CN114835104A - Hard carbon material, preparation method and application thereof, and sodium ion battery - Google Patents
Hard carbon material, preparation method and application thereof, and sodium ion battery Download PDFInfo
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- CN114835104A CN114835104A CN202210665737.XA CN202210665737A CN114835104A CN 114835104 A CN114835104 A CN 114835104A CN 202210665737 A CN202210665737 A CN 202210665737A CN 114835104 A CN114835104 A CN 114835104A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a hard carbon material, a preparation method and application thereof and a sodium ion battery. The preparation method of the hard carbon material comprises the following steps: pre-carbonizing, acid-washing, pyrolyzing and ball-milling the carbon precursor; wherein the raw material of the carbon precursor is hazelnut shell; the concentration of each raw material acid in the mixed acid used for pickling is 2-7 mol/L; in the ball milling process, the mass ratio of the adopted milling balls to the materials is 15: 1-25: 1. the hard carbon material has wide raw material source, simple preparation method and low cost, and can realize kilogram-level preparation; low impurity content, uniform particle size, surface and interior enriched sodium adsorption active sites and simultaneous prevention of electrolyte ingress into about 0.53nm ultramicropores; the hard carbon material has remarkable advantages in mass coating when the pole piece is prepared; when the hard carbon material prepared by the method is used for preparing a sodium ion battery, the effects of higher specific capacity of sodium storage and good first coulombic efficiency can be realized.
Description
Technical Field
The invention particularly relates to a hard carbon material, a preparation method and application thereof and a sodium ion battery.
Background
Energy is the basis of human society relying on survival, and with the increasing high-efficiency and clean energy demand in the world, the large-scale energy storage technology solves the contradiction between the discontinuity of renewable clean energy and the continuity of energy demand. Electrochemical energy storage based on secondary battery technology, which is an emerging energy storage technology, has been emerging in recent years in a number of large-scale energy storage technologies. Compared with other secondary batteries, the lithium ion battery has the advantages of high specific energy, stable discharge, good safety, no memory effect and the like, and is widely applied to the fields of electronic equipment, power batteries and the like. However, because of the limited storage capacity of lithium resources, scientists in various countries are looking for secondary batteries or technologies that can meet the increasing demand for energy storage. Under such circumstances, sodium ion batteries have been receiving attention again because of the abundance of natural resources and the close chemical proximity of lithium to the same main group of the periodic table, i.e., the chemical properties, and are considered to be a promising next-generation secondary battery system for large-scale energy storage as a substitute for lithium ion batteries.
However, to realize commercialization of sodium ion batteries, it is critical to select a suitable anode material. Currently, the main negative electrode materials in sodium ion batteries include graphite, soft carbon, hard carbon, and the like. Graphite is the main negative electrode material of commercial lithium batteries, and the actual specific capacity of 360mAh/g is close to the theoretical specific capacity of 372 mAh/g. However, due to the poor sodium removal performance of graphite and the limited sodium storage capacity in carbonate electrolytes, a large number of researchers have paid attention to various disordered carbon materials having a low degree of graphitization, a high degree of disordering, and a large interlayer spacing. The disordered carbon material mainly includes soft carbon and hard carbon. Since soft carbon has a certain interlayer slip ability similar to graphite, van der waals force between soft carbon layers is weak, and a carbon layer thereof has a large movement ability at a high temperature, crystalline graphite is easily formed, and thus hard carbon having a very low degree of order and not being completely graphitized becomes the first choice for the cathode of a commercial sodium ion battery. The biomass material for preparing the hard carbon material has the advantages of wide source, simple synthesis process, environmental protection, reproducibility, certain economic benefit and the like, and is a high-quality carbon source of the cathode material of the sodium-ion battery. However, the existing hard carbon material has the problems of complex preparation method, higher cost, larger particle size of the obtained hard carbon particles, difficulty in subsequent mass coating operation and poor performance in the application of sodium ion batteries.
