRTEM of fig. 7 shows that the hard carbon material of example 4 exhibits a typical amorphous structure and has a large number of short-range ordered graphitic layers with an interlayer spacing of 0.379 nm.
As shown in table 1, it can be seen from comparative examples 3,4 and 5 that, by changing the pyrolysis temperature of the hard carbon material, the reversible specific capacity of the material tends to increase and decrease with the increase of the temperature, and 1300 ℃ is the optimal carbonization temperature; by comparing examples 1,2 and 4 with comparative examples 1 and 2, it can be seen that by reducing the temperature rise rate of the material during pyrolysis, the first coulombic efficiency of the material is increased from 67.5% to 82.8%, and the initial specific capacity is increased from 242.6mAh/g to 324.6 mAh/g; by reducing the temperature rise rate in the carbonization process, the defect concentration of the material is reduced, the interlayer spacing and the graphitization degree of the material are improved, the first coulomb efficiency and the specific capacity of the material can be effectively improved, and the sodium storage performance of the material is improved.
The above-described embodiments 1 to 9 are merely preferred embodiments of the present invention, and the basic principles and features of the present invention are described, and the present invention is not limited to the above-described embodiments, and all modifications, improvements and the like which are made within the methods disclosed by the present invention are within the protection of the present invention.
Claims (10)
1. A method for preparing a sodium ion battery carbon negative electrode material based on waste wood chips is characterized by comprising the following steps:
the method comprises the following steps: carrying out ultrasonic washing pretreatment on the waste wood chip biomass raw material to remove surface dust impurities, and drying to obtain a biomass precursor;
step two: transferring the treated biomass precursor into a muffle furnace to carry out pre-carbonization in the atmosphere of air, wherein the temperature rise rate of the pre-carbonization is 1-20 ℃/min, the pyrolysis temperature is 200-400 ℃, and the heat preservation time is 1-5 hours; naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
step three: transferring the pre-carbonized product into a high-temperature tube furnace for high-temperature carbonization under the protection of inert gas, wherein the heating rate of the high-temperature carbonization is 0.25-1 ℃/min, the pyrolysis temperature is 1200-2+95% Ar) for 1-10 hours; naturally cooling, grinding and sieving;
step four: and washing the treated hard carbon material with an acid solution to remove metal heteroatoms, centrifugally washing the hard carbon material with deionized water and ethanol to be neutral, and drying the hard carbon material to obtain the hard carbon material.
2. The method of claim 1, wherein:
in the first step, the waste wood chips are one of the following wood chips of arbor trees: camphor wood chips, walnut tree wood chips, elm wood chips and chinaberry wood chips.
3. The method of claim 1, wherein:
in the first step, the liquid selected for washing the biomass raw material is one or more of deionized water, absolute ethyl alcohol and acetone, the ultrasonic washing time is 6-12 hours, and the temperature of the liquid for washing is 30-80 ℃.
4. The method of claim 1, wherein:
in the second step, the temperature rise rate of the pre-carbonization is 3 ℃/min, the pyrolysis temperature is 300 ℃, and the heat preservation time is 2 hours.
5. The method of claim 1, wherein:
in the third step, the heating rate of high-temperature carbonization is 0.25 ℃/min, the pyrolysis temperature is 1300 ℃, and the heat preservation time is 2 hours.
6. The method of claim 1, wherein: in the fourth step, the acid solution is selected from one of hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid and sulfuric acid, the concentration of the acid solution is 1-5M, and the soaking and washing time is 1-24 hours.
7. A carbon negative electrode material of a sodium ion battery is characterized in that: prepared by the process of any one of claims 1 to 6.
8. The electrode plate made of hard carbon materials is characterized in that: the carbon cathode material of the sodium-ion battery as claimed in claim 7, acetylene black, sodium carboxymethylcellulose and polyacrylic acid are ground uniformly according to a certain proportion, deionized water is added for magnetic stirring to obtain uniformly mixed electrode slurry, the battery slurry is uniformly coated on copper foil by using a coating machine, the copper foil is placed in a vacuum drying oven for vacuum drying for hours, and then a sheet punching machine is used for preparing a wafer electrode, so that the hard carbon electrode sheet is obtained.
9. The hard carbon material electrode sheet according to claim 8, wherein: the mass ratio of the acetylene black to the sodium carboxymethyl cellulose to the polyacrylic acid is 8:1:0.5: 0.5.
10. A sodium ion battery, characterized by: an electrode sheet comprising the hard carbon material of claim 8 or 9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678130A (en) * | 2018-12-20 | 2019-04-26 | 电子科技大学 | A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery |
| CN113193196A (en) * | 2021-04-25 | 2021-07-30 | 大连理工大学 | Multifunctional aqueous binder for sodium ion battery and application thereof |
-
2021
- 2021-08-09 CN CN202110907187.3A patent/CN113651307B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678130A (en) * | 2018-12-20 | 2019-04-26 | 电子科技大学 | A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery |
| CN113193196A (en) * | 2021-04-25 | 2021-07-30 | 大连理工大学 | Multifunctional aqueous binder for sodium ion battery and application thereof |
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