CN107579249B - Hard carbon negative electrode material prepared from traditional Chinese medicine residues and preparation method thereof - Google Patents
Hard carbon negative electrode material prepared from traditional Chinese medicine residues and preparation method thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues, which comprises the following steps: A) soaking the Chinese medicine residues by adopting an acid solution to obtain soaked Chinese medicine residues; B) carrying out heat treatment on the soaked traditional Chinese medicine residues under the protection of inert gas to obtain a hard carbon precursor; the heat treatment temperature is 200-700 ℃; the heat treatment time is 0.5-5 h; C) carbonizing the hard carbon precursor under the protection of inert gas to obtain a carbonaceous material; the carbonization temperature is 1000-1600 ℃; the carbonization time is 1-10 h; D) and (3) modifying, ball-milling and grading the carbonaceous material to obtain the hard carbon negative electrode material. The invention adopts the waste traditional Chinese medicine residues as raw materials to prepare the hard carbon material, and has low cost and wide source; meanwhile, the invention adopts acid treatment, specific heat treatment and carbonization parameters, and combines modification treatment, so that the loss of lithium ions can be reduced, and the finally prepared hard carbon material has high first coulombic efficiency and high discharge capacity.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a hard carbon cathode material prepared from traditional Chinese medicine residues and a preparation method thereof.
Background
With the increasingly prominent problem of living environment, people have an increasing demand for electric vehicles and hybrid electric vehicles, and the development of lithium ion battery electrode materials with high energy density, good load characteristics, fast charge and discharge, high safety performance, long cycle life and low cost becomes an international research hotspot. The negative electrode material is used as an important electrode material, the most widely used is graphite or a graphite modified material, although the graphite or the graphite modified material has good conductivity, high crystallinity and a good charging and discharging platform, due to the layered structure of the graphite and poor intermiscibility with an organic solvent, the co-intercalation of solvent ions is easy to occur in the charging and discharging process of a lithium ion battery to cause structural damage, so that the cycle stability and the coulombic efficiency of the graphite negative electrode material are influenced, particularly the rate capability of the graphite negative electrode material is reduced, and the application of the graphite negative electrode material to a power battery is limited to a certain extent.
The soft carbon is usually modified to be used as a lithium ion battery cathode material due to low output voltage and no obvious charge and discharge platform; the hard carbon is generally formed by high-temperature cracking of high-molecular polymer or biomass, has the advantages of high specific capacity, good rate capability and excellent cycle performance compared with graphite cathode materials, has good intermiscibility with propylene carbonate PC electrolyte, and is more suitable for being applied to power batteries.
At present, raw materials for producing hard carbon mainly comprise thermoplastic resin, thermosetting resin, asphalt and the like, the cost is high, the process is complex, organic matters from plants such as coffee grounds, coconut shells, straws, rice husks and the like are also patented, but the prepared negative electrode material still has the disadvantages of low coulombic efficiency and low discharge capacity for the first time.
China is a big country for producing and using traditional Chinese medicines, the discharge amount of only plant medicine residues in each year in China is up to 65 million tons according to statistics, and the medicine residues are mostly stacked, buried and incinerated, so that the treatment cost is high, and the resource waste and the environmental pollution are caused. Therefore, it is urgent to find a method for preparing hard carbon material from herb residue.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues, and the method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues provided by the present invention not only can utilize wastes, but also has high first coulombic efficiency and high discharge capacity.
The invention provides a method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues, which comprises the following steps:
A) soaking the Chinese medicine residues by adopting an acid solution to obtain soaked Chinese medicine residues;
B) carrying out heat treatment on the soaked traditional Chinese medicine residues under the protection of inert gas to obtain a hard carbon precursor; the heat treatment temperature is 200-700 ℃; the heat treatment time is 0.5-5 h;
C) carbonizing the hard carbon precursor under the protection of inert gas to obtain a carbonaceous material; the carbonization temperature is 1000-1600 ℃; the carbonization time is 1-10 h;
D) and (3) modifying, ball-milling and grading the carbonaceous material to obtain the hard carbon negative electrode material.
Preferably, the acid solution of step a) is a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is 2-5 mol/L; the volume of the acid solution and the mass of the traditional Chinese medicine residues are 0.5-2L: 90-110 g.
Preferably, the soaking temperature in the step A) is 20-60 ℃; the soaking time is 1-3 h; stirring while soaking; the stirring speed is 100-400 rpm.
Preferably, the heat treatment temperature in the step B) is 250-500 ℃; the heat treatment time is 1-3 h; the flow rate of the inert gas is 5-30 ml/min.
Preferably, the carbonization temperature in the step C) is 1050-1500 ℃; the carbonization time is 1.5-8 h; the flow rate of the inert gas is 5-30 ml/min.
Preferably, the carbonization step C) further comprises pre-carbonization before carbonization, wherein the pre-carbonization temperature is 300-900 ℃; the pre-carbonization time is 0.5-5 h.
Preferably, the modification treatment in the step D) is specifically: soaking a carbonaceous material in an organic matter aqueous solution containing acidic groups, washing to be neutral, filtering and drying; the soaking time is 0.5 to 2 hours, the concentration of the acidic organic matter is preferably 1 to 5mol/L, and the structural formula of the organic matter containing acidic groups is R-COOH or R-SO3H, wherein R is a hydrocarbyl group.
Preferably, the ball milling in the step D) is water ball milling; the mass ratio of the water to the carbonaceous material is 1-5: 1; the mass ratio of the grinding balls to the carbonaceous material is 5-30: 1; the grinding balls are selected from one or more of zirconia balls, stainless steel balls and alumina ceramic balls; the grinding speed is 200-1000 rpm.
The invention provides a hard carbon cathode material which is prepared by the preparation method of the technical scheme.
The invention provides a preparation method of a battery, and the cathode material is prepared by the preparation method of the technical scheme.
Compared with the prior art, the invention provides a method for preparing a hard carbon anode material from traditional Chinese medicine residues, which comprises the following steps: A) soaking the Chinese medicine residues by adopting an acid solution to obtain soaked Chinese medicine residues; B) carrying out heat treatment on the soaked traditional Chinese medicine residues under the protection of inert gas to obtain a hard carbon precursor; the heat treatment temperature is 200-700 ℃; the heat treatment time is 0.5-5 h; C) carbonizing the hard carbon precursor under the protection of inert gas to obtain a carbonaceous material; the carbonization temperature is 1000-1600 ℃; the carbonization time is 1-10 h; D) and (3) modifying, ball-milling and grading the carbonaceous material to obtain the hard carbon negative electrode material. The invention adopts the waste traditional Chinese medicine residues as raw materials to prepare the hard carbon material, and has low cost and wide source; meanwhile, the invention adopts acid treatment, specific heat treatment and carbonization parameters, and combines modification treatment, so that the loss of lithium ions can be reduced, and the finally prepared hard carbon material has high first coulombic efficiency and high discharge capacity.
Detailed Description
The invention provides a method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues, which comprises the following steps:
A) soaking the Chinese medicine residues by adopting an acid solution to obtain soaked Chinese medicine residues;
B) carrying out heat treatment on the soaked traditional Chinese medicine residues under the protection of inert gas to obtain a hard carbon precursor; the heat treatment temperature is 200-700 ℃; the heat treatment time is 0.5-5 h;
C) carbonizing the hard carbon precursor under the protection of inert gas to obtain a carbonaceous material; the carbonization temperature is 1000-1600 ℃; the carbonization time is 1-10 h;
D) and (3) modifying, ball-milling and grading the carbonaceous material to obtain the hard carbon negative electrode material.
The method for preparing the hard carbon cathode material by using the traditional Chinese medicine residues adopts the traditional Chinese medicine residues, namely the traditional Chinese medicine residues.
The invention does not limit the traditional Chinese medicine residues, and the traditional Chinese medicine residues are preferably rhizomes, fruit shells and flower leaves; more preferably, the herb residue is rhizome or fruit shell type herb residue.
The invention firstly pretreats the traditional Chinese medicine dregs to remove impurities in the traditional Chinese medicine dregs.
The pretreatment is preferably as follows: soaking the residue in water; preferably deionized water. The mass ratio of the traditional Chinese medicine residues to the water is preferably 1: 5-15; more preferably 1: 6-13; most preferably 1: 8-12; the soaking temperature is preferably 20-60 ℃; more preferably 30-60 ℃; the soaking time is preferably 2-6 h; more preferably 3 to 5 hours.
The invention can remove impurities which are easy to dissolve in water through pretreatment, and improves the preparation efficiency.
Filtering after soaking; drying and crushing filter residues after filtering; the present invention is not limited to the specific operations of drying and pulverizing, and those skilled in the art are familiar with the present invention.
After pretreatment, soaking the traditional Chinese medicine residues by adopting an acid solution to obtain soaked traditional Chinese medicine residues.
The acid solution is preferably a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is preferably 2-5 mol/L; more preferably 3-5 mol/L; the volume of the acid solution and the mass of the traditional Chinese medicine residues are preferably 0.5-2L: 90-110 g; more preferably 0.5-2L: 100g of the total weight of the mixture; the soaking temperature is preferably 20-60 ℃; more preferably 30 to 60 ℃; the soaking time is preferably 1-3 h; more preferably 1.5 to 3 hours.
Stirring while soaking; the stirring speed is preferably 100-400 rpm; more preferably 200 to 400 rpm.
The present invention is not limited to the specific operation of soaking and stirring with the acid solution, and those skilled in the art can easily understand this.
Filtering after soaking, collecting the Chinese medicine residue, and drying; the drying is preferably vacuum drying; the drying time is preferably 8-12 h; more preferably 10 to 12 hours.
And (4) after drying, carrying out heat treatment on the traditional Chinese medicine residues under the protection of inert gas to obtain a hard carbon precursor.
After crushing, heat treatment is carried out under the protection of inert gas; the inert gas is not limited in the present invention, and preferably may be one or more of nitrogen, argon and helium. The flow rate of the inert gas is preferably 5-30 ml/min; more preferably 10 to 30 ml/min.
The control of the flow of the inert gas is also critical, the excessive gas flow easily brings out the heat-treated or carbonized materials and volatile matters to cause waste, and the excessive gas flow hardly brings out the volatile components from the carbonization furnace to cause the condensation of the volatile components on the inner wall of the furnace and pipelines to cause blockage.
The heat treatment according to the invention is preferably carried out in a carbonization furnace.
The heat treatment temperature is 200-700 ℃; preferably 250 to 500 ℃; the heat treatment time is 0.5-5 h; preferably 1 to 3 hours.
The heat treatment process of the invention is mainly to remove volatile components such as CO2、CO、CH4、H2And tar components are removed to reduce the burden on carbonization equipment, and if the temperature is too low, tar removal cannot be completed, and tar components and gases generated in the carbonization step may adhere to the particle surface, and the surface properties during pulverization cannot be maintained, resulting in a decrease in battery performance. When the heat treatment temperature is too high, the tar produced causes secondary decomposition reaction, and the product adheres to the particle surface, resulting in deterioration of the properties.
After the heat treatment, preferably cooling to obtain a hard carbon precursor; the specific way of cooling is not limited in the present invention, and those skilled in the art are familiar with the cooling; the temperature after the temperature reduction is preferably room temperature.
And after cooling, carbonizing the hard carbon precursor under the protection of inert gas to obtain the carbonaceous material.
The method also comprises pre-carbonization before carbonization, wherein the pre-carbonization temperature is preferably 300-900 ℃; more preferably 350-900 ℃; most preferably 400-850 ℃; the pre-carbonization time is preferably 0.5-5 h; more preferably 1-5 h; most preferably 1-4 h.
Inert gas is introduced during the pre-carbonization and carbonization; the flow rate of the inert gas is preferably 5-30 ml/min; more preferably 10-25 ml/min; most preferably 10-20 ml/min; the inert gas is not limited in the present invention, and preferably may be one or more of nitrogen, argon and helium.
After pre-carbonization, continuously heating and carbonizing; the carbonization temperature is preferably 1000-1600 ℃; more preferably 1050-1600 ℃; most preferably 1050-1500 ℃; the carbonization time is preferably 1-10 h; more preferably 1.5-9 h; most preferably 1.5 to 8 hours.
The pre-carbonization and carbonization according to the invention are preferably carried out in a carbonization furnace.
And carbonizing to obtain the carbonaceous material.
And (3) modifying, ball-milling and grading the carbonaceous material to obtain the hard carbon negative electrode material.
The carbonaceous material modification treatment is preferably embodied as follows: soaking carbonaceous material in aqueous solution of organic matter containing acidic group, washing to neutrality, filtering and drying.
According to the invention, the soaking time is preferably 0.5 h-2 h, more preferably 1 h-2 h, the concentration of the acidic organic substance is preferably 1 mol/L-5 mol/L, more preferably 2 mol/L-5 mol/L, and the structural formula of the organic substance containing acidic groups is R-COOH or R-SO3H, wherein R is preferably a hydrocarbyl group; more preferably formic acid, acetic acid, propionic acid, citric acid, methanesulfonic acid; most preferred are formic acid, acetic acid, methanesulfonic acid.
According to the invention, the carbonized hard carbon is modified by organic acid and the pH value of the carbonized hard carbon is controlled to be neutral, so that the loss of lithium ions is effectively reduced and the first efficiency is improved.
Ball milling is carried out after modification treatment; the ball milling is preferably wet ball milling, and more preferably ball milling by using water as a solvent; the mass ratio of the water to the carbonaceous material is preferably 1-5: 1; more preferably 2 to 5: 1; the mass ratio of the grinding balls to the carbonaceous material is preferably 5-30: 1; more preferably 10 to 25: 1; the grinding balls are preferably selected from one or more of zirconia balls, stainless steel balls and alumina ceramic balls; the grinding rotating speed is preferably 200-1000 rpm; more preferably 300 to 1000 rpm; most preferably 500 to 1000 rpm.
And performing ball milling and grading to obtain the hard carbon cathode material.
The classification is not limited in the present invention, and the classification preferably includes screen classification, wet classification, or dry classification.
The invention provides a method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues, which comprises the following steps: A) soaking the Chinese medicine residues by adopting an acid solution to obtain soaked Chinese medicine residues; B) crushing the soaked traditional Chinese medicine residues, and carrying out heat treatment under the protection of inert gas to obtain a hard carbon precursor; the heat treatment temperature is 200-700 ℃; the heat treatment time is 0.5-5 h; C) carbonizing the hard carbon precursor under the protection of inert gas to obtain a carbonaceous material; the carbonization temperature is 1000-1600 ℃; the carbonization time is 1-10 h; D) and (3) modifying, ball-milling and grading the carbonaceous material to obtain the hard carbon negative electrode material. The invention adopts the waste traditional Chinese medicine residues as raw materials to prepare the hard carbon material, and has low cost and wide source; meanwhile, the invention adopts acid treatment, specific heat treatment and carbonization parameters, and combines modification treatment, so that the loss of lithium ions can be reduced, and the finally prepared hard carbon material has high first coulombic efficiency and high discharge capacity. Experimental results show that the first coulombic efficiency of the hard carbon material reaches more than 81%, the discharge capacity is higher than 500mAh/g, and the hard carbon material is suitable for power and energy storage batteries; the preparation method is simple in preparation process, convenient to operate and suitable for industrial production.
The invention provides a hard carbon cathode material which is prepared by the preparation method of the technical scheme.
The preparation method of the hard carbon anode material of the present invention has been described clearly above, and is not repeated herein.
The invention provides a preparation method of a battery, and the cathode material is prepared by the preparation method of the technical scheme.
The remaining components of the battery are not limited in the present invention and may be known to those skilled in the art.
The cell used for the assay of the invention was as follows:
mixing the prepared hard carbon negative electrode material, a binder (PVDF) and acetylene black according to a ratio of 90: 10: 5 (mass ratio) in N-methyl pyrrolidone, coating the obtained slurry on copper foil, drying and rolling to obtain the pole piece. Taking a metal lithium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and 1mol/L of LiP6+ EC: and (3) assembling a simulation battery by using DEC (decamethylene dichloride)/DM C (volume ratio of 1: 1: 1) as an electrolyte.
In order to further illustrate the present invention, the method for preparing a hard carbon negative electrode material from herb residue provided in the present invention is described in detail below with reference to examples.
Example 1
Mixing rhizome traditional Chinese medicine residues with deionized water according to a mass ratio of 1:10, soaking at 30 ℃ for 4h, removing impurities in the residues, filtering, drying and crushing the filter residues, soaking the traditional Chinese medicine residues in a hydrochloric acid solution of 3mol/L at a soaking ratio of 1.5L/100g for 2h at a soaking temperature of 40 ℃ and a stirring rotation speed of 250rpm, filtering and collecting the traditional Chinese medicine residues, vacuum-drying for 10h, loading the traditional Chinese medicine residues into a carbonization furnace, heating to 500 ℃ under the protection of nitrogen for heat treatment for 3h with a nitrogen flow of 15ml/min, cooling to room temperature to obtain a hard carbon precursor, pre-carbonizing the precursor at 600 ℃ for 3h, introducing nitrogen at a flow of 12ml/min, continuously heating to 1300 ℃, keeping the temperature for 5h for carbonization to obtain a carbonaceous material, soaking the carbonaceous material in a formic acid solution of 3mol/L for 1.3h, washing with water to neutrality, filtering, drying, and then grinding the hard carbon material by liquid phase ball milling, wherein the mass ratio of water to the carbon material is 3:1, the ball-to-material ratio is 25:1, and zirconium oxide is used as grinding balls and the rotating speed is 600 rpm. And drying the ball-milled materials, and grading to obtain the hard carbon material.
Mixing the prepared hard carbon negative electrode material, a binder (PVDF) and acetylene black according to a ratio of 90: 10: 5 (mass ratio) in N-methyl pyrrolidone, coating the obtained slurry on copper foil, drying and rolling to obtain the pole piece. Taking a metal lithium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and 1mol/L of LiP6+ EC: and (3) assembling a simulation battery by using DEC (decamethylene dichloride)/DM C (volume ratio of 1: 1: 1) as an electrolyte. Constant current charge and discharge performance test is carried out on a Land CT2100 charge and discharge instrument, the charge and discharge rate is 0.1C, and the voltage range is 0.001-1.0V. The electrochemical performance results are shown in table 1.
Example 2
Mixing shell type Chinese medicine residues with deionized water according to a mass ratio of 1:5, soaking for 2h at 60 ℃, removing impurities in the shell type Chinese medicine residues, drying and crushing the filter residues after filtering, soaking the Chinese medicine residues by adopting a hydrochloric acid solution of 2mol/L, wherein the soaking ratio of the hydrochloric acid solution to the Chinese medicine residues is 2L/100g, soaking for 3h, the soaking temperature is 60 ℃, the stirring speed is 100rpm, filtering and collecting the Chinese medicine residues, vacuum drying for 10h, putting the Chinese medicine residues into a carbonization furnace, heating to 200 ℃ under the protection of nitrogen for heat treatment for 5h, the nitrogen flow is set to 5ml/min, cooling to room temperature to obtain a hard carbon precursor, pre-carbonizing the precursor at 350 ℃ for 5h, introducing nitrogen with the flow of 20ml/min, continuously heating to 1600 ℃, keeping the temperature for 1h for carbonization to obtain a carbonaceous material, soaking the carbonaceous material in an acetic acid solution of 1mol/L for 2h, washing with water to neutrality, filtering, drying, and then grinding the hard carbon material by liquid phase ball milling, wherein the mass ratio of water to the carbon material is 1:1, the ball-to-material ratio is 30:1, and stainless steel balls are selected as grinding balls and rotate at the speed of 200 rpm. And drying the ball-milled materials, and grading to obtain the hard carbon material.
The battery was fabricated in the same manner as in example 1.
Example 3
Mixing fruit shell type medicine residues with deionized water according to a mass ratio of 1:15, soaking at 20 ℃ for 6h, removing impurities in the fruit shell type medicine residues, filtering, drying and crushing the filter residues, soaking the traditional Chinese medicine residues in a hydrochloric acid solution of 5mol/L at a soaking ratio of 0.5L/100g, soaking for 1h at a soaking temperature of 20 ℃, stirring at a rotating speed of 400rpm, filtering, collecting the traditional Chinese medicine residues, vacuum drying for 10h, putting the traditional Chinese medicine residues into a carbonization furnace, heating to 250 ℃ under the protection of nitrogen for heat treatment for 4h, setting the nitrogen flow to 10ml/min, cooling to room temperature to obtain a hard carbon precursor, pre-carbonizing the precursor at 900 ℃ for 0.5h, introducing nitrogen at a flow of 20ml/min, continuously heating to 1050 ℃, keeping the temperature for 8h for carbonization to obtain a carbonaceous material, soaking the carbonaceous material in an acetic acid solution of 5mol/L for 0.5h, washing with water to neutrality, filtering, drying, and then grinding the hard carbon material by liquid phase ball milling, wherein the mass ratio of water to the carbon material is 5:1, the ball-to-material ratio is 5:1, and zirconium oxide is selected as grinding balls and the rotating speed is 1000 rpm. And drying the ball-milled materials, and grading to obtain the hard carbon material.
The battery was fabricated in the same manner as in example 1.
Example 4
Mixing shell type Chinese medicine residues with deionized water according to a mass ratio of 1:10, soaking at 50 ℃ for 1.5h, removing impurities in the shell type Chinese medicine residues, filtering, drying and crushing the filter residues, soaking the Chinese medicine residues by adopting 4mol/L hydrochloric acid solution, wherein the soaking ratio of the hydrochloric acid solution to the Chinese medicine residues is 1L/100g, soaking for 1.5h, the soaking temperature is 30 ℃, the stirring speed is 300rpm, filtering and collecting the Chinese medicine residues, vacuum drying for 10h, putting the Chinese medicine residues into a carbonization furnace, heating to 700 ℃ under the protection of nitrogen, carrying out heat treatment for 1h, setting the nitrogen flow to be 30ml/min, cooling to room temperature to obtain a hard carbon precursor, pre-carbonizing the precursor at 800 ℃ for 1h, introducing nitrogen into the carbonization furnace at the flow of 15ml/min, continuously heating to 1500 ℃, keeping the temperature for 1.5h for carbonization to obtain a carbonaceous material, soaking the carbonaceous material in 4mol/L methanesulfonic acid solution for 1, and then washing the hard carbon material with water to be neutral, filtering and drying the hard carbon material, and then crushing the hard carbon material by utilizing liquid phase ball milling, wherein the mass ratio of water to the carbon material is 2:1, the ball material ratio is 10:1, corundum is selected as a grinding ball, and the rotating speed is 800 rpm. And drying the ball-milled materials, and grading to obtain the hard carbon material.
The battery was fabricated in the same manner as in example 1.
Comparative example 1
Mixing rhizome traditional Chinese medicine residues with deionized water according to a mass ratio of 1:10, soaking at 30 ℃ for 4h to remove impurities in the residues, filtering, drying and crushing the filter residues, soaking the traditional Chinese medicine residues with 1mol/L hydrochloric acid solution at a soaking ratio of 3L/100g, soaking for 0.5h at a soaking temperature of 10 ℃, stirring at a rotating speed of 100rpm, filtering and collecting the traditional Chinese medicine residues, vacuum drying for 10h, loading the traditional Chinese medicine residues into a carbonization furnace, heating to 150 ℃ under the protection of nitrogen, performing heat treatment for 7h with a nitrogen flow of 3ml/min, cooling to room temperature to obtain a hard carbon precursor, pre-carbonizing the precursor at 200 ℃ for 6h, introducing nitrogen at a flow of 3ml/min, continuously heating to 800 ℃, maintaining for 0.5h to perform carbonization to obtain a carbonaceous material, soaking the carbonaceous material in 0.5mol/L formic acid solution for 1h, filtering and drying, and then, grinding the hard carbon material by liquid phase ball milling, wherein the mass ratio of water to the carbonaceous material is 3:1, the ball-to-material ratio is 3:1, and zirconium oxide is selected as grinding balls and rotates at the speed of 100 rpm. And drying the ball-milled materials, and grading to obtain the hard carbon material.
The battery was fabricated in the same manner as in example 1.
Comparative example 2
The raw material was replaced with coffee grounds for pretreatment, and the preparation method was the same as example 1.
Comparative example 3
Mixing rhizome traditional Chinese medicine residues with deionized water according to a mass ratio of 1:10, soaking at 30 ℃ for 4h, removing impurities in the residues, filtering, drying and crushing filter residues, soaking the traditional Chinese medicine residues with 3mol/L hydrochloric acid solution at a soaking ratio of 1.5L/100g, soaking for 2h at a soaking temperature of 40 ℃, stirring at a rotating speed of 250rpm, filtering and collecting the traditional Chinese medicine residues, vacuum drying for 10h, loading the traditional Chinese medicine residues into a carbonization furnace, heating to 500 ℃ under the protection of nitrogen, performing heat treatment for 3h with a nitrogen flow of 15ml/min, cooling to room temperature to obtain a hard carbon precursor, pre-carbonizing the precursor at 600 ℃ for 3h, introducing nitrogen at a flow of 12ml/min, continuously heating to 1300 ℃, maintaining for 5h for carbonization to obtain a hard carbonaceous material, grinding the hard carbon material by liquid phase ball milling, wherein the mass ratio of water to the carbonaceous material is 3:1, the ball-to-material ratio is 25:1, zirconium oxide is selected as grinding balls, and the rotating speed is 600 rpm. And drying the ball-milled materials, and grading to obtain the hard carbon material.
The battery was fabricated in the same manner as in example 1.
TABLE 1 electrochemical Performance test results
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for preparing a hard carbon negative electrode material from traditional Chinese medicine residues is characterized by comprising the following steps:
A) soaking the Chinese medicine residues by adopting an acid solution to obtain soaked Chinese medicine residues; the acid solution is a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is 2-5 mol/L; the volume of the acid solution and the mass of the traditional Chinese medicine residues are 0.5-2L: 90-110 g; the Chinese medicinal residue is residue of rhizomes, fruit shells and leaves; the soaking temperature is 20-60 ℃; the soaking time is 1-3 h; stirring while soaking; the stirring speed is 100-400 rpm;
B) carrying out heat treatment on the soaked traditional Chinese medicine residues under the protection of inert gas to obtain a hard carbon precursor; the heat treatment temperature is 200-700 ℃; the heat treatment time is 0.5-5 h; the flow rate of the inert gas is 5-30 ml/min;
C) carbonizing the hard carbon precursor under the protection of inert gas to obtain a carbonaceous material; the carbonization temperature is 1000-1600 ℃; the carbonization time is 1-10 h; the carbonization process also comprises pre-carbonization before carbonization, wherein the pre-carbonization temperature is 300-900 ℃; the pre-carbonization time is 0.5-5 h;
D) modifying, ball-milling and grading the carbonaceous material to obtain a hard carbon negative electrode material;
the modification treatment specifically comprises the following steps: soaking a carbonaceous material in an organic matter aqueous solution containing acidic groups, washing to be neutral, filtering and drying; the structural formula of the organic matter containing the acidic groups is R-COOH or R-SO3H, wherein R is a hydrocarbyl group; the soaking time is 0.5-2 h, and the concentration of the acidic organic matters is 1-5 mol/L.
2. The method according to claim 1, wherein the heat treatment temperature in step B) is 250 to 500 ℃; the heat treatment time is 1-3 h; the flow rate of the inert gas is 5-30 ml/min.
3. The method according to claim 1, wherein the carbonization temperature in step C) is 1050 to 1500 ℃; the carbonization time is 1.5-8 h.
4. The preparation method according to claim 1, wherein the ball milling in step D) is performed using water as a solvent; the mass ratio of the water to the carbonaceous material is 1-5: 1; the mass ratio of the grinding balls to the carbonaceous material is 5-30: 1; the ball-milled grinding balls are selected from one or more of zirconia balls, stainless steel balls and alumina ceramic balls; the ball milling rotating speed is 200-1000 rpm.
5. A hard carbon negative electrode material, characterized by being prepared by the preparation method of any one of claims 1 to 4.
6. A preparation method of a battery is characterized in that the negative electrode material is prepared by the preparation method of any one of claims 1 to 4.
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| CN110357061B (en) * | 2018-09-25 | 2022-12-23 | 昆明理工大学 | Recovery method of overdue waste drug acute bronchitis particles |
| CN109592660A (en) * | 2018-11-22 | 2019-04-09 | 上海杉杉科技有限公司 | A kind of hard carbon presoma using carbon containing biological mass shell preparation, hard carbon/graphite composite material and its preparation method and application |
| CN110064026B (en) * | 2019-03-19 | 2022-07-29 | 安徽拂旦生物科技有限公司 | Utilization method of dendrobe |
| CN111204731B (en) * | 2020-01-07 | 2022-05-27 | 大连理工大学 | Preparation method of hard carbon negative electrode material of sodium ion battery |
| CN112811409A (en) * | 2021-01-06 | 2021-05-18 | 宁夏大学 | Method for preparing hard carbon negative electrode material and high-specific-capacity lithium ion battery by using salix purpurea as carbon source |
| CN115285969A (en) * | 2022-08-06 | 2022-11-04 | 华南理工大学 | Biomass-derived nitrogen-doped hard carbon material and preparation method and application thereof |
| EP4442641A1 (en) * | 2023-04-06 | 2024-10-09 | Haycarb Plc | A process for preparing a high purity hard carbon material for sodium ion battery application |
| CN117623278B (en) * | 2024-01-26 | 2024-05-07 | 碳一新能源(杭州)有限责任公司 | Soft-hard carbon composite material and preparation method and application thereof |
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