Disclosure of Invention
The invention provides a hard carbon material, a preparation method and application thereof and a sodium ion battery, aiming at overcoming the defects that the preparation method of the hard carbon material is complex, the cost is high, the particle size of the obtained hard carbon particles is large, the subsequent mass coating operation is not easy to perform, and the performance is not good in the application of the sodium ion battery in the prior art. The hard carbon material prepared by the invention has the characteristics of higher specific capacity of sodium storage and good first coulombic efficiency when used for preparing the sodium ion battery, and has the advantages of simple preparation method, low cost and obvious advantages in mass coating when used for preparing pole pieces. The invention solves the technical problems through the following technical scheme:
the invention provides a preparation method of a hard carbon material, which comprises the following steps:
pre-carbonizing, acid-washing, pyrolyzing and ball-milling the carbon precursor;
wherein the raw material of the carbon precursor is hazelnut shell; the concentration of each raw material acid in the mixed acid used for pickling is 2-7 mol/L; in the ball milling process, the mass ratio of the adopted milling balls to the materials is 15: 1-25: 1.
in the invention, in the ball milling process, the mass ratio of the adopted milling balls to the materials can be 20: 1-25: 1.
in the invention, the hazelnut shell can be one or more of hazelnut, hazel, spiny hazel and big-fruit hazel.
In the present invention, the preparation method of the carbon precursor may be conventional in the art, and generally the hazelnut shell is sequentially washed, dried and pulverized.
The washing operation may be conventional in the art, and typically employs deionized water and ethanol for washing. Mechanical agitation may be employed during the cleaning process. The number of times of washing is generally three times to remove soil and other organic and inorganic impurities attached to the surface of the hazelnut shell. The washing is typically completed with filtration, as is conventional in the art.
Wherein, the drying can be conventional in the field, preferably air-blast drying and vacuum drying, so as to remove the surface solvent to obtain the hazelnut shell which is fully dried and uniformly dispersed.
The forced air drying is generally carried out in a forced air drying oven.
The vacuum drying is generally carried out in a vacuum drying oven.
The temperature of the forced air drying can be 80-90 ℃, for example 80 ℃. The time for the forced air drying may be 8 hours.
The temperature of the vacuum drying may be 110 ℃. The vacuum drying time may be 12 hours.
Wherein, the pulverization is generally carried out in a traditional Chinese medicine pulverizer.
In the present invention, the pre-carbonization is generally carried out in a shaft furnace.
In the present invention, the pre-carbonization atmosphere may be an atmosphere formed by a gas that does not chemically react with the system under the pre-carbonization condition, such as a nitrogen atmosphere, or an atmosphere formed by an inert gas that is conventional in the chemical field. The inert gas may be helium.
In the invention, the rate of heating to the pre-carbonization temperature can be 2-3 ℃/min, for example 2 ℃/min.
In the present invention, the pre-carbonization temperature may be 400 to 700 ℃, for example, 400 ℃, 500 ℃, 600 ℃ or 700 ℃.
In the invention, the pre-carbonization time can be 2-7 h, such as 6 h.
In the present invention, the kind of the acid in the acid washing is preferably one or more of nitric acid, hydrochloric acid and hydrofluoric acid, and more preferably nitric acid, a mixed acid of hydrochloric acid and hydrofluoric acid, a mixed acid of nitric acid and hydrofluoric acid, a mixed acid of hydrochloric acid and hydrofluoric acid, or a mixed acid of nitric acid and hydrochloric acid.
Wherein, the concentration of each raw material acid in the mixed acid used for acid cleaning can be 3-7 mol/L, such as 5mol/L, 6mol/L or 7 mol/L.
In the present invention, the temperature of the acid washing may be 40 ± 5 ℃.
In a preferred embodiment, when the acid solution in the acid washing is a mixed acid of nitric acid, hydrochloric acid and hydrofluoric acid, the concentrations of the raw material acids are respectively: the concentration of the nitric acid is 7mol/L, the concentration of the hydrochloric acid is 6mol/L, and the concentration of the hydrofluoric acid is 5 mol/L.
In a preferred embodiment, when the acid solution in the acid washing is a mixed acid of nitric acid and hydrofluoric acid, the concentrations of the raw material acids are respectively: the concentration of the nitric acid is 7mol/L, and the concentration of the hydrofluoric acid is 5 mol/L.
In a preferred embodiment, when the acid solution in the acid cleaning is a mixed acid of hydrochloric acid and hydrofluoric acid, the concentrations of the raw material acids are respectively: the concentration of the hydrochloric acid is 6mol/L, and the concentration of the hydrofluoric acid is 5 mol/L.
In a preferred embodiment, when the acid solution in the acid washing is a mixed acid of nitric acid and hydrochloric acid, the concentrations of the raw material acids are respectively: the concentration of the nitric acid is 7mol/L, and the concentration of the hydrochloric acid is 6 mol/L.
In the invention, in the pickling process, the solid-to-liquid ratio can be 1: 3-2: 1, preferably 1: 1. The general definition of solid-to-liquid ratio refers to the ratio of the mass of the solid phase to the liquid phase in a suspension.
In the present invention, the pickling is generally completed by washing to neutrality and drying, as is conventional in the art.
Wherein, the washing is generally washed to be neutral by using clear water.
The temperature of drying may be conventional in the art, such as 80 ℃.
In the present invention, the pyrolysis atmosphere may be an atmosphere formed by a gas that does not chemically react with the system under the pre-carbonization condition, which is conventional in the art, such as a nitrogen atmosphere, or an atmosphere formed by an inert gas, which is conventional in the chemical art. The inert gas may be argon.
In the invention, the rate of heating to the pyrolysis temperature can be 1-3 ℃/min, for example 2 ℃/min.
In the invention, the pyrolysis temperature can be 1000-1300 ℃, such as 1000 ℃, 1100 ℃, 1200 ℃ or 1300 ℃.
In the invention, the pyrolysis time can be 2-6 h, such as 3h, 4h, 5h or 6 h.
In the present invention, the pyrolysis may be naturally cooled to room temperature.
In the present invention, the ball milling is generally carried out in a planetary ball mill.
In the invention, the ball milling time can be 20-60 min, such as 30 min.
In the invention, the rotation speed of the ball mill can be 100-300 rpm, such as 300rpm or 200 rpm.
In the ball milling process, the diameter of the adopted grinding ball can be 5-8 mm, and the grinding ball with the diameter of 8mm and the grinding ball with the diameter of 5mm are better. The mass ratio of the grinding ball with the diameter of 8mm to the grinding ball with the diameter of 5mm is preferably 1: 10.
the invention also provides the hard carbon material prepared by the preparation method of the hard carbon material.
In the invention, the hard carbon material can be black powder with uniform particle size, and the particle size range can be 6-15 μm.
In the present invention, the surface and the inside of the hard carbon material are mainly ultra-micro pores of about 0.53 nm.
The invention also provides an application of the hard carbon material in a sodium ion battery.
The invention also provides a negative pole piece which comprises the hard carbon material.
The invention also provides a sodium-ion battery which comprises the hard carbon material or the negative pole piece.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the hard carbon material has wide raw material source, simple preparation method and low cost, and can realize kilogram-level preparation;
(2) the hard carbon material prepared by the invention has low impurity content and uniform particle size, can be rich in sodium adsorption active sites on the surface and inside, and simultaneously prevents electrolyte from entering about 0.53nm ultramicropores;
(3) the hard carbon material has remarkable advantages in mass coating when the pole piece is prepared; when the sodium ion battery is prepared, the effects of higher specific capacity of sodium storage and good first coulombic efficiency can be realized.
Drawings
Fig. 1 is a scanning electron microscope picture of the hard carbon material prepared in example 1.
Fig. 2 is a pore size distribution diagram of the hard carbon material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The reagents or apparatus used in the following examples and comparative examples are all conventionally commercially available.
Example 1
(1) Pretreatment: putting the hazelnut shell into a plastic beaker, adding a proper amount of deionized water and ethanol (the material with the liquid surface being over the liquid surface is a proper amount), mechanically stirring for 2 hours at normal temperature, and repeating the operation for three times; then filtering, washing the filter cake with deionized water and ethanol, air-drying at 80 deg.C for 8h, and vacuum-drying at 110 deg.C for 12h to obtain dried hazelnut shell; pulverizing the cleaned and dried hazelnut shell by using a traditional Chinese medicine pulverizer.
