CN113292065B - Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof - Google Patents

Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof Download PDF

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CN113292065B
CN113292065B CN202110573981.9A CN202110573981A CN113292065B CN 113292065 B CN113292065 B CN 113292065B CN 202110573981 A CN202110573981 A CN 202110573981A CN 113292065 B CN113292065 B CN 113292065B
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白莹
吴锋
董瑞琪
吴川
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Abstract

The invention discloses a large interlayer spacing monodisperse nano hard carbon material, a synthesis method and application thereof, wherein the synthesis method comprises the following steps: (1) dissolving xylose in deionized water, stirring the solution uniformly, preparing a solution with the concentration of 0.3-1.5M, and heating the solution to 160-200 ℃ for dehydration condensation reaction; (2) centrifugally cleaning the material obtained in the step (1), and drying in vacuum; (3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the protective atmosphere; the temperature is 900-1500 ℃, the carbonization time is 2-5 h, and the heating rate is 2-8 ℃/min; obtaining the large interlayer distance monodisperse nano hard carbon material. The hard carbon material is used for the sodium ion battery, shows excellent electrochemical performance, has very good commercial prospect, and is very suitable for being applied to a large-scale energy storage system.

Description

Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof
Technical Field
The invention relates to a nano hard carbon material, in particular to a large interlayer spacing monodisperse nano hard carbon material, a synthesis method and application thereof.
Background
Under the strategy of carbon peak-to-peak carbon neutralization, how to construct a novel energy system for effectively utilizing clean energy such as solar energy, wind energy and water energy draws wide attention. The large-scale energy storage technology is one of core technologies required for realizing the application and popularization of a smart grid system, and currently, the electrochemical energy storage technology based on a lithium ion battery is most concerned. In recent years, the application requirements of lithium ion batteries in the fields of power batteries, 3C and the like are gradually and rapidly increased, but the reserves of lithium resources in the earth crust are not abundant, and more than 80% of lithium in China needs to be imported, which is very unfavorable for guaranteeing the energy safety in China. In addition, the scarce lithium resource makes the energy storage system based on the lithium ion battery have little cost reduction space. As an effective replacement and supplement of a lithium ion battery, the sodium ion battery has the advantages of abundant resources and low price, and is an important choice for the energy storage technology of the future smart power grid.
Sodium is an element of the same group as lithium and has physicochemical properties similar to those of lithium. Similar to lithium ion batteries, sodium ion batteries are also composed of anode and cathode, electrolyte and other key materials. In order to meet the requirement of large-scale energy storage application, a reasonable sodium ion battery has the characteristics of high safety, low cost, long service life and the like, and the key materials are key factors for determining whether the performance of the sodium ion battery can meet the requirement, so that the research and development of the key materials are crucial to promoting the marketization of the sodium ion battery. Suitable anode materials are one of the keys to the development of sodium ion batteries.
The graphite negative electrode for commercialization of lithium ion batteries cannot be applied because it cannot form a thermodynamically stable compound with sodium ions in an ester-based electrolyte. Although it was discovered later that solvated sodium ions in ether-based electrolytes could co-intercalate into graphite to contribute capacity, the specific capacity was only around 150mAh/g, which is very disadvantageous for developing high energy density sodium ion full cells. The hard carbon material is considered to be the most promising negative electrode material of the sodium ion battery for commercialization due to the larger carbon layer spacing, abundant micropores and defect sites, abundant sodium storage active sites, and specific capacity of more than 300 mAh/g. Especially, the hard carbon based on the biomass raw material has low cost, is green and environment-friendly, and has attracted wide attention in recent years. A series of biomass hard carbons prepared by using biological wastes such as orange peel, banana peel and seaweed as carbon sources are widely reported, but the carbon yield of hard carbon materials prepared based on the biological wastes is very low (generally lower than 10%), the prepared hard carbon state is very dependent on the state of raw materials, the consistency is difficult to guarantee, the first week coulombic efficiency is often low (generally lower than 60%), the rate capability and the cycle life are generally poor, and the commercialization requirement of a sodium ion battery is difficult to meet. At present, no or few commercial high-end hard carbon material supply enterprises exist in China, and individual foreign Japanese enterprises have high-end hard carbon materials, but are expensive, and belong to special new energy strategy demand materials which do not allow export, so that the demand of exploring hard carbon materials with simple synthesis methods, controllable consistency, low cost and excellent sodium storage performance to meet the demand of developing sodium-ion batteries in China is urgently needed.
