CN110921647B - Hard carbon microsphere with adjustable morphology and pore structure, preparation method and application thereof - Google Patents

Hard carbon microsphere with adjustable morphology and pore structure, preparation method and application thereof Download PDF

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CN110921647B
CN110921647B CN201911254976.0A CN201911254976A CN110921647B CN 110921647 B CN110921647 B CN 110921647B CN 201911254976 A CN201911254976 A CN 201911254976A CN 110921647 B CN110921647 B CN 110921647B
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hard carbon
water
sodium
carbon microsphere
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项宏发
李昌豪
孙毅
梁鑫
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Hefei University of Technology
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a hard carbon microsphere with adjustable morphology and pore structure, a preparation method thereof, a negative electrode material of a sodium ion battery containing the hard carbon microsphere, and a sodium ion battery containing the negative electrode material. The surface of the hard carbon microsphere is provided with a depression, the particle size of the hard carbon microsphere is 1-5 mu m, and 1343cm is obtained in the Raman spectrum of the hard carbon microsphere ‑1 The peak of the nearby D band caused by defects is at 1589cm ‑1 Ratio I of intensity of near peak of G band formed of crystalline graphite D /I G Is 1.0 to 1.1, and preferably the average interlayer spacing d of the (002) plane in the microsphere 002 Is 0.395-0.420 nm.

Description

Hard carbon microsphere with adjustable morphology and pore structure, preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a hard carbon microsphere with adjustable morphology and pore structure, a preparation method thereof, a negative electrode material of a sodium ion battery containing the hard carbon microsphere, and a sodium ion battery containing the negative electrode material.
Background
The lithium ion battery is widely applied to various electronic products, new energy automobiles and the field of energy storage by the advantages of high energy density, high voltage, low self-discharge, excellent cycle performance and the like. However, the lithium resources on the earth are limited and unevenly distributed, and the lithium ion battery is widely used, so that the cost of the lithium ion battery is high, and the large-scale energy storage application is difficult to meet, and the development of the next generation of energy storage battery system with excellent comprehensive performance is urgently needed. Sodium and lithium belong to the same group elements, have similar physicochemical properties with lithium, and abundant reserves, low price, and in addition, no alloying effect occurs between sodium and aluminum, so the copper foil can be replaced to be used as a current collector of a sodium ion battery cathode, and the cost is further reduced, therefore, the sodium ion battery has wider application prospect in a large-scale energy storage system.
However, the relative atomic mass of sodium element is much higher than that of lithium, resulting in a small theoretical specific capacity, and the radius of sodium ion is larger than that of lithium ion, making it more difficult for sodium ion to be inserted and extracted in the battery material. In recent years, good progress has been made in the positive electrode material, however, the graphite negative electrode that has been successfully commercialized in the lithium ion battery has no sodium storage property, and a suitable negative electrode material has been one of the key problems that limit the development of the sodium ion battery, so for the sodium ion battery, it is of great significance to develop a negative electrode material having excellent performance.
Researches find that hard carbon is an amorphous carbon material which is difficult to graphitize, is mainly obtained by pyrolysis of high molecular polymers, has larger graphite-like interlayer spacing, and has higher capacity (300 mAh.g) when applied to a sodium ion battery -1 ) And better cycle performance. However, the first coulombic efficiency of hard carbon is low, and secondly, the disordered and irregular arrangement of carbon layers inside results in poor conductivity and poor rate capability. In addition, the precursors of hard carbons currently used, such as sugars, polymers, lead to high production costs of hard carbons. At present, in order to solve these problems, researchers have conducted researches on both carbon source selection and synthesis methods to prepare a series of anode materials with excellent performance. The results reported by Lu et al (Lu P, sun Y, xiang H, liang X, yu Y.3D Amorphous Carbon with Controlled ports and distributed Structures as a High-Rate Anode Material for Sodium-Ion batteries. Adv Energy Material 2018;8 (8): 1702434) show that the microstructure of the negative electrode Material (e.g., disorder and graphitic regions) significantly affects the Sodium storage capacity and the first coulombic efficiency of Amorphous Carbon. However, higher reversible capacity can often be obtained by sacrificing first coulombic efficiency through the introduction of defects and porous structures. Fortunately, recent findings by ZHao et al (ZHao X, ding Y, xu Q, yu X, liu Y, shen H. Low-Temperature Growth of Hard Carbon with Graphite Crystal for Sodium-Ion Storage with High Initial compatibility. A General method. Adv Energy Mater.2019;9 (10): 1803648) indicate that growing Graphite crystals and pseudo-Graphite regions on microspheres obtained from eggshells and sucrose can improve both the first effect and the reversible capacity.However, the yield of biomass hard carbon is low, and the source of the precursor is too dispersed, which hinders large-scale commercial application of biomass hard carbon. It follows that this remains a great challenge for developing low cost hard carbon anode materials with high first-pass and reversible capacity.
