CN111564630B - Hard carbon material and preparation method thereof - Google Patents
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- CN111564630B CN111564630B CN202010517188.2A CN202010517188A CN111564630B CN 111564630 B CN111564630 B CN 111564630B CN 202010517188 A CN202010517188 A CN 202010517188A CN 111564630 B CN111564630 B CN 111564630B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
- C07H17/065—Benzo[b]pyrans
- C07H17/07—Benzo[b]pyran-4-ones
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a hard carbon material and a preparation method thereof, wherein the hard carbon material is prepared by the following steps: washing pericarpium Citri Junoris with water, cutting, placing in a hydrothermal reaction kettle, reacting for a certain time, cooling, mashing, filtering, cleaning, and freeze drying to obtain carbon precursor; heating the obtained carbon precursor, and performing pre-carbonization treatment; carrying out high-temperature pyrolysis treatment on the pre-carbonized carbon precursor in a protective atmosphere; and washing the obtained product with an acid solution, washing the product with clear water to be neutral, and drying the product to obtain the hard carbon material. The method realizes waste utilization, the operation process is simple and easy to implement, the obtained hard carbon material is uniform in size, the granularity is 0.5-5 mu m, and the hard carbon material serving as a negative electrode material of a sodium ion battery has high specific capacity density (290 mAh/g) and good cycle performance. The hard carbon material obtained by the method is an excellent sodium ion battery cathode material.
Description
Technical Field
The invention relates to the field of novel secondary battery electrode materials, in particular to a hard carbon material and a preparation method thereof.
Background
Lithium ion batteries are the most common electrochemical energy storage device in the current society, and with the development of large-scale energy storage technologies for portable electronic equipment, electric automobiles and new energy power generation, the demand increases day by day and the demand of lithium also increases. Because the reserve of lithium is limited and the distribution is uneven, the price of the lithium-related material is greatly increased, and the cost of the lithium ion battery is improved. The limited lithium resources also make sustainable use of lithium ion batteries challenging. To solve this problem, the development of inexpensive non-lithium-based electrochemical energy storage devices with excellent performance has become a new research focus in recent years. Among them, similar to the working principle of lithium ion batteries, sodium ion batteries that are not limited by resources are receiving much attention.
Graphite is the most mature and widely applied negative electrode material of the lithium ion battery, but sodium ions are difficult to be embedded into a graphite layer because the ion radius of the sodium ions is larger than that of the lithium ions, and the graphite cannot be used as the negative electrode material of the sodium ion battery. The hard carbon is microscopically in an irregular amorphous structure and is formed by stacking single-layer graphene sheets with small sizes in a disordered mode, so that a structure similar to a card house is constructed, more storage active points can be provided for ions, the diffusion of the ions in the structure is facilitated, the storage and the de-intercalation of sodium ions are facilitated, and the high stability can be kept in the sodium ion de-intercalation process, so that the hard carbon is a preferred cathode material of a sodium ion battery at present.
The preparation of hard carbon cathode materials by using biomass materials is a research hotspot in the field of electrochemical energy storage. The preparation of hard carbon and other carbonaceous materials from biomass is usually carried out by cleaning, drying and crushing the raw materials, and then pyrolyzing at high temperature. Because plant fibers or biological macromolecules have strong toughness and are difficult to break after drying, the size of the pyrolyzed hard carbon particles is large and uneven, the subsequent processes such as electrode coating and the like are not facilitated, and a thin coating or a coating with uniform thickness is difficult to obtain.
Disclosure of Invention
The invention aims to overcome the defects that the existing hard carbon negative electrode material is uneven in size and difficult to perform electrode coating, and provides a hard carbon material prepared from orange peels as a raw material, wherein black powder with uniform size is obtained by means of a unique net-shaped internal organization structure of the orange peels and a specific process, the particle size is 0.5-5 mu m, and the hard carbon material is very favorable for electrode coating.
In the traditional technology, the preparation of the biomass hard carbon material can also adopt a mode of firstly carbonizing and then ball milling to reduce the size of hard carbon particles, so that the effect of uniform size is obtained. However, the ball milling process is not only time consuming and energy consuming, but also introduces additional impurities, requiring additional electromagnetic or acid washing impurity removal steps. In addition, the hard carbon powder obtained by ball milling needs to be sieved to remove the excessively fine carbon powder particles, so that the bulk density of the hard carbon is improved, and therefore, the advantage of directly obtaining a refined material is not provided.
The orange peel contains a large amount of colloid, vitamin C and essential oil, and microscopically presents network tissues. Unlike biomass of high cellulose content such as wood and bamboo, orange peel is easily degraded by a suitable hydrothermal treatment, so that an organic carbonaceous feedstock with uniform particles can be obtained.
The orange peel also contains pectin such as pectin and essential oil, and plays a role of a binder in the natural drying process of the orange peel, so that the dried orange peel is hard and is not easy to mechanically break. The impurities are easy to decompose and volatilize in the high-temperature carbonization process, block the air outlet of heat treatment equipment, are adsorbed on the surface of the carbon material and generate chemical vapor deposition of carbon, and influence the hard carbon to obtain an ideal interlayer spacing and microstructure.
In order to overcome the above difficulties, the present invention is carried out by: 1) the method comprises the following steps of carrying out hydrothermal treatment on the orange peels, wherein the orange peels contain substances such as hesperidin, the substances are directly heated to volatilize strong smell, the texture structure of the orange peels is protected, in addition, the decomposition and volatilization of colloid in the orange peels can cause the blockage of an air outlet of heat treatment equipment, and the influence on the microstructure structure of a hard carbon material is not good, so that the method firstly carries out hydrothermal treatment on the orange peels, decomposes and removes the colloid from the orange peels by utilizing the hydrothermal treatment, firstly obtains raw materials with uniform size, and solves the problems that the dried biomass is not easy to crush, the hard carbon material has large particles and uneven size; meanwhile, useful substances such as hesperidin in the orange peels are collected into a liquid phase for other purposes through hydrothermal degradation; the hydrothermal residue filter cake is freeze-dried, the fluffy state of the raw materials is kept, and the key is that the powdery raw materials are obtained by later heating. 2) According to the invention, the freeze-dried fluffy carbon precursor is pre-carbonized and then pyrolyzed at high temperature, so that the carbon particles are prevented from being seriously agglomerated in the pyrolysis process, and the particle size uniformity of the material is kept. As the organic matters which are easy to cause adhesion are removed in the pre-carbonization process, the material is ensured to keep uniformly dispersed during high-temperature pyrolysis. 3) The method comprises the steps of carrying out high-temperature pyrolysis on the material, heating the material to 1000-1500 ℃ under the protection of flowing nitrogen or argon to carry out carbonization, and when the temperature is lower than 1000 ℃, carbonizing a carbon precursor insufficiently and mainly taking an amorphous state; above 1600 ℃ the short-range ordered graphite interlayer spacing of the hard carbon is reduced, which is not beneficial to sodium ion storage. 4) Finally, the material is washed by acid solution to remove impurities, so that the material can exert electrochemical activity and is safe to use.
The specific scheme is as follows:
a method of preparing a hard carbon material, comprising the steps of:
step 1): washing and cutting orange peels with water, placing the orange peels into a hydrothermal reaction kettle, adding a proper amount of water, carrying out hydrothermal reaction for a certain time under a sealing condition to recover hesperidin in the orange peels, then cooling, mashing, filtering, washing, freeze-drying, and carrying out freeze-drying to obtain fluffy carbon precursor;
step 2): heating the carbon precursor obtained in the step 1), and carrying out pre-carbonization treatment at the temperature of 200-;
step 3): carrying out high-temperature pyrolysis treatment on the pre-carbonized carbon precursor in a protective atmosphere;
step 4): washing the product obtained in the step 3) with an acid solution, washing the product with clear water to be neutral, and drying the product to obtain the hard carbon material.
Further, the orange peel in the step 1) is one or more of navel orange, ice orange, sweet orange and orange, and is preferably fresh orange peel.
Further, the hydrothermal reaction in the step 1) is carried out at the temperature of 150-180 ℃, and the reaction time is 4-8 hours.
Further, the step 1) of freeze drying is carried out in a freeze dryer, the freezing temperature is below minus 55 ℃, the freezing time is 24-36 hours, and the shape of the mesh tissue in the orange peel is kept through freeze drying, so that the fluffy carbon precursor is obtained.
Further, the pre-carbonization in the step 2) is carried out in a muffle furnace under an air atmosphere, the pre-carbonization temperature is 210-290 ℃, and the pre-carbonization time is 2-12 hours.
Further, the high-temperature pyrolysis temperature in the step 3) is 1000-1500 ℃, the heat preservation time is 1-5 hours, and the heating rate is 3-5 ℃/min;
optionally, the protective atmosphere is high purity nitrogen or argon or a mixture of both.
Further, the acid solution in the step 4) may be any one of aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid, and the concentration is 0.1-1 mol/L.
The invention also protects the hard carbon material prepared by the preparation method of the hard carbon material, wherein the hard carbon material is black powder with uniform particle size, the particle size range is 0.5-5 mu m, the graphitized amorphous carbon content is lower than 5wt%, the short-range ordered graphite content is higher than 95wt%, and the short-range ordered graphite interlayer spacing is 0.3-0.5nm, preferably 0.3-0.4 nm.
The invention also discloses a sodium ion battery negative electrode material which comprises an active material, a conductive agent and a binder, wherein the active material is the hard carbon material, and the sodium ion battery negative electrode material can be directly coated on a current collecting sheet to form an electrode.
Further, the specific sodium storage capacity of the negative electrode material of the sodium ion battery at 0.05A/g is not lower than 290mAh/g, the maximum specific sodium storage capacity at 2A/g reaches 90mAh/g, and the specific sodium storage capacity after the negative electrode material is circulated for 500 times at a multiplying power of 0.5A/g is still kept above 200 mAh/g.
Has the advantages that:
the hard carbon material prepared by the method has uniform granularity and excellent sodium storage performance, the specific capacity of sodium storage at 0.05A/g is not less than 290mAh/g, the specific capacity of sodium storage at 2A/g reaches 90mAh/g, the specific capacity of sodium storage after circulation for 500 times at 0.5A/g multiplying power is still kept above 200mAh/g, and the hard carbon material has better market development prospect.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
Fig. 1 is a scanning electron microscope image of a hard carbon material provided in an embodiment 1 of the present invention;
fig. 2 is a rate performance graph of a hard carbon anode material provided in one embodiment 5 of the present invention;
fig. 3 is a graph of cycle performance of a hard carbon anode material provided in one embodiment 5 of the present invention;
FIG. 4 is a scanning electron micrograph of comparative example 1 according to the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 180 deg.C for 4 hr under sealed condition, cooling, mashing, filtering, cleaning, and lyophilizing at-55 deg.C for 36 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 210 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1300 ℃ at the speed of 3 ℃/min under the protective high-purity nitrogen atmosphere, preserving the heat for 3h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Fig. 1 is a scanning electron micrograph of the hard carbon material obtained in this example, which shows that the hard carbon particles have a uniform size of 0.5 to 5 μm. This granularity scope is favorable to electrode coating very much, because need mix thick dress with active material and auxiliary reagent during the coating, coats on the electrode surface, forms the thick coating of 100 ~ 200um, consequently, active material's granularity is little, and the size is all the key that obtains high quality electrode.
Example 2
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 150 deg.C for 8 hr under sealed condition, cooling, mashing, filtering, cleaning, and lyophilizing at-55 deg.C for 24 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 200 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1000 ℃ at the speed of 3 ℃/min under the protective high-purity nitrogen atmosphere, preserving the heat for 5h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Example 3
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 160 deg.C for 7 hr under sealed condition, cooling, mashing, filtering, cleaning, and freeze drying at-55 deg.C for 30 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 300 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1400 ℃ at the speed of 3 ℃/min under the protective high-purity nitrogen atmosphere, preserving the heat for 2h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Example 4
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 170 deg.C for 5 hr under sealed condition, cooling, mashing, filtering, cleaning, and lyophilizing at-55 deg.C for 36 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 290 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1500 ℃ at the speed of 3 ℃/min in the protective high-purity nitrogen atmosphere, preserving the heat for 1h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Example 5
Mixing the hard carbon material prepared in the example 1, conductive carbon black and sodium alginate in a mass ratio of 80: 10: 10 mixing in deionized water, grinding into paste, coating on copper foil current collector, drying at 80 deg.C for 12 hr, cutting into several pole pieces with diameter of 12mm, weighing, calculating the mass of hard carbon material (active substance), placing in argon protective glove box, using metal sodium sheet as counter electrode, using glass fiber as diaphragm, and using 1mol/L NaClO4And the/PC solution is used as an electrolyte, a 2032 button type mobile battery is assembled, and a sodium ion half-battery is subjected to charge-discharge test in a constant current charge-discharge mode, wherein the current density range is 0.05-3A/g, and the voltage range is 0-2.5V.
The test results are shown in fig. 2 and fig. 3, and fig. 2 is a curve of the specific mass capacity of the hard carbon material in relation to the current density. The charge and discharge tests show that the specific mass capacity of the material exceeds 290mAh/g at 0.05A/g and is 90/g at 2A/g. FIG. 3 is a cycle curve of the hard carbon material, and it can be seen that the specific sodium storage capacity after 500 cycles at a rate of 0.5A/g is still maintained above 200 mAh/g. The hard carbon material prepared by the invention has the advantages of high specific capacity and good cycle performance.