Disclosure of Invention
The invention aims to provide a synthesis method and application of a nano hard carbon material with a large interlayer spacing monodisperse morphology. The hard carbon material prepared by the invention has the advantages of monodisperse spherical morphology with the average particle size of about 200nm, lower specific surface area, abundant micropores and large interlayer spacing, has excellent electrochemical performance, and is a metal ion battery cathode material with great commercial prospect. And the provided preparation process is simple and is suitable for large-scale production.
According to a first aspect of the present invention, there is provided a method for synthesizing a nano hard carbon material having a large interlayer spacing monodisperse morphology, comprising the steps of:
(1) dissolving xylose in deionized water, stirring the solution uniformly, preparing a solution with the concentration of 0.3-1.5M, and heating the solution to 160-200 ℃ for dehydration condensation reaction;
(2) centrifugally cleaning the material obtained in the step (1), and drying in vacuum;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under a protective atmosphere; the temperature is 900-1500 ℃, the carbonization time is 2-5 h, and the heating rate is 2-8 ℃/min; obtaining the monodisperse nano hard carbon material with large interlayer spacing.
Further, in the step (1), the stirring speed is 100-1000 rpm, the stirring time is 0.2-2 h, and the stirring temperature is 20-60 ℃.
Further, the reaction vessel of the dehydration condensation reaction in the step (1) is a sealed reaction kettle, the solution filling amount is about 70-80% of the volume of the inner container of the reaction kettle, and the internal reaction pressure is provided by water vapor generated at high temperature.
Further, the protective gas in the step (2) is argon or nitrogen, and the flow rate of the protective gas is 150-400 sccm.
Preferably, the heating device for the dehydration condensation reaction in the step (1) is a microwave reaction device. The microwave reactor can be quickly heated to the dehydration condensation temperature, so that the nucleation rate is increased, a monodisperse nano hard carbon precursor with smaller particle size and more uniformity is formed, the reaction speed is extremely high, the dehydration reaction can be completed within 0.5-2 hours, and the time cost is effectively saved.
According to another aspect of the invention, the large interlayer distance monodisperse nano hard carbon material prepared by the synthesis method and the application thereof in the metal ion battery negative electrode are provided. The metal ions include lithium, sodium, potassium, calcium, magnesium, aluminum, and the like, and are preferably used as a negative electrode material of the sodium ion battery.
In particular, the sodium ion battery comprises a cathode prepared from the hard carbon cathode material prepared by the synthesis method, a cathode and an electrolyte, wherein the electrolyte contains NaBF 4 、NaPF 6 、NaClO 4 Sodium salts of NaFSI and NaTFSI and an organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Preferably, in the sodium ion battery according to the present invention, the electrolyte preferably contains 1m naff 6 Wherein the volume ratio of Ethylene Carbonate (EC) to diethyl carbonate (DEC) is 1: 1.
Preferably, the sodium ion battery is prepared by uniformly grinding the hard carbon negative electrode material, acetylene black and a binder (such as Sodium Alginate (SA)) in a mass ratio of 8:1:1, mixing the ground hard carbon negative electrode material with a solvent (such as deionized water) to prepare negative electrode slurry, and coating the negative electrode slurry on a copper foil current collector.
Compared with the prior art, the invention has the following advantages and technical effects:
the hard carbon material prepared by the invention uses xylose as a carbon source. Xylose is a pentose obtained by hydrolyzing hemicellulose-rich plants such as wood chips, straws and corncobs, so that the xylose used as a carbon source can have very low raw material cost, and is beneficial to reducing the cost of a negative electrode material, thereby effectively reducing the cost of a battery. The xylose used in the invention is pentose, and can be dehydrated to generate intermediate product furfural in the heating dehydration process, wherein the furfural has hydrophobicity, so that monodisperse nano carbon spheres tend to be generated in the nucleation growth process of the carbon spheres. In the hydrothermal process of common raw materials such as sucrose, glucose and the like, the intermediate product is hydroxymethyl furfural, and the hydroxyl groups on the hydroxymethyl furfural enable the hydroxymethyl furfural to have hydrophilicity, so that the final hydrothermal product is often carbon spheres which are adhered to each other. The monodisperse nano carbon sphere has the advantages that the surface active sites are fully utilized, the sodium ion diffusion path is shorter, the adsorption and diffusion of sodium ions are facilitated, and the specific capacity is improved. The preparation method provided by the invention can effectively control the consistency of the hard carbon, the carbon yield is higher than 20%, the carbon yield is far higher than that of reported biomass hard carbon, the synthesized hard carbon material has larger carbon layer spacing exceeding 0.4nm, the carbon layer spacing is far larger than that of graphite and some reported hard carbon materials, and the large layer spacing can provide channels and spaces for rapid transmission and storage of sodium ions; the nano-scale particle size is beneficial to shortening a diffusion path and ensures that the material has rapid dynamics during rapid charging; the nano-scale particle size has relatively low specific surface area, so that the multiplying power performance is ensured, excessive decomposition of the electrolyte is avoided, and high multiplying power and high first effect are achieved; the abundant microporous structure can provide abundant desorption and adsorption sites of sodium ions, contribute capacity, and realize high specific capacity by superposing the capacity contribution of large interlayer spacing; finally, the monodispersed morphology is beneficial to the effective utilization of the active specific surface and the improvement of the specific capacity and the rate capability. In conclusion, the large-interlayer-distance monodisperse nano hard carbon material has the advantages of low cost, high specific capacity, high first efficiency, high rate performance and the like, and has very good commercial prospect.
Drawings
Fig. 1 is an SEM image of a nano hard carbon material with a large interlayer spacing monodisperse morphology prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the nano hard carbon material with large interlayer spacing monodisperse morphology prepared in example 1 of the present invention.
Fig. 3 is a nitrogen adsorption and desorption graph of the nano hard carbon material with the large interlayer spacing and the monodisperse morphology prepared in example 1 of the present invention.
Fig. 4 is a pore size distribution diagram of the nano hard carbon material with large interlayer spacing monodisperse morphology prepared in example 1 of the present invention.
Detailed Description
In order that the invention may be better understood, the invention is further illustrated by the following examples, which are intended to be illustrative only and are not to be construed as limiting the invention.
Example 1
A preparation method of a nano hard carbon material with a large interlayer spacing and a monodisperse morphology comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1200 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Fig. 1 is an SEM image of the nano hard carbon material with large interlayer distance and monodispersion prepared in the present embodiment, and it can be seen that the material has a particle size range of 160 to 230nm and a monodispersion characteristic.
Fig. 2 shows an XRD pattern of the nano hard carbon material with monodisperse large interlayer spacing prepared in this example, and the carbon-layer spacing can be calculated by bragg equation to be 0.41nm, which is much larger than the carbon-layer spacing of graphite and some reported hard carbon materials, and the large interlayer spacing can effectively accommodate the de-intercalation of sodium ions.
FIG. 3 shows N of the large interlayer spacing monodisperse nano hard carbon material prepared in the embodiment 2 Adsorption and desorption graph, and the BET specific surface area is 292m 2 Lower specific surface area is beneficial to reduce the decomposition of electrolyte on the surface of the material, thereby reducing the irreversible capacity of the first week.
Fig. 4 is a pore size distribution diagram of the nano hard carbon material with large interlayer spacing and monodispersity prepared in the embodiment, the prepared hard carbon material is rich in micropores and basically does not contain mesopores, and the micropores can be used as active sites for sodium storage, so that the rich micropores can provide higher specific capacity.
Example 2
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 190 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1200 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 3
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 200 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1200 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 4
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 170 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1200 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 5
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 160 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1200 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 6
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 900 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 7
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1000 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 8
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1100 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 9
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1300 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 10
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1400 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 11
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ for carrying out dehydration condensation reaction for 24 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1500 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 12
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ by adopting microwaves to perform dehydration condensation reaction for 0.5 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1400 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of argon is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersion is obtained.
Example 13
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ by adopting microwaves to perform dehydration condensation reaction for 1 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1400 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Example 14
A preparation method of a large interlayer spacing monodisperse nano hard carbon material comprises the following steps:
(1) dissolving xylose in deionized water, stirring uniformly, preparing a solution with the concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, the stirring temperature is 30 ℃, and heating the solution to 180 ℃ by adopting microwaves to perform dehydration condensation reaction for 2 h;
(2) centrifuging and cleaning the material obtained in the step (1) at a high speed, and drying in vacuum at the drying temperature of 60 ℃ for 24 hours;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the argon atmosphere; the temperature is 1400 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min; the flow rate of the argon gas is 200sccm, and the nano hard carbon material with large interlayer spacing and monodispersity is obtained.
Test examples
Sodium ion battery assembly and electrochemical performance testing
(1) Uniformly mixing the hard carbon powder material prepared in the example 1, acetylene black and Sodium Alginate (SA) serving as a binder with deionized water serving as a solvent according to the mass ratio of 8:1:1 by adopting a smear method, magnetically stirring at the speed of 1200r/min for 12 hours to prepare negative electrode slurry, coating the negative electrode slurry on a copper foil current collector, and drying in a vacuum drying oven at the temperature of 100 ℃ for 24 hours; and rolling and cutting to obtain the hard carbon negative pole piece.
(2) Selecting a partially cut, uniform and complete pole piece, weighing by using a precision balance, and calculating the mass ((mtotal-mcopper) × 0.8) of the active material; and (3) assembling a sodium sheet counter electrode and a reference electrode, a positive electrode shell, a negative electrode shell, a glass fiber diaphragm, a sodium sheet (the diameter is 12mm and the thickness is 1mm) and an electrolyte into the CR2025 type button cell according to correct operation steps in a glove box in an argon atmosphere. The electrolyte used is dissolved with 1M NaPF 6 The assembled battery was sealed with a button cell sealer, taken out of the glove box, and allowed to stand at room temperature for 4 hours.
The electrochemical performance of the prepared sodium ion batteries is respectively tested, the test used instrument is a LAND CT2001A tester (blue electronic Co., Ltd., Wuhan city), the test cycle period is set to be 500 weeks, and specifically: cycling the battery for 500 weeks at a voltage in the range of 0.001-2.5V and a current density of 100 mA/g; the specific charge capacity (mAh/g) after 500 cycles of charge and discharge was measured, and the capacity retention rate after 500 cycles of charge and discharge was calculated (specific charge capacity after 500 cycles of charge and discharge divided by initial specific charge capacity × 100%).
The results of the first charge specific capacity and the capacity retention rate after 500 cycles of the large interlayer distance monodisperse nano hard carbon materials prepared in the examples 1 to 14 are shown in table 1.
TABLE 1
Figure GDA0003119320100000151
Comparing example 1 in table 1 with examples 2 to 5, it can be seen that too high a temperature for dehydration reaction will result in larger average particle size of the particles, since the high temperature promotes nucleation and growth process during dehydration, however, the increased particle size means a decrease in the active specific surface area and an increase in diffusion distance, which will eventually decrease the sodium storage capacity of the hard carbon; the dehydration process can not be fully carried out due to too low temperature, the oxygen content in the obtained precursor is too high, the interlayer spacing is too large due to too high oxygen content in the high-temperature carbonization process, the structural stability is poor, the circulation stability is reduced, and the irreversible capacity is reduced due to the oxygen-containing groups. The hydrothermal temperature is preferably 180-190 ℃ through comparison, and is a proper hydrothermal temperature range, and the optimal hydrothermal temperature is preferably 180 ℃.
Comparing example 1 with examples 6-11 in table 1, it can be seen that the carbonization temperature has a significant effect on the prepared large interlayer spacing monodisperse nano hard carbon material, and the low carbonization temperature can result in excessive oxygen-containing groups, insufficient graphitization degree, too small short-range ordered micro-domains, and excessive interlayer spacing, which can result in increased electrolyte decomposition, increased irreversible capacity, decreased reversible capacity, and decreased structural stability. High carbonization temperatures reduce defect sites and decrease interlamellar spacing, resulting in reduced sodium storage active sites and thus reduced sodium storage capacity. Through comparison, the carbonization temperature is preferably 1100-1300 ℃ which is a proper carbonization temperature range, and the optimal carbonization temperature is preferably 1200 ℃.
Further selecting a microwave hydrothermal method to rapidly prepare the large interlayer spacing monodisperse hard carbon nanoparticles, comparing example 1 with examples 12-14 in table 1, it can be seen that the microwave hydrothermal method can rapidly complete a dehydration condensation reaction within 0.5-2 h, and the particle size of the obtained product is more uniform due to more uniform microwave heating and higher consistency of particle nucleation and growth processes, which is beneficial to consistency of electrodes and can further increase effective active specific surface, thereby further optimizing electrochemical performance. Comparison of examples 12-14 shows that the microwave hydrothermal time is the best at 1 h.
In conclusion, the good hydrothermal temperature (180-190 ℃) and carbonization temperature (1100-1300 ℃) are selected, the large interlayer spacing monodisperse hard carbon nanoparticles with uniform particle size and interlayer spacing exceeding 0.4nm can be obtained, and the hard carbon material with the optimized structure is used as the negative electrode material of the sodium-ion battery to show the optimal comprehensive performance, including high specific capacity, high first-cycle coulombic efficiency, high capacity retention rate and the like.

Claims (5)

1. A synthetic method of a large interlayer spacing monodisperse nano hard carbon material is characterized by comprising the following steps:
(1) dissolving xylose in deionized water, stirring the solution uniformly, preparing a solution with the concentration of 0.3-1.5M, and heating the solution to 160-200 ℃ for dehydration condensation reaction;
(2) centrifugally cleaning the material obtained in the step (1), and drying in vacuum;
(3) carrying out high-temperature carbonization on the material obtained in the step (2) in a high-temperature furnace under the protective atmosphere; the temperature is 900-1500 ℃, the carbonization time is 2-5 h, and the heating rate is 2-8 ℃/min; obtaining the large interlayer distance monodisperse nano hard carbon material.
2. The synthesis method according to claim 1, wherein the protective gas in step (3) is argon or nitrogen, and the flow rate of the protective gas is 150-400 sccm.
3. A large interlayer spacing monodisperse nano hard carbon material prepared by the synthesis method of any one of claims 1-2.
4. The use of the large interlayer spacing monodisperse nano hard carbon material of claim 3 in metal ion battery negative electrodes.
5. A sodium ion battery comprising a negative electrode prepared using the hard carbon material according to claim 3, a positive electrode and an electrolyte, wherein the electrolyte contains NaBF selected from the group consisting of 4 、NaPF 6 、NaClO 4 Sodium salts of NaFSI and NaTFSI and an organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109004199A (en) * 2018-08-01 2018-12-14 北京理工大学 A kind of preparation method of sodium-ion battery cathode biomass hard carbon material
CN111847418A (en) * 2019-04-24 2020-10-30 香港理工大学深圳研究院 Preparation method and application of biomass hard carbon for negative electrode material of sodium-ion battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109004199A (en) * 2018-08-01 2018-12-14 北京理工大学 A kind of preparation method of sodium-ion battery cathode biomass hard carbon material
CN111847418A (en) * 2019-04-24 2020-10-30 香港理工大学深圳研究院 Preparation method and application of biomass hard carbon for negative electrode material of sodium-ion battery

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