Disclosure of Invention
Technical problem
In order to solve the problems, the invention aims to provide hard carbon microspheres with adjustable shapes and pore structures, a preparation method thereof and a sodium ion battery comprising the hard carbon microspheres. The hard carbon microsphere is used as a negative electrode material of a sodium ion battery, and has low preparation cost and excellent electrical property.
Technical scheme
According to a first aspect of the present invention, there is provided a hard carbon microsphere having a surface with depressions and a morphology similar to preserved plum, the hard carbon microsphere having a particle size of 1 to 5 μm, preferably 1 to 3 μm.
1343cm in the Raman spectrum of the hard carbon microsphere -1 The peak of the near D band caused by defects is at 1589cm -1 Ratio I of intensity of near peak of G band formed of crystalline graphite D /I G Is 1.0 to 1.1. The ratio I of the D peak to the G peak is generally used D /I G The order degree or disorder degree of the material is reflected, a lower ratio in a proper range indicates that the material has higher order degree, so that the first coulombic efficiency is favorably improved, and a higher ratio in the proper range indicates that the material has higher disorder degree, so that the defects are favorable for the rapid transmission of sodium ions, and the multiplying power performance is improved.
Preferably, in the microspheres, the average interlayer spacing d of the (002) plane 002 0.395-0.420 nm, which is obtained by an X-ray diffraction method using CuK α rays as a radiation source, and calculated based on the bragg equation. An interlayer distance in this range is very advantageous for high reversible capacity, since an interlayer distance in this range is very suitable for intercalation and deintercalation of sodium ions.
Preferably, the BET surface area of the hard carbon microspheres is 10-550 m 2 ·g -1 (ii) a Preferably 10 to 15m 2 ·g -1 Or 100 to 550m 2 ·g -1 (ii) a More preferably 10 to 15m 2 ·g -1 Or 200 to 505m 2 ·g -1 . The BET within the range of the present invention, a lower specific surface area contributes to the reduction of the formation of a solid electrolyte interface film (SEI), thereby improving the first effect and reversible capacity, while a larger specific surface area increases the contact area of the electrode active material with the electrolyte, promotes the transport of sodium ions and reduces the diffusion distance of sodium ions, contributing to the improvement of rate performance.
Preferably, the pore volume of the hard carbon microspheres is 0.01-0.07 cm 3 ·g -1 . Pore volume within the above range, when the pore volume is small, mesopores are few, which is favorable for reducing the occurrence of side reactions of the electrode material and the electrolyte, thereby improving the first effect and reversible capacity. When the pore volume is larger, a large number of micropores and mesopores exist, the micropores provide a large number of sodium ion active sites, and the mesopores provide a rapid channel for sodium ion transmission, so that the transmission of sodium ions is promoted, the diffusion distance of the sodium ions is reduced, and the rate capability is favorably improved.