(2) Pre-carbonization: and (3) placing the crushed hazelnut shells into a crucible, heating to 600 ℃ at a heating rate of 2 ℃/min in a well type furnace under the nitrogen atmosphere, and preserving heat for 6 hours to obtain the pre-carbonized carbon precursor.
(3) Acid washing: washing the pre-carbonized carbon precursor by using mixed acid of nitric acid, hydrochloric acid and hydrofluoric acid, wherein the concentrations of the raw material acids are respectively as follows: the concentration of nitric acid is 7mol/L, the concentration of hydrochloric acid is 6mol/L, the concentration of hydrofluoric acid is 5mol/L, and the solid-liquid ratio is 1: the effect is optimal, the pickling temperature is 40 +/-5 ℃, the acid is washed by clear water to be neutral, the washing temperature is 40 +/-5 ℃, and then the hard carbon precursor is obtained after drying at 80 ℃.
(4) Pyrolysis: and (3) heating the acid-washed hard carbon precursor to 1000 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 6h, and then cooling.
(5) Ball milling: further crushing the sample by using a planetary ball mill, wherein grinding balls adopted by the ball mill are 8 mm-diameter grinding balls and 5 mm-diameter grinding balls, and the mass ratio of the 8 mm-diameter grinding balls to the 5 mm-diameter grinding balls is 1: 10, the mass ratio of the grinding balls to the materials is 20: 1, the rotation speed of ball milling is 300rpm, and the ball milling time is 30min, so as to obtain the hard carbon material.
Example 2
(1) Pretreatment: putting the hazelnut shell into a plastic beaker, adding a proper amount of deionized water and ethanol (the material is a proper amount when the liquid surface of the hazelnut shell is submerged), mechanically stirring for 2 hours at normal temperature, and repeating the operation for three times; then filtering, washing the filter cake with deionized water and ethanol, air-drying at 80 deg.C for 8h, and vacuum-drying at 110 deg.C for 12h to obtain dried hazelnut shell; pulverizing the cleaned and dried hazelnut shell by using a traditional Chinese medicine pulverizer.
(2) Pre-carbonization: and (3) placing the crushed hazelnut shells into a crucible, heating to 400 ℃ at a heating rate of 2 ℃/min in a well type furnace under the nitrogen atmosphere, and preserving heat for 6 hours to obtain the pre-carbonized carbon precursor.
(3) Acid washing: washing the pre-carbonized carbon precursor by using mixed acid of nitric acid and hydrofluoric acid, wherein the concentrations of the raw material acids are respectively as follows: the concentration of nitric acid is 7mol/L, the concentration of hydrofluoric acid is 5mol/L, and the solid-liquid ratio is 1: the effect is optimal, the pickling temperature is 40 +/-5 ℃, the acid is washed by clear water to be neutral, the washing temperature is 40 +/-5 ℃, and then the hard carbon precursor is obtained after drying at 80 ℃.
(4) Pyrolysis: and (3) heating the acid-washed hard carbon precursor to 1300 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 4h, and then cooling.
(5) Ball milling: further crushing the sample by using a planetary ball mill, wherein grinding balls adopted by the ball mill are 8 mm-diameter grinding balls and 5 mm-diameter grinding balls, and the mass ratio of the 8 mm-diameter grinding balls to the 5 mm-diameter grinding balls is 1: 10, the mass ratio of the grinding balls to the materials is 20: 1, the rotation speed of ball milling is 300rpm, and the ball milling time is 30min, so as to obtain the hard carbon material.
Example 3
(1) Pretreatment: putting the hazelnut shell into a plastic beaker, adding a proper amount of deionized water and ethanol (the material is a proper amount when the liquid surface of the hazelnut shell is submerged), mechanically stirring for 2 hours at normal temperature, and repeating the operation for three times; then filtering, washing the filter cake with deionized water and ethanol, air-drying at 80 deg.C for 8h, and vacuum-drying at 110 deg.C for 12h to obtain dried hazelnut shell; pulverizing the cleaned and dried hazelnut shell by using a traditional Chinese medicine pulverizer.
(2) Pre-carbonization: and (3) placing the crushed hazelnut shells into a crucible, heating to 500 ℃ at a heating rate of 2 ℃/min in a well type furnace under the nitrogen atmosphere, and preserving heat for 6 hours to obtain the pre-carbonized carbon precursor.
(3) Acid washing: washing the pre-carbonized carbon precursor with mixed acid of hydrochloric acid and hydrofluoric acid, wherein the concentrations of the raw material acids are respectively as follows: the concentration of hydrochloric acid is 6mol/L, the concentration of hydrofluoric acid is 5mol/L, and the solid-liquid ratio is 1: the effect is optimal, the pickling temperature is 40 +/-5 ℃, the acid is washed by clear water to be neutral, the washing temperature is 40 +/-5 ℃, and then the hard carbon precursor is obtained after drying at 80 ℃.
(4) Pyrolysis: and (3) heating the acid-washed hard carbon precursor to 1100 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 5h, and then cooling.
(5) Ball milling: further crushing the sample by using a planetary ball mill, wherein grinding balls adopted by the ball mill are 8 mm-diameter grinding balls and 5 mm-diameter grinding balls, and the mass ratio of the 8 mm-diameter grinding balls to the 5 mm-diameter grinding balls is 1: 10, the mass ratio of the grinding balls to the materials is 20: 1, the rotation speed of ball milling is 300rpm, and the ball milling time is 30min, so as to obtain the hard carbon material.
Example 4
(1) Pretreatment: putting the hazelnut shell into a plastic beaker, adding a proper amount of deionized water and ethanol (the material is a proper amount when the liquid surface of the hazelnut shell is submerged), mechanically stirring for 2 hours at normal temperature, and repeating the operation for three times; then filtering, washing the filter cake with deionized water and ethanol, air-drying at 80 deg.C for 8h, and vacuum-drying at 110 deg.C for 12h to obtain dried hazelnut shell; pulverizing the cleaned and dried hazelnut shell by using a traditional Chinese medicine pulverizer.
(2) Pre-carbonization: and (3) placing the crushed hazelnut shells into a crucible, heating to 700 ℃ at a heating rate of 2 ℃/min in a well type furnace under the nitrogen atmosphere, and preserving heat for 6 hours to obtain the pre-carbonized carbon precursor.
(3) Acid washing: washing the pre-carbonized carbon precursor by using mixed acid of nitric acid and hydrochloric acid, wherein the concentrations of the raw material acids are respectively as follows: the concentration of nitric acid is 7mol/L, the concentration of hydrochloric acid is 6mol/L, and the solid-liquid ratio is 1: the effect is optimal, the pickling temperature is 40 +/-5 ℃, the acid is washed by clear water to be neutral, the washing temperature is 40 +/-5 ℃, and then the hard carbon precursor is obtained after drying at 80 ℃.
(4) Pyrolysis: and (3) heating the acid-washed hard carbon precursor to 1200 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 3h, and then cooling.
(5) Ball milling: further crushing the sample by using a planetary ball mill, wherein grinding balls adopted by the ball mill are 8 mm-diameter grinding balls and 5 mm-diameter grinding balls, and the mass ratio of the 8 mm-diameter grinding balls to the 5 mm-diameter grinding balls is 1: 10, the mass ratio of the grinding balls to the materials is 20: 1, the rotation speed of ball milling is 300rpm, and the ball milling time is 30min, so as to obtain the hard carbon material.
Comparative example 1
(1) Pretreatment: putting the hazelnut shell into a plastic beaker, adding a proper amount of deionized water and ethanol (the material is a proper amount when the liquid surface of the hazelnut shell is submerged), mechanically stirring for 2 hours at normal temperature, and repeating the operation for three times; then filtering, washing the filter cake with deionized water and ethanol, air-drying at 80 deg.C for 8h, and vacuum-drying at 110 deg.C for 12h to obtain dried hazelnut shell; pulverizing the cleaned and dried hazelnut shell by using a traditional Chinese medicine pulverizer.
(2) Pre-carbonization: and (3) placing the crushed hazelnut shells into a crucible, heating to 600 ℃ at a heating rate of 2 ℃/min in a well type furnace under the nitrogen atmosphere, and preserving heat for 6 hours to obtain the pre-carbonized carbon precursor.