Comparative example 1
Washing fresh navel orange peel with water, chopping, and directly drying in a heating furnace at 80 deg.C to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 210 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1300 ℃ at the speed of 3 ℃/min under the protective atmosphere, preserving the heat for 3h, and cooling along with the furnace; and washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing the product with clear water to be neutral, and drying the product at 60 ℃ to obtain the contrast material.
FIG. 4 is a scanning electron micrograph of a comparative material. It can be seen that the hard carbon particles are not uniform in size, vary in particle size from 0.5 to 30 μm, and present difficulties in electrode coating.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a hard carbon material is characterized by comprising the following steps: the method comprises the following steps:
step 1): washing and cutting orange peels with water, placing the orange peels into a hydrothermal reaction kettle, adding a proper amount of water, carrying out hydrothermal reaction for a certain time under a sealing condition to recover hesperidin in the orange peels, then cooling, mashing, filtering, washing, freeze-drying, and carrying out freeze-drying to obtain fluffy carbon precursor; the freeze drying is carried out in a freeze dryer, the freezing temperature is below-55 ℃, the freezing time is 24-36 hours, and the shape of the mesh tissue in the orange peel is kept through freeze drying, so that a fluffy carbon precursor is obtained;
step 2): heating the carbon precursor obtained in the step 1), and performing pre-carbonization treatment, wherein the pre-carbonization temperature is 210-290 ℃, and the pre-carbonization time is 2-12 hours;
step 3): carrying out high-temperature pyrolysis treatment on the pre-carbonized carbon precursor in a protective atmosphere; the high-temperature pyrolysis temperature is 1300-1500 ℃, the heat preservation time is 1-5 hours, and the heating rate is 3-5 ℃/min;
step 4): washing the product obtained in the step 3) with an acid solution, washing the product with clear water to be neutral, and drying the product to obtain the hard carbon material, wherein the hard carbon material is black powder with uniform particle size, and the particle size range is 0.5-5 mu m; wherein the graphitized amorphous carbon content is less than 5wt%, the short-range ordered graphite content is more than 95wt%, and the short-range ordered graphite interlayer spacing is 0.3-0.5 nm.
2. The method for producing a hard carbon material according to claim 1, characterized in that: the orange peel in the step 1) is the peel of one or more orange fruits selected from navel orange, ice orange, sweet orange and orange.
3. The method for producing a hard carbon material according to claim 2, characterized in that: the pericarpium Citri Junoris is fresh pericarpium Citri Junoris.
4. The method for producing a hard carbon material according to claim 1, characterized in that: the hydrothermal reaction in the step 1) is carried out at the temperature of 150-180 ℃, and the reaction time is 4-8 hours.
5. The method for producing a hard carbon material according to claim 1, characterized in that: and 2) pre-carbonizing in a muffle furnace under an air atmosphere.
6. The method for producing a hard carbon material according to claim 1 or 4, characterized in that: the protective atmosphere in the step 3) is high-purity nitrogen or argon or the mixture of the high-purity nitrogen and the argon.
7. The method for producing a hard carbon material according to claim 1, characterized in that: the acid solution in the step 4) is any one of aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid, and the concentration of the acid solution is 0.1-1 mol/L.
8. The hard carbon material produced by the method for producing a hard carbon material according to any one of claims 1 to 7, wherein: the hard carbon material is black powder with uniform particle size, the particle size range is 0.5-5 mu m, the graphitized amorphous carbon content is lower than 5wt%, the short-range ordered graphite content is higher than 95wt%, and the short-range ordered graphite interlayer spacing is 0.3-0.5 nm.
9. The negative electrode material of the sodium-ion battery comprises an active material, a conductive agent and a binder, and is characterized in that: the active material is the hard carbon material in claim 8, and the negative electrode material of the sodium-ion battery is directly coated on a current collecting sheet to form an electrode.
10. The negative electrode material for sodium-ion batteries according to claim 9, wherein: the sodium storage specific capacity of the sodium ion battery negative electrode material at 2A/g can reach 90mAh/g at most, and the sodium storage specific capacity can still be maintained above 200mAh/g after the sodium ion battery negative electrode material is cycled for 500 times under the multiplying power of 0.5A/g.
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| CN108996504A (en) * | 2018-08-31 | 2018-12-14 | 广东工业大学 | A kind of absorbent charcoal material and its preparation method and application of porous structure Heteroatom doping |
| 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 |
| CN110627037A (en) * | 2019-06-26 | 2019-12-31 | 陕西科技大学 | Preparation method of nitrogen-doped biomass porous carbon nano electrode material |
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