According to another aspect of the present invention, there is provided a method for preparing the hard carbon microspheres, comprising the steps of:
1) Dissolving a mixture of sodium lignosulfonate and water-soluble inorganic salt in water to prepare a precursor spraying solution;
2) Carrying out spray drying treatment on the precursor spray solution obtained in the step 1) to obtain precursor powder;
3) Calcining and pre-carbonizing the precursor powder at 500-800 ℃ under a protective atmosphere;
4) Washing the powder obtained in the step 3) with dilute acid aqueous solution and water for many times and drying;
5) And 4) carbonizing the powder obtained in the step 4) at high temperature of 1100-1500 ℃ under the protective atmosphere to obtain the hard carbon microspheres.
The water-soluble inorganic salt is a water-soluble sodium salt or potassium salt, and more preferably sodium chloride.
The weight ratio of the sodium lignin sulfonate to the water-soluble inorganic salt is 1:0 to 6, preferably 1:0 or 1:1 to 6.
Preferably, the water in step 1) and step 4) is deionized water.
Preferably, the dilute aqueous acid solution in step 4) is dilute hydrochloric acid, and the concentration of the dilute aqueous acid solution is 0.1-8 mol/L, and more preferably 0.5-3 mol/L.
Preferably, the solid content in the precursor spray solution is 3 to 5wt%.
Preferably, the parameters of the spray drying process are set as follows: the inlet temperature is 120-140 ℃, the outlet temperature is 70-110 ℃, the circulating air quantity of the circular fan is 50-70%, and the rotating speed of the peristaltic pump is 40-50%.
Preferably, the pre-carbonization treatment time is 1 to 3 hours, and the temperature rise rate is 1 to 5 ℃ per minute -1 。
Preferably, the time of further high-temperature carbonization is 1 to 3 hours, and the temperature rise rate is 1 to 5 ℃ min -1 。
According to a third aspect of the present invention, there is provided an anode material for a sodium ion battery comprising the hard carbon microspheres.
According to a fourth aspect of the present invention, there is provided a sodium ion battery whose anode comprises the anode material.
Advantageous effects
1. The hard carbon microsphere provided by the invention takes sodium lignosulfonate as a precursor, has a larger interlayer spacing and is very suitable for sodium storage. The invention can regulate and control the appearance, structure and performance of the hard carbon microspheres according to the selection of raw materials. When the raw material only contains sodium lignosulfonate, the obtained hard carbon microspheres have a plum-shaped special appearance and a small specific surface area, so that the side reactions of the electrode active material and the electrolyte are reduced, the first coulombic efficiency is improved, and the good circulation stability is achieved. When the raw materials comprise sodium lignosulfonate and a water-soluble inorganic salt pore-forming agent, the obtained hard carbon microsphere has a rich pore channel structure, provides an active site of sodium ions and a rapid transmission channel, and simultaneously has a large specific surface area, so that the contact area of an electrode active material and an electrolyte is increased, the transmission of the sodium ions is promoted, and the diffusion distance of the sodium ions is reduced. Furthermore, the regulation and control of the morphology and the pore structure can be realized by adjusting the proportion of the sodium lignosulfonate to the water-soluble inorganic salt pore-forming agent.
2. The method for preparing the adjustable hard carbon microspheres is characterized in that precursor solution is subjected to spray drying and then is subjected to high-temperature calcination and carbonization in protective atmosphere to prepare the adjustable hard carbon microspheres. The preparation method is simple to operate, good in repeatability, low in preparation cost and very suitable for large-scale production. In addition, the sodium lignosulfonate is used as a byproduct in the paper making industry, has rich source and low price, further reduces the product cost, and is beneficial to commercialization of sodium ion batteries.
3. When the raw material only contains sodium lignosulfonate, the hard carbon microspheres have high capacity and first coulombic efficiency, and when the raw material contains sodium lignosulfonate and a water-soluble inorganic salt pore-forming agent, the hard carbon microspheres have high rate performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a Scanning Electron Micrograph (SEM) of hard carbon microspheres prepared in example 1 of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of hard carbon microspheres prepared in examples 2 to 5 of the present invention;
fig. 3 is a nitrogen adsorption and desorption graph of hard carbon microspheres prepared in examples 2 to 5 of the present invention;
fig. 4 is a pore size distribution diagram of hard carbon microspheres prepared in examples 2 to 5 of the present invention;
fig. 5 is a charge and discharge graph of a sodium ion battery assembled using hard carbon microspheres prepared in example 1 of the present invention;
fig. 6 is a graph of rate performance of sodium ion batteries assembled using hard carbon microspheres prepared in examples 2 to 5 of the present invention;
fig. 7 is a raman spectrum of hard carbon microspheres prepared in examples 2 to 5 of the present invention.
Detailed Description
In order to clearly, completely and clearly describe the technical solution of the present invention, the following embodiments are provided. It is to be understood that the illustrated embodiments are only a few, and not all, of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation process of the hard carbon microspheres comprises the following steps: first, 12g of sodium lignosulfonate was weighed and dissolved in 400ml of deionized water to prepare a precursor spray solution. And then, carrying out spray drying treatment on the precursor spray solution to obtain precursor powder, wherein the inlet temperature is 130 ℃, the circulating air quantity of the ring fan is 60%, and the rotating speed of the peristaltic pump is 45%. Subsequently, the precursor powder was placed in a tube furnace under an argon atmosphere at 3 ℃ min -1 Heating to 500 deg.C, keeping the temperature for 3h, and naturally cooling to room temperature. And next, washing the obtained black powder with 1M diluted hydrochloric acid, heating to 80 ℃ each time, stirring at constant temperature for 2 hours, washing with deionized water to be neutral after acid washing, heating to 80 ℃ each time, stirring at constant temperature for 1 hour, and drying in a vacuum drying oven. Finally, a further carbonization is carried out, the powder being placed in a tube furnace under an argon atmosphere at 3 ℃ min -1 Heating to 1300 ℃, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the hard carbon microspheres 1 which are marked as C-N-1-0.
Referring to fig. 1, it is a scanning electron microscope image of the hard carbon microsphere in example 1 of the present invention, the hard carbon microsphere has a "plum" shape, similar to the hard carbon microsphere with folds, and the size is 1-3 μm.
Referring to fig. 5, a first and second charge/discharge curve of the sodium ion battery assembled with the hard carbon material of example 1 shows that the first coulombic efficiency of the hard carbon microsphere is 88.3% and the reversible capacity is 339mAh · g at 0.1C rate -1 Among the known hard carbon anode materials, this is at a higher level. Such high first effect and capacity are related to its small specific surface area and large interlayer spacing, and on the one hand, the specific surface area of the hard carbon microspheres in example 1 of the invention is only 12m 2 ·g -1 The smaller specific surface area is beneficial to the formation of an SEI film, the reduction of side reactions of an electrode active material and an electrolyte and the reduction of irreversible capacity, and on the other hand, the larger interlayer spacing is beneficial to the storage of sodium ions.
Comparative example 1
Example 1 was repeated, except that no spray drying process was used, and the procedure was as follows: weighing 12g of sodium lignosulfonate, directly placing the sodium lignosulfonate in a tube furnace, and performing temperature control and min at 3 ℃ in an argon protective atmosphere -1 Heating to 500 deg.C, keeping the temperature for 3h, and naturally cooling to room temperature. And next, washing the obtained black powder with 1M diluted hydrochloric acid, heating to 80 ℃ each time, stirring at constant temperature for 2 hours, washing with deionized water to be neutral after acid washing, heating to 80 ℃ each time, stirring at constant temperature for 1 hour, and drying in a vacuum drying oven. Finally, a further carbonization is carried out, the powder being placed in a tube furnace under an argon atmosphere at 3 ℃ min -1 Heating to 1300 ℃, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the conventional hard carbon material 1 marked as C.
Comparative example 2
Example 1 was repeated, with the difference that the carbon source was selected, and the preparation was as follows: 12g of phenolic resin is weighed and dissolved in 400ml of ethanol to prepare a precursor spray solution. And then, carrying out spray drying treatment on the precursor spray solution to obtain precursor powder, wherein the inlet temperature is 130 ℃, the circulating air quantity of the ring fan is 60%, and the rotating speed of the peristaltic pump is 45%. Subsequently, the precursor powder was placed in a tube furnace under an argon atmosphere at 3 ℃ min -1 Heating to 500 deg.C, keeping the temperature for 3h, and naturally cooling to room temperature. Finally, a further carbonization was carried out, the powder being placed in a tube furnace under an argon atmosphere at 3 ℃ for min -1 Heating to 1300 ℃, preserving the heat for 2h, naturally cooling to room temperature to obtain the conventional hard carbon material 2, namelyIs marked as C-P.
As shown in table 1, is a price table for sodium lignosulfonate and phenolic resin.
TABLE 1
Carbon source Lignosulfonic acid sodium salt Phenolic resin
Price 5000/ton 18000/ton
* Price in 12 months of 2019
Therefore, the price of the sodium lignosulfonate is far lower than that of the phenolic resin, and the production cost of the sodium lignosulfonate as a raw material is low.
Example 2
The preparation process of the hard carbon microsphere comprises the following steps: firstly, 6g of sodium lignosulfonate and 6g of sodium chloride are weighed and dissolved in 400ml of deionized water to prepare a precursor spraying solution. And then, carrying out spray drying treatment on the precursor spray solution to obtain precursor powder, wherein the inlet temperature is 130 ℃, the circulating air quantity of the ring fan is 60%, and the rotating speed of the peristaltic pump is 45%. Subsequently, the precursor powder was placed in a tube furnace under an argon atmosphere at 3 ℃ min -1 Heating to 750 deg.C, keeping the temperature for 2h, and naturally cooling to room temperature. And next, washing the obtained black powder with 1M diluted hydrochloric acid, heating to 80 ℃ each time, stirring at constant temperature for 2 hours, washing with deionized water to be neutral after acid washing, heating to 80 ℃ each time, stirring at constant temperature for 1 hour, and drying in a vacuum drying oven. Finally, further carbonization is carried out, the powder is placed in a tube furnace,under the protection of argon gas, at 3 ℃ for min -1 Heating to 1300 ℃, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the hard carbon microspheres 2 marked as C-N-1-1.
Example 3
Hard carbon microspheres 3, labeled C-N-1-2, were prepared in the same manner as in example 2, except that 4g of sodium lignosulfonate and 8g of sodium chloride were used.
Example 4
Hard carbon microspheres 4, labeled C-N-1-3, were prepared in the same manner as in example 2, except that 3g of sodium lignosulfonate and 9g of sodium chloride were used.
Example 5
Hard carbon microspheres 5, labeled C-N-1-4, were prepared in the same manner as in example 2, except that 2.4g of sodium lignosulfonate and 9.6g of sodium chloride were used.
Example 6
Hard carbon microspheres 6, labeled C-N-1-5, were prepared in the same manner as in example 2, except that 2g of sodium lignosulfonate and 10g of sodium chloride were used.
Example 7
Hard carbon microspheres 7, labeled C-N-1-6, were prepared in the same manner as in example 2, except that 1.7g of sodium lignosulfonate and 10.3g of sodium chloride were used.
Example 8
Hard carbon microspheres 8, labeled C-N-2-1, were prepared in the same manner as in example 2, except that 8g of sodium lignosulfonate and 4g of sodium chloride were used.
Example 9
Hard carbon microspheres 9, labeled C-N-3-1, were prepared in the same manner as in example 2, except that 9g of sodium lignosulfonate and 3g of sodium chloride were used.
Example 10
Hard carbon microspheres 10, labeled C-N-4-1, were prepared in the same manner as in example 2, except that 9.6g of sodium lignosulfonate and 2.4g of sodium chloride were used.
Example 11
Hard carbon microspheres 11, labeled C-N-5-1, were prepared in the same manner as in example 2, except that 10g of sodium lignin sulfonate and 2g of sodium chloride were used.
Example 12
Hard carbon microspheres 12, labeled C-N-6-1, were prepared in the same manner as in example 2, except that 10.3g of sodium lignosulfonate and 1.7g of sodium chloride were used.
Experimental examples
Electrochemical performance test, the hard carbon microspheres 1 to 5 prepared in examples 1 to 5 of the present invention were used as negative electrode active materials, acetylene Black (AB) was used as a conductive agent, carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) were used as binders, and the ratio of hard carbon: AB: CMC: SBR =80:10:5:5, mixing with deionized water, coating the mixture on a copper foil, drying, rolling and punching to prepare the electrode plate. A CR2032 button half-cell was assembled in a glove box filled with argon, the negative electrode was a cut metal sodium sheet, the separator was glass fiber, and the electrolyte was a 1M sodium perchlorate solution (the solvents were ethylene carbonate and diethyl carbonate, the volume ratio of the two was 1. The assembled battery was subjected to a charge and discharge test at 0.01-3V.
Referring to fig. 2, which is a scanning electron microscope image of the hard carbon microspheres in examples 2 to 5 of the present invention, fig. (a) to (d) correspond to C-N-1-1, C-N-1-2, C-N-1-3, and C-N-1-4, respectively, when the raw material contains a sodium chloride pore-forming agent, the surface wrinkles of the hard carbon microspheres are more serious, and the amount of sodium chloride increases more significantly, and the surface can see the pore structure, and the size of the hard carbon microspheres is 1 to 3 μm.
Referring to fig. 3 and 4, graphs of nitrogen adsorption and desorption and pore size distribution of hard carbon microspheres in examples 2 to 5 of the present invention are shown. Detailed results of examples 1 to 12 and comparative examples 1 to 2 are shown in table 2, and it can be seen that the hard carbon microspheres have a smaller specific surface area without the addition of sodium chloride, which is advantageous in reducing the generation of an SEI film and reducing side reactions, and also have a more excellent structure than the hard carbon materials prepared without using a spray drying technique and other carbon sources. When sodium chloride is added, the hard carbon microsphere has a larger specific surface area and rich pore channel structures including micropores and mesopores, so that the contact area of an electrode active material and electrolyte is increased, the transmission of sodium ions is promoted, the diffusion distance of the sodium ions is reduced, and active sites and a rapid transmission channel of the sodium ions are provided. Meanwhile, the invention can also realize the regulation and control of the shape and the pore structure of the hard carbon microsphere by adjusting the proportion of the sodium lignosulfonate and the sodium chloride pore-forming agent.
TABLE 2
Figure BDA0002309970650000091
Fig. 6 is a graph showing rate performance of sodium ion batteries assembled with hard carbon microspheres in examples 2 to 5 of the present invention. The detailed data of examples 1 to 12 and comparative examples 1 to 2 are shown in table 3, and it can be seen that the hard carbon microsphere has excellent rate capability, and in addition, examples 2 to 12 have different rate capability, and the structure of the hard carbon microsphere can be controlled by adjusting the ratio of the sodium lignosulfonate to the sodium chloride pore-forming agent, so as to improve the electrochemical performance.
TABLE 3
Figure BDA0002309970650000092
In addition, the average interlayer spacing d of the microspheres in examples 1 to 12 and comparative examples 1 to 2 002 The measurement results of (b) are shown in table 4 below. The average layer interval is obtained by an X-ray diffraction method using CuK α rays as a radiation source, and calculated based on a bragg equation. Measurement of 1343cm using Raman Spectroscopy -1 The peak of the near D band caused by defects is at 1589cm -1 Ratio I of intensity of near peak of G band formed of crystalline graphite D /I G The results are shown in table 3 below, where a lower ratio in the appropriate range indicates that the material has a higher degree of order, which is beneficial to improving the first effect, and a higher ratio in the appropriate range indicates that the material has a higher degree of disorder, and the defects are beneficial to the rapid transmission of sodium ions, which improves the rate performance.
TABLE 4
Sample (I) d 002 I D /I G
Example 1 0.396 1.015
Comparative example 1 0.392 0.990
Comparative example 2 0.390 0.981
Example 2 0.395 1.031
Example 3 0.395 1.037
Example 4 0.396 1.039
Example 5 0.412 1.069
Example 6 0.411 1.061
Example 7 0.410 1.050
Example 8 0.394 1.110
Example 9 0.394 1.112
Example 10 0.393 1.115
Example 11 0.393 1.115
Example 12 0.392 1.113

Claims (9)

1. A hard carbon microsphere, the surface of which is provided with a dent, the grain diameter of the hard carbon microsphere is 1 to 5 μm,
1343cm in the Raman spectrum of the hard carbon microsphere −1 The peak of the nearby D band caused by defects is at 1589cm −1 Near crystalline graphite formRatio I of the intensities of the peaks of the G band D /I G Is 1.031 to 1.069,
the BET surface area of the hard carbon microsphere is 200 to 505m 2 ·g -1 The pore volume of the hard carbon microsphere is 0.040 to 0.067 cm 3 ·g -1 ，
In the microspheres, the average interlayer spacing d of the (002) planes 002 0.395 to 0.412 nm, which is obtained by X-ray diffraction using CuK alpha rays as a radiation source and calculated based on the Bragg equation,
and the hard carbon microspheres are prepared by a method comprising the following steps:
1) Dissolving a mixture of sodium lignosulfonate and water-soluble inorganic salt in water to prepare a precursor spraying solution, wherein the weight ratio of the sodium lignosulfonate to the water-soluble inorganic salt is 1: 1-6;
2) Carrying out spray drying treatment on the precursor spray solution obtained in the step 1) to obtain precursor powder;
3) Calcining and pre-carbonizing the precursor powder at 500-800 ℃ under a protective atmosphere;
4) Washing the powder obtained in step 3) with dilute acid aqueous solution and water for many times and drying;
5) Carbonizing the powder obtained in the step 4) at high temperature of 1100-1500 ℃ under the protective atmosphere to obtain the hard carbon microspheres,
the water-soluble inorganic salt is water-soluble sodium salt or potassium salt.
2. The hard carbon microsphere according to claim 1, wherein the particle size of the hard carbon microsphere is 1 to 3 μm.
3. A method of preparing hard carbon microspheres according to claim 1 or 2 comprising the steps of:
1) Dissolving a mixture of sodium lignosulfonate and water-soluble inorganic salt in water to prepare a precursor spray solution, wherein the weight ratio of the sodium lignosulfonate to the water-soluble inorganic salt is 1: 1-6;
2) Carrying out spray drying treatment on the precursor spray solution obtained in the step 1) to obtain precursor powder;
3) Calcining and pre-carbonizing the precursor powder at 500-800 ℃ under a protective atmosphere;
4) Washing the powder obtained in step 3) with dilute acid aqueous solution and water for many times and drying;
5) Carbonizing the powder obtained in the step 4) at high temperature of 1100-1500 ℃ under the protective atmosphere to obtain the hard carbon microspheres,
the water-soluble inorganic salt is water-soluble sodium salt or potassium salt.
4. The method of claim 3, wherein the water-soluble inorganic salt is sodium chloride.
5. The method of claim 3 or 4,
the water in the step 1) and the step 4) is deionized water;
the dilute acid aqueous solution in the step 4) is dilute hydrochloric acid, and the concentration of the dilute acid aqueous solution is 0.1 to 8mol/L.
6. The method as claimed in claim 5, wherein the diluted acid aqueous solution in the step 4) is diluted hydrochloric acid, and the concentration of the diluted hydrochloric acid is 0.5 to 3mol/L.
7. The method of claim 3 or 4,
the pre-carbonization treatment time is 1 to 3 hours, and the heating rate is 1 to 5 ℃ min -1 ；
The high-temperature carbonization time is 1 to 3 hours, and the heating rate is 1 to 5 ℃ min -1 。
8. An anode material for a sodium ion battery comprising the hard carbon microspheres according to claim 1 or 2.
9. A sodium ion battery whose anode comprises the anode material of claim 8.
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