CN113666356B - Shell biomass-based hard carbon negative electrode material of sodium ion battery and preparation method - Google Patents
Shell biomass-based hard carbon negative electrode material of sodium ion battery and preparation method Download PDFInfo
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Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a shell biomass-based hard carbon negative electrode material of a sodium ion battery and a preparation method thereof. The invention takes shell biomass material as biomass raw material, and the biomass raw material is sequentially immersed in hydrochloric acid alcohol solution and sulfuric acid solution and stirred to obtain suspension; dispersing the suspension in water, filtering and drying to obtain a precursor; heating the precursor under the protection of inert gas for pre-carbonization treatment, cooling and then ball-milling to obtain pre-carbon powder; and heating the pre-carbon powder under the protection of inert gas, carrying out high-temperature carbonization treatment, and cooling to obtain the biomass hard carbon negative electrode material for the sodium ion battery. The method has simple process, and the prepared hard carbon negative electrode material for the sodium ion battery has high first coulombic efficiency and reversible specific capacity.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery cathode material and a preparation method thereof.
Background
The lithium ion battery has already been on a mature industrial scale, but the sodium ion battery is still in an initial development stage at present and is not used in a large-scale industrial manner. The cathode materials prepared by the same process are applied to lithium ion batteries and sodium ion batteries respectively, and show completely different results, for example, carbon-based materials represented by graphite can be completely used as cathode materials of lithium ion batteries and can obtain better performance, but when the cathode materials are applied to the cathode materials of the sodium ion batteries, stable intercalation compounds cannot be formed at all, so that the graphite cannot be used as the cathode materials of the sodium ion batteries.
In the prior art, a carbon negative electrode material for a sodium ion battery is prepared by taking biological wastes (such as corn cobs, pumpkin vines, straw stalks and the like) as raw materials, and biomass is washed, dried, calcined and crushed, treated by a treatment solution and then dried, sieved and calcined again to obtain the carbon negative electrode material suitable for the sodium ion battery. In the prior art, wood dust is used as a raw material, the wood dust and ethers are crosslinked, and high-temperature carbonization is performed again to obtain the negative electrode material for the sodium-ion battery, so that the preparation process is complicated, the initial coulombic efficiency is low (lower than 85%), and the industrial economic benefit is low. In conclusion, the existing negative electrode material for the sodium-ion battery has the defects of complex preparation process, high production cost and low coulombic efficiency for the first time, so that the biomass charcoal negative electrode material is difficult to realize large-scale application production in industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a hard carbon cathode material of a sodium ion battery based on shell biomass, which has the advantages of abundant raw material sources, environmental protection, reproducibility, simple process and high coulombic efficiency for the first time, and a preparation method thereof.
The invention also relates to preparation of the hard carbon negative plate of the sodium ion battery and the sodium ion battery using the negative plate.
The invention provides a preparation method of a hard carbon cathode material of a sodium ion battery, which takes shell biomass materials as biomass raw materials and comprises the following steps:
s1, sequentially immersing a biomass raw material into a hydrochloric acid alcohol solution and a sulfuric acid solution, stirring, removing ash and ethanol extracts in the biomass raw material, and carrying out oxidation modification on functional groups which are easy to oxidize in the biomass raw material to obtain a suspension;
s2, dispersing the suspension obtained in the step S1 in water, filtering and drying to obtain a precursor;
s3, heating the precursor obtained in the step S2 to 450-550 ℃ under the protection of inert gas, carrying out pre-carbonization treatment, cooling and then carrying out ball milling to obtain pre-carbon powder;
and S4, heating the pre-carbon powder obtained in the step S3 to 1100-1600 ℃ under the protection of inert gas, carrying out high-temperature carbonization treatment, and cooling to obtain the hard carbon negative electrode material for the sodium ion battery.
As a further improvement to the above technical solution.
The shell biomass material is one or more of oil tea fruit shell, peanut shell, rice hull and coconut shell.
In the step S1, the stirring time of the biomass raw material in the hydrochloric acid alcohol solution is 3-6 h; the hydrochloric acid alcohol solution is a mixed solution of dilute hydrochloric acid and ethanol, the molar concentration of the dilute hydrochloric acid is 0.1-1 mol/L, and the mass concentration of the ethanol is 20% -70%.
In the step S1, the molar concentration of the sulfuric acid solution is 3-6 mol/L, and the volume ratio of the mass of the biomass raw material to the sulfuric acid solution is 10-60 g: 60 And (mL).
In the step S2, the dispersion is ultrasonic dispersion, and the ultrasonic dispersion time is 30-60 min.
In the step S3, the heating rate of the temperature rise is 5-10 ℃/min; the temperature of the pre-carbonization treatment is 450-550 ℃; the time is 1-3h.
In the step S3, the ball milling rotating speed is 300-700 r/min, and the ball milling time is 0.5-2 h.
In the step S4, the heating rate of the heating is 3-10 ℃/min, and the heat preservation time of the high-temperature carbonization treatment is 1-4 h.
The hard carbon negative electrode material for the sodium ion battery is prepared by the preparation method, is amorphous carbon, