CN117747817A - Organic acid modified biomass hard carbon material and preparation method and application thereof - Google Patents
Organic acid modified biomass hard carbon material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 150
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 75
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- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 75
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 23
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- 238000003756 stirring Methods 0.000 claims description 30
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an organic acid modified biomass hard carbon material and a preparation method and application thereof, and relates to the technical field of sodium ion battery electrode material preparation. Firstly, drying the bamboo, then crushing, and sieving to obtain bamboo powder; mixing bamboo powder with citric acid to increase the oxygen-containing functional group content of the material, assisting in pore-forming, adding deionized water, and performing hydrothermal carbonization to obtain hydrothermal carbon; then soaking the hydrothermal carbon in sulfuric acid solution, washing ash, and washing with deionized water and ethanol to neutrality; and (3) after drying, carrying out high-temperature carbonization under the protection of inert gas, and cooling to obtain the biomass hard carbon material modified by the organic acid. Firstly, carrying out hydrothermal carbonization and then carrying out high-temperature carbonization, so that carbon elements in the raw materials are fixed in solid carbon as much as possible, and the yield is increased; the used raw materials are easy to obtain, the price is low, the preparation method is simple, and the preparation method has the advantages of large reversible capacity, high initial charge and discharge coulomb efficiency, good cycle performance and the like when being applied to sodium ion batteries.
Description
Technical Field
The invention belongs to the technical field of preparation of sodium ion battery electrode materials, and particularly relates to an organic acid modified biomass hard carbon material, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in many fields such as mobile communication, electric vehicles and aerospace since commercialization was realized in 1991 due to high energy density and long cycle life, and the increasing energy demand has presented challenges to limited lithium storage on earth. In recent years, sodium ion batteries are considered as supplements to lithium ion batteries in specific applications due to their high abundance and low cost. Up to now, various cathode materials suitable for sodium ion batteries, such as intercalation transition metal oxides, polyanion compounds, organic compounds and the like, have been studied. However, the performance of graphite is poor due to the large radius of sodium ions and instability of the sodium-graphite intercalation compound. Therefore, it is imperative to find a suitable anode to facilitate further development of sodium ion battery systems.
Carbon materials are widely studied because of their abundance and low cost. Among the numerous carbon materials, hard carbon having a large interlayer spacing and a high specific capacity is one of the most promising anode materials. In recent years, biomass hard carbon materials such as waste grass, wheat starch and banana peel have attracted attention. Their natural porous structure is an accelerator for electrolyte permeation and can also reduce the diffusion distance of ions. However, it is this complexity that makes its microstructure difficult to manipulate. In recent years, various strategies have been employed to control microstructure, including methods of building layered pore structures, doping heteroatoms, and compounding with other materials. Heteroatom doping can enhance sodium ion storage by providing additional active sites, promoting electron conductivity and diffusion kinetics, and expanding interlayer distance. However, irreversible trapping of sodium ions at defect sites can result in lower Initial Coulombic Efficiency (ICE). The higher the carbonization degree, the more closed the micropores, and the temperature favors the increase of the capacity of the plateau, but the increase of the capacity of the slope. Thus, the ideal strategy for modifying biomass hard carbon materials with excellent electrochemical properties remains challenging.
Aiming at the problems of few active sites, low inclined capacity, low Initial Coulomb Efficiency (ICE) and the like of the existing biomass hard carbon material, the modified research is urgently needed to find a biomass hard carbon material with excellent performance, which provides additional active sites for sodium ions, increases the reversible adsorption capacity of sodium ions in a slope region, promotes the storage of sodium ions in a platform region, improves the electrochemical performance of the material and improves the initial coulomb efficiency of the material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an organic acid modified biomass hard carbon material, and a preparation method and application thereof, so as to solve the problems of few reversible sodium ion adsorption active sites, low tilting capacity and low initial coulomb efficiency of the existing biomass hard carbon material.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of an organic acid modified biomass hard carbon material, which comprises the following steps:
1) Preparation of hydrothermal carbon
Mixing bamboo powder and citric acid to obtain a mixture of the bamboo powder and the citric acid, adding deionized water into the mixture of the bamboo powder and the citric acid, uniformly stirring, performing hydrothermal carbonization, and performing vacuum suction filtration to obtain hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking the hydrothermal carbon obtained in the step 1) in sulfuric acid solution, washing with deionized water and ethanol to be neutral, drying, carbonizing at a high temperature of 900-1500 ℃ under inert gas, and cooling to room temperature to obtain the biomass hard carbon material modified by organic acid.
Preferably, in step 1), the bamboo powder: the mass ratio of the citric acid is (3-6): (1-2), a mixture of bamboo powder and citric acid: the mass ratio of deionized water is (1-7): (1-14).
Preferably, in step 1), the conditions of the hydrothermal carbonization are: and stirring for 1-2 h at 180-300 ℃ in an air atmosphere.
Further preferably, stirring is assisted in the hydrothermal carbonization process, and the stirring speed is 90-150 r/min.
Preferably, in the step 1), the bamboo powder is obtained by drying the bamboo and then crushing for 5-15 min.
Preferably, in the step 2), the concentration of the sulfuric acid solution is 1-6 mol/L, and the soaking time is 1-6 hours.
Preferably, in the step 2), the inert gas is argon, and the flow rate of the inert gas is 30-80 mL/min.
Preferably, in step 2), the conditions of high temperature carbonization are: heating to 900-1500 ℃ at a heating rate of 3-5 ℃/min, and carbonizing at a high temperature of 900-1500 ℃ for 2-5 h.
The invention also discloses the biomass hard carbon material modified and modified by the organic acid prepared by the preparation method.
The invention also discloses application of the organic acid modified biomass hard carbon material in preparing a sodium ion battery anode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of biomass hard carbon material modified by organic acid, which comprises the steps of mixing bamboo powder and citric acid to obtain a mixture of the bamboo powder and the citric acid, adding the citric acid to improve the content of oxygen-containing functional groups, providing additional active sites for sodium ions, assisting in pore-forming, adding deionized water into the mixture of the bamboo powder and the citric acid, uniformly stirring, carrying out hydrothermal carbonization and vacuum filtration to obtain a solid product, wherein carbon elements escape in a gas form due to direct high-temperature carbonization, so that the carbon elements are firstly carbonized by the hydrothermal method to be transferred into a solid phase as much as possible, and the yield is increased; soaking the hydrothermal carbon in sulfuric acid solution, so that the ash content in the biomass hydrothermal carbon material is effectively reduced; washing with deionized water and ethanol to neutrality, and washing off residual sulfuric acid on the surface of the hydrothermal carbon; after drying, carbonizing at high temperature under inert gas, wherein the high temperature carbonization is used for enabling the microcrystalline structure of the material to be more orderly, changing into a graphite-like state and enabling sodium ions to be inserted; and cooling to room temperature to obtain the biomass hard carbon material modified by the organic acid. The bamboo powder is used as a precursor to synthesize the bamboo source hard carbon material with relatively low specific surface area, and the carbonyl and closed micropores are introduced into the bamboo source hard carbon material by combining the acid treatment and the two-step carbonization method, so that additional active sites are provided for sodium ions, the reversible adsorption capacity of sodium ions in a slope area is increased, the storage of sodium ions in a plateau area is promoted, the electrochemical performance of the material is obviously improved, and the initial coulomb efficiency of the material is effectively improved.
Further, in step 1), the bamboo powder: the mass ratio of the citric acid is (3-6): (1-2), a mixture of bamboo powder and citric acid: the mass ratio of deionized water is (1-7): (1-14); the content of oxygen-containing functional groups is further controlled by controlling the addition amount of citric acid, so that an additional active site is provided for sodium ions, and pore-forming is assisted.
Further, in step 1), the conditions of the hydrothermal carbonization are: stirring for 1-2 h at 180-300 ℃ in an air atmosphere; the upper limit of the hydrothermal carbonization temperature is 180 ℃, the lower limit is 300 ℃, the carbonization degree is not high below 180 ℃, and saccharification can occur above 300 ℃.
Further, stirring is assisted in the hydrothermal carbonization process, and the stirring speed is 90-150 r/min; the stirring speed is controlled, so that the whole reaction kettle is heated uniformly, and the carbonization degree is consistent, so that the conditions can be basically met as long as the stirring speed is more than 90 r/min, but the energy cost is also controlled, and the rotating speed cannot be too high.
Further, in the step 1), the bamboo powder is obtained by drying wood and bamboo and then crushing for 5-15 min; the wood and bamboo is crushed completely, and the powder with small particle size is obtained.
Further, in the step 2), the concentration of the sulfuric acid solution is 1-6 mol/L, and the soaking time is 1-6 hours; ash remaining on the surface of the hydrothermal carbon can be sufficiently washed.
Further, in the step 2), the inert gas is argon, and the flow rate of the inert gas is 30-80 mL/min; the surface of the material can be effectively prevented from being oxidized by controlling the flow rate of gas through vacuum high-temperature carbonization.
Further, in the step 2), the conditions of high-temperature carbonization are: heating to 900-1500 ℃ at a heating rate of 3-5 ℃/min, and carbonizing at a high temperature of 900-1500 ℃ for 2-5 h; the interlayer spacing of the carbonized hard carbon material with the reaction temperature lower than 900 ℃ is too large, and the graphitization degree of the carbon material is increased, namely the interlayer spacing is reduced, so that sodium ions are difficult to insert when the reaction temperature is higher than 1500 ℃.
The invention also discloses the biomass hard carbon material modified by the organic acid, which is prepared by the preparation method, has more oxygen-containing functional groups, provides more reversible adsorption sites for sodium ions and assists in pore-forming.
The invention also discloses application of the organic acid modified biomass hard carbon material in preparing a sodium ion battery anode material, wherein the initial specific capacity of the sodium ion battery anode material prepared from the organic acid modified biomass hard carbon material is 246.58~282.49 mAh/g; the first coulomb efficiency is 65% -72%. The prepared organic acid modified biomass hard carbon material has the advantages of large reversible capacity and high initial charge-discharge coulomb efficiency when used in sodium ion batteries.
Drawings
FIG. 1 is an SEM image of an organic acid-modified biomass hard carbon material prepared in example 1 of the invention;
FIG. 2 is a graph showing the nitrogen adsorption/desorption curves of the organic acid-modified biomass hard carbon material prepared in example 1 of the present invention;
FIG. 3 is a graph showing pore size distribution of the organic acid modified biomass hard carbon material prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of the organic acid modified biomass hard carbon material prepared in example 1 of the present invention;
fig. 5 is a raman image of an organic acid modified biomass hard carbon material prepared in example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
the invention discloses an organic acid modified biomass hard carbon material and a preparation method and application thereof, and the biomass hard carbon material comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the wood and bamboo, crushing the dried wood and bamboo by using a crusher to obtain bamboo powder, mixing the bamboo powder with citric acid to obtain a mixture of the bamboo powder and the citric acid, adding deionized water into the mixture, uniformly stirring the mixture, placing the mixture into a reaction kettle for hydrothermal carbonization, and carrying out vacuum suction filtration on a carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking the hydrothermal carbon obtained in the step 1) in sulfuric acid solution to wash ash, washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality, drying, then placing the filtrate into a tubular furnace, carbonizing at high temperature in an inert gas environment, cooling to room temperature, and taking out to finally obtain the biomass hard carbon material modified and modified by organic acid.
In the step 1), the operation time of the pulverizer is 5-15 min.
In the step 1), the hydrothermal carbonization reaction conditions are as follows, and the bamboo powder is: the mass ratio of the citric acid is (3-6): (1-2), a mixture of bamboo powder and citric acid: the mass ratio of deionized water is (1-7): (1-14); in an air atmosphere, the temperature of the hydrothermal carbonization is 180-300 ℃, the time of the hydrothermal carbonization is 1-2 h, and the stirring is assisted in the process of the hydrothermal carbonization, wherein the stirring speed is 90-150 r/min.
In the step 2), the pickling condition is as follows, the concentration of the sulfuric acid solution is 1-6 mol/L, 0.1-5 g of hydrothermal carbon is soaked in every 50-100 mL of sulfuric acid solution, and the pickling is carried out for 1-6 h at room temperature.
In the step 2), high-temperature carbonization conditions are as follows, argon atmosphere, argon flow rate is 30-80 mL/min, heating rate is 3-5 ℃/min, high-temperature carbonization temperature is 900-1500 ℃, and high-temperature carbonization time is 2-5 h.
According to another aspect of the present invention, there is provided an organic acid modified biomass hard carbon material prepared by the above method.
According to another aspect of the present invention, there is provided a sodium ion battery comprising a negative electrode prepared from the above organic acid modified biomass hard carbon material.
The bamboos used in the following examples of the present invention were purchased from Shandong Elpi powder technology Co., ltd, and were dried and stored after retrieval.
Example 1
The preparation method of the biomass hard carbon material modified and modified by the organic acid comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the bamboo, and pulverizing with a pulverizer to obtain bamboo powder for 10 min; the bamboo powder and citric acid are mixed according to the mass ratio of 3:1, mixing to obtain a mixture of bamboo powder and citric acid, and mixing the mixture of bamboo powder and citric acid with deionized water according to a mass ratio of 1:14, mixing and stirring uniformly; then placing the mixture into a reaction kettle for hydrothermal carbonization, wherein the hydrothermal carbonization conditions are as follows: stirring 1 h under the air atmosphere at 240 ℃ at the stirring speed of 120 r/min in the reaction process; vacuum filtering the carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking 0.1g of the hydrothermal carbon obtained in the step 1) in a sulfuric acid solution of 50 mL and 1 mol/L for 6 h, washing ash, and washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality; and (3) after drying, placing the biomass hard carbon material into a tubular furnace, carbonizing at a high temperature under an argon atmosphere, wherein the argon gas flow rate is 80 mL/min, the heating rate is 5 ℃/min, the high-temperature carbonization temperature is 1300 ℃, the high-temperature carbonization time is 2 h, and taking out the biomass hard carbon material after cooling to room temperature to obtain the biomass hard carbon material modified and modified by the organic acid.
FIG. 1 is an SEM image of an organic acid-modified biomass hard carbon material prepared in example 1 of the invention; as can be seen from fig. 1, the prepared biomass hard carbon material modified by modification with organic acid has smooth hard carbon surface and almost no visible pores.
FIG. 2 is a graph showing the nitrogen adsorption/desorption curves of the organic acid-modified biomass hard carbon material prepared in example 1 of the present invention; fig. 3 is a pore size distribution diagram of the organic acid modified biomass hard carbon material prepared in example 1 of the present invention, and it can be seen from fig. 2 and fig. 3 that the main pore structure of the organic acid modified biomass hard carbon material is mesoporous and contains a small number of micropores.
FIG. 4 is an XRD pattern of the organic acid modified biomass hard carbon material prepared in example 1 of the present invention; as can be seen from fig. 4, the organic acid modified biomass hard carbon material has a distinct peak (002) of graphite microcrystals, the sharper the peak is indicative of the higher graphitization degree of the material, and as can be seen from fig. 4, the organic acid modified biomass hard carbon material has a broad peak, conforms to the graphite-like structure of the material, and meets the requirement of pore diameter capable of inserting sodium ions.
FIG. 5 is a Raman image of the organic acid modified biomass hard carbon material prepared in example 1 of the present invention; from the slaveAs can be seen in fig. 5, the organic acid modified biomass hard carbon material was found to be 1350 cm in the range of -1 And 1590 cm -1 The left and right characteristic peaks of amorphous carbon are shown, corresponding to disordered carbon bands (D bands) and in-plane vibration bands (G bands), respectively. The intensity ratio of D-band and G-band (ID/IG) is typically used to characterize the graphitization degree of the material. The lower the ID/IG, the higher the graphitization degree, the more ordered the structure, and it can be seen from fig. 5 that the crystals of the organic acid modified biomass hard carbon material are more disordered.
Example 2
The preparation method of the biomass hard carbon material modified and modified by the organic acid comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the bamboo, and pulverizing with a pulverizer to obtain bamboo powder for 5 min; the bamboo powder and citric acid are mixed according to the mass ratio of 3:2, mixing to obtain a mixture of bamboo powder and citric acid, and mixing the mixture of bamboo powder and citric acid with deionized water according to a mass ratio of 2:9, mixing and stirring uniformly; then placing the mixture into a reaction kettle for hydrothermal carbonization, wherein the hydrothermal carbonization conditions are as follows: 2, h is treated under the air atmosphere at 180 ℃ and the stirring speed in the reaction process is 90 r/min; vacuum filtering the carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking 3g of the hydrothermal carbon obtained in the step 1) in 5mol/L sulfuric acid solution of 70 mL for 3 h, washing ash, and washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality; and (3) after drying, placing the biomass hard carbon material into a tubular furnace, carbonizing at a high temperature under an argon atmosphere, wherein the argon gas flow rate is 70 mL/min, the heating rate is 4 ℃/min, the high-temperature carbonization temperature is 1500 ℃, the high-temperature carbonization time is 3 h, and taking out the biomass hard carbon material after cooling to room temperature to obtain the biomass hard carbon material modified and modified by the organic acid.
Example 3
The preparation method of the biomass hard carbon material modified and modified by the organic acid comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the bamboo, and pulverizing with a pulverizer to obtain bamboo powder for 15 min; the bamboo powder and citric acid are mixed according to the mass ratio of 6:1, mixing to obtain a mixture of bamboo powder and citric acid, and mixing the mixture of bamboo powder and citric acid with deionized water according to a mass ratio of 1:7, mixing and stirring uniformly; then placing the mixture into a reaction kettle for hydrothermal carbonization, wherein the hydrothermal carbonization conditions are as follows: treating 1.5. 1.5 h in an air atmosphere at 300 ℃ with stirring rate of 150 r/min during the reaction; vacuum filtering the carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking 5g of the hydrothermal carbon obtained in the step 1) in a sulfuric acid solution of 100 mL and 6mol/L for 1 h, washing ash, and washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality; and (3) after drying, placing the biomass hard carbon material into a tubular furnace, carbonizing at a high temperature under an argon atmosphere, wherein the argon gas flow rate is 30 mL/min, the heating rate is 3 ℃/min, the high-temperature carbonization temperature is 900 ℃, the high-temperature carbonization time is 5 h, and taking out the biomass hard carbon material after cooling to room temperature to obtain the biomass hard carbon material modified and modified by the organic acid.
Example 4
The preparation method of the biomass hard carbon material modified and modified by the organic acid comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the bamboo, and pulverizing with a pulverizer to obtain bamboo powder for 7 min; the bamboo powder and citric acid are mixed according to the mass ratio of 4:1, mixing to obtain a mixture of bamboo powder and citric acid, and mixing the mixture of bamboo powder and citric acid with deionized water according to a mass ratio of 1:1, mixing and stirring uniformly; then placing the mixture into a reaction kettle for hydrothermal carbonization, wherein the hydrothermal carbonization conditions are as follows: treating 1 h in an air atmosphere at 200 ℃ at a stirring rate of 100 r/min during the reaction; vacuum filtering the carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking 2g of the hydrothermal carbon obtained in the step 1) in a sulfuric acid solution of 60 mL and 2 mol/L for 2 h, washing ash, and washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality; and (3) after drying, placing the biomass hard carbon material into a tubular furnace, carbonizing at a high temperature under an argon atmosphere, wherein the argon gas flow rate is 40 mL/min, the heating rate is 5 ℃/min, the high-temperature carbonization temperature is 1000 ℃, the high-temperature carbonization time is 4 h, and taking out the biomass hard carbon material after cooling to room temperature to obtain the biomass hard carbon material modified and modified by the organic acid.
Example 5
The preparation method of the biomass hard carbon material modified and modified by the organic acid comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the bamboo, and pulverizing with a pulverizer to obtain bamboo powder for 9 min; the bamboo powder and citric acid are mixed according to the mass ratio of 5:1, mixing to obtain a mixture of bamboo powder and citric acid, and mixing the mixture of bamboo powder and citric acid with deionized water according to the mass ratio of 7:1, mixing and stirring uniformly; then placing the mixture into a reaction kettle for hydrothermal carbonization, wherein the hydrothermal carbonization conditions are as follows: treating 1.5. 1.5 h in an air atmosphere at 220 ℃ with stirring rate of 130 r/min during the reaction; vacuum filtering the carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking 4g of the hydrothermal carbon obtained in the step 1) in a sulfuric acid solution of 80 mL and 3 mol/L for 4 h, washing ash, and washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality; and (3) after drying, placing the biomass hard carbon material into a tubular furnace, carbonizing at a high temperature under an argon atmosphere, wherein the argon gas flow rate is 50 mL/min, the heating rate is 4 ℃/min, the high-temperature carbonization temperature is 1100 ℃, the high-temperature carbonization time is 2 h, and taking out the biomass hard carbon material after cooling to room temperature to obtain the biomass hard carbon material modified and modified by the organic acid.
Example 6
The preparation method of the biomass hard carbon material modified and modified by the organic acid comprises the following steps:
1) Preparation of hydrothermal carbon by citric acid-assisted bamboo powder
Drying the bamboo, and pulverizing with a pulverizer to obtain bamboo powder for 12 min; the bamboo powder and citric acid are mixed according to the mass ratio of 3:1, mixing to obtain a mixture of bamboo powder and citric acid, and mixing the mixture of bamboo powder and citric acid with deionized water according to a mass ratio of 1:2, mixing and stirring uniformly; then placing the mixture into a reaction kettle for hydrothermal carbonization, wherein the hydrothermal carbonization conditions are as follows: 2, processing h under the air atmosphere at 260 ℃ with the stirring rate of 110 r/min in the reaction process; vacuum filtering the carbonized product to obtain a solid product hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking 4.5g of the hydrothermal carbon obtained in the step 1) in a 4 mol/L sulfuric acid solution of 90 mL for 5 h, washing ash, and washing with deionized water and ethanol until the pH value of the filtrate reaches neutrality; and (3) after drying, placing the biomass hard carbon material into a tubular furnace, carbonizing at a high temperature under an argon atmosphere, wherein the argon gas flow rate is 60 mL/min, the heating rate is 3 ℃/min, the high-temperature carbonization temperature is 1200 ℃, the high-temperature carbonization time is 3 h, and taking out the biomass hard carbon material after cooling to room temperature to obtain the biomass hard carbon material modified and modified by the organic acid.
Comparative example 1
Unlike example 1, no citric acid was added.
Comparative example 2
Unlike example 1, no citric acid was added and no pickling was performed.
The biomass hard carbon materials modified and modified by organic acid obtained in each example and comparative example, acetylene black and sodium carboxymethylcellulose (CMC) are uniformly ground according to the mass ratio of 8:1:1, then a proper amount of deionized water is added to prepare slurry, the slurry is uniformly coated on copper foil by a coating machine, the copper foil is placed in a vacuum drying oven to be dried in vacuum at 80 ℃ for 12 h, and then a wafer electrode with the diameter of 12 mm is prepared by a sheet punching machine. The obtained wafer electrode was used as a negative electrode, a glass fiber wafer with a diameter of 19 mm was used as a separator, a sodium metal sheet with a diameter of 12 mm and a thickness of 0.2 mm was used as a counter electrode and a reference electrode, an electrolyte solution was 1 mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution, a sodium ion battery was assembled in a high-purity argon-filled glove box according to the construction of a CR2016 standard button cell, and a charge and discharge test was performed on the sodium ion battery with a current density of 30 mA/g on a battery test platform. The initial specific capacity of the sodium ion battery made of the organic acid modified biomass hard carbon material prepared in the embodiment 1 is 282.49 mAh/g, and the initial coulomb efficiency is 72%; the initial specific capacity of the sodium ion battery made of the organic acid modified biomass hard carbon material prepared in the example 2 is 246.58 mAh/g, and the initial coulomb efficiency is 65%; the initial specific capacity of the sodium ion battery made of the organic acid modified biomass hard carbon material prepared in the embodiment 3 is 276.54 mAh/g, and the initial coulomb efficiency is 68%; the initial specific capacity of the sodium ion battery made of the organic acid modified biomass hard carbon material prepared in the comparative example 1 is 232.61 mAh/g, and the initial coulomb efficiency is 63%; the initial specific capacity of the sodium ion battery made of the organic acid modified biomass hard carbon material prepared in the comparative example 2 is 204.56 mAh/g, and the initial coulomb efficiency is 61%.
In summary, the invention adopts two-step carbonization, namely hydrothermal carbonization and high-temperature carbonization, so that carbon elements in the raw materials are fixed in solid carbon as much as possible, and the yield is increased; citric acid is added in the preparation process of the material, so that the content of oxygen-containing functional groups of the material is improved, and the pore-forming is assisted, and after acid treatment and two-step carbonization, the capacity and initial coulomb efficiency of the biomass hard carbon material modified by organic acid modification are effectively improved. The bamboo is used as a precursor to synthesize the bamboo-derived hard carbon anode material with relatively low specific surface area, and the carbonyl and the closed micropores are jointly introduced into the hard carbon material by combining acid treatment and a two-step carbonization method, so that the problems of few reversible sodium ion adsorption active sites, low inclined capacity and low initial coulomb efficiency of the existing biomass hard carbon material are solved.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the biomass hard carbon material modified and modified by the organic acid is characterized by comprising the following steps of:
1) Preparation of hydrothermal carbon
Mixing bamboo powder and citric acid to obtain a mixture of the bamboo powder and the citric acid, adding deionized water into the mixture of the bamboo powder and the citric acid, uniformly stirring, performing hydrothermal carbonization, and performing vacuum suction filtration to obtain hydrothermal carbon;
2) Preparation of biomass hard carbon material modified by organic acid
Soaking the hydrothermal carbon obtained in the step 1) in sulfuric acid solution, washing with deionized water and ethanol to be neutral, drying, carbonizing at a high temperature of 900-1500 ℃ under inert gas, and cooling to room temperature to obtain the biomass hard carbon material modified by organic acid.
2. The method for preparing the biomass hard carbon material modified and modified by organic acid according to claim 1, wherein in the step 1), bamboo powder is obtained by: the mass ratio of the citric acid is (3-6): (1-2), a mixture of bamboo powder and citric acid: the mass ratio of deionized water is (1-7): (1-14).
3. The method for preparing the biomass hard carbon material modified and modified by organic acid according to claim 1, wherein in the step 1), the hydrothermal carbonization conditions are as follows: and stirring for 1-2 h at 180-300 ℃ in an air atmosphere.
4. The method for preparing the biomass hard carbon material modified and modified by organic acid according to claim 3, wherein stirring is assisted in the hydrothermal carbonization process, and the stirring speed is 90-150 r/min.
5. The method for preparing the biomass hard carbon material modified and modified by organic acid according to claim 1, wherein in the step 1), the bamboo powder is obtained by drying wood and bamboo and then crushing for 5-15 min.
6. The method for preparing the biomass hard carbon material modified and modified by organic acid according to claim 1, wherein in the step 2), the concentration of the sulfuric acid solution is 1-6 mol/L, and the soaking time is 1-6 h.
7. The method for preparing the organic acid modified biomass hard carbon material according to claim 1, wherein in the step 2), the inert gas is argon, and the flow rate of the inert gas is 30-80 mL/min.
8. The method for preparing a biomass hard carbon material modified and modified by organic acid according to claim 1, wherein in the step 2), the conditions of high-temperature carbonization are as follows: heating to 900-1500 ℃ at a heating rate of 3-5 ℃/min, and carbonizing at a high temperature of 900-1500 ℃ for 2-5 h.
9. The organic acid modified biomass hard carbon material prepared by the preparation method of any one of claims 1-8.
10. The use of the organic acid modified biomass hard carbon material of claim 9 in the preparation of sodium ion battery anode materials.
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