(3) Acid washing: washing the pre-carbonized carbon precursor by using mixed acid of nitric acid, hydrochloric acid and hydrofluoric acid, wherein the concentrations of the raw material acids are respectively as follows: the concentration of nitric acid is 7mol/L, the concentration of hydrochloric acid is 6mol/L, the concentration of hydrofluoric acid is 5mol/L, and the solid-liquid ratio is 1: the effect is optimal, the pickling temperature is 40 +/-5 ℃, the acid is washed by clear water to be neutral, the washing temperature is 40 +/-5 ℃, and then the hard carbon precursor is obtained after drying at 80 ℃.
(4) Pyrolysis: and (3) heating the acid-washed hard carbon precursor to 1000 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 6h, and then cooling.
(5) Ball milling: and (3) further crushing the sample by using a planetary ball mill, wherein grinding balls adopted by the ball mill are 8 mm-diameter grinding balls and 5 mm-diameter grinding balls, and the mass ratio of the 8 mm-diameter grinding balls to the 5 mm-diameter grinding balls is 1: 10, the mass ratio of the grinding balls to the materials is 10: 1, the rotation speed of ball milling is 200rpm, and the ball milling time is 30min, so as to obtain the hard carbon material.
Comparative example 2
(1) Pretreatment: putting the hazelnut shell into a plastic beaker, adding a proper amount of deionized water and ethanol (the material is a proper amount when the liquid surface of the hazelnut shell is submerged), mechanically stirring for 2 hours at normal temperature, and repeating the operation for three times; then filtering, washing the filter cake with deionized water and ethanol, air-drying at 80 deg.C for 8h, and vacuum-drying at 110 deg.C for 12h to obtain dried hazelnut shell; pulverizing the cleaned and dried hazelnut shell by using a traditional Chinese medicine pulverizer.
(2) Pre-carbonization: and (3) placing the crushed hazelnut shells into a crucible, heating to 600 ℃ at a heating rate of 2 ℃/min in a well type furnace under the nitrogen atmosphere, and preserving heat for 6 hours to obtain the pre-carbonized carbon precursor.
(3) Acid washing: washing the pre-carbonized carbon precursor by using mixed acid of nitric acid, hydrochloric acid and hydrofluoric acid, wherein the concentrations of the raw material acids are respectively as follows: the concentration of nitric acid is 1mol/L, the concentration of hydrochloric acid is 1mol/L, the concentration of hydrofluoric acid is 1mol/L, and the solid-liquid ratio is 1: the effect is optimal, the pickling temperature is 40 +/-5 ℃, the acid is washed by clear water to be neutral, the washing temperature is 40 +/-5 ℃, and then the hard carbon precursor is obtained after drying at 80 ℃.
(4) Pyrolysis: and (3) heating the acid-washed hard carbon precursor to 1000 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 6h, and then cooling.
(5) Ball milling: further crushing the sample using a planetary ball mill; the grinding ball that the ball-milling adopted is that the diameter is 8 mm's grinding ball and diameter are 5 mm's grinding ball, and the quality ratio of diameter is 1 for 8 mm's grinding ball and diameter is 5 mm's grinding ball: 10, the mass ratio of the grinding balls to the materials is 20: 1, the rotation speed of ball milling is 200rpm, and the ball milling time is 30min, so as to obtain the hard carbon material.
Effect example 1
1、SEM
An SEM picture of the hard carbon material prepared in example 1 of the present invention is shown in fig. 1. It can be seen from fig. 1 that the hard carbon particles are uniform in size, range in size from 6 to 15 μm, and are in the form of irregular blocks.
2、BET
The pore size distribution diagram of the hard carbon material prepared in example 1 of the present invention is shown in fig. 2. As can be seen from the figure, the surface and the interior of the hard carbon material particles are mainly ultra-micropores with the size of about 0.53nm, the ultra-micropores with the size are rich in sodium adsorption sites, and the electrolyte is prevented from entering, so that the sodium storage specific capacity and the first cycle efficiency of the material are improved.
Claims (10)
1. A preparation method of a hard carbon material is characterized by comprising the following steps:
pre-carbonizing, acid-washing, pyrolyzing and ball-milling the carbon precursor;
wherein the raw material of the carbon precursor is hazelnut shell; the concentration of each raw material acid in the mixed acid used for pickling is 2-7 mol/L; in the ball milling process, the mass ratio of the adopted milling balls to the materials is 15: 1-25: 1.
2. the method for preparing a hard carbon material according to claim 1, wherein in the ball milling process, the mass ratio of the adopted grinding balls to the materials is 20: 1-25: 1.
3. the method of preparing a hard carbon material according to claim 1, wherein the hazelnut shell is one or more of hazelnut, hazel, spiny hazel and hazel;
and/or the preparation method of the carbon precursor comprises the steps of washing, drying and crushing the hazelnut shell in sequence.
4. The method for preparing a hard carbon material according to claim 1, wherein the rate of heating up to the pre-carbonization temperature is 2 to 3 ℃/min, such as 2 ℃/min;
and/or the pre-carbonization temperature is 400-700 ℃, such as 400 ℃, 500 ℃, 600 ℃ or 700 ℃;
and/or the pre-carbonization time is 2-7 h, such as 6 h.
5. The method for producing a hard carbon material according to claim 1, wherein the kind of acid in the acid washing is one or more of nitric acid, hydrochloric acid and hydrofluoric acid, preferably nitric acid, a mixed acid of hydrochloric acid and hydrofluoric acid, a mixed acid of nitric acid and hydrofluoric acid, a mixed acid of hydrochloric acid and hydrofluoric acid, or a mixed acid of nitric acid and hydrochloric acid;
preferably, the temperature of the acid washing is 40 +/-5 ℃;
preferably, in the acid washing process, the solid-to-liquid ratio is 1: 3-2: 1, more preferably 1: 1;
preferably, the concentration of each raw material acid in the mixed acid used for acid washing is 3-7 mol/L, such as 5mol/L, 6mol/L or 7 mol/L;
when the acid solution in the acid cleaning is a mixed acid of nitric acid, hydrochloric acid and hydrofluoric acid, the concentrations of the raw material acids are respectively as follows: the concentration of the nitric acid is 7mol/L, the concentration of the hydrochloric acid is 6mol/L, and the concentration of the hydrofluoric acid is 5 mol/L;
when the acid solution in the acid cleaning is a mixed acid of nitric acid and hydrofluoric acid, the concentrations of the raw material acids are respectively as follows: the concentration of the nitric acid is 7mol/L, and the concentration of the hydrofluoric acid is 5 mol/L;
when the acid solution in the acid cleaning is a mixed acid of hydrochloric acid and hydrofluoric acid, the concentrations of the raw material acids are respectively as follows: the concentration of the hydrochloric acid is 6mol/L, and the concentration of the hydrofluoric acid is 5 mol/L;
when the acid solution in the acid washing is a mixed acid of nitric acid and hydrochloric acid, the concentrations of the raw material acids are respectively as follows: the concentration of the nitric acid is 7mol/L, and the concentration of the hydrochloric acid is 6 mol/L.
6. The method for preparing a hard carbon material according to claim 1, wherein the rate of heating to the pyrolysis temperature is 1 to 3 ℃/min, such as 2 ℃/min;
and/or the pyrolysis temperature is 1000-1300 ℃, such as 1000 ℃, 1100 ℃, 1200 ℃ or 1300 ℃;
and/or the pyrolysis time is 2-6 h, such as 3h, 4h, 5h or 6 h.
7. The method for preparing a hard carbon material according to claim 1, wherein the ball milling time is 20 to 60min, such as 30 min;
and/or the rotation speed of the ball mill is 100-300 rpm, such as 300rpm or 200 rpm;
and/or in the ball milling process, the adopted grinding balls have the diameter of 5-8 mm, preferably the grinding balls with the diameter of 8mm and the grinding balls with the diameter of 5 mm; the mass ratio of the grinding ball with the diameter of 8mm to the grinding ball with the diameter of 5mm is preferably 1: 10.
8. a hard carbon material produced by the method for producing a hard carbon material according to any one of claims 1 to 7;
the particle size of the hard carbon material is preferably 6 to 15 μm.
9. Use of the hard carbon material of claim 8 in a sodium ion battery.
10. A sodium ion battery comprising the hard carbon material of claim 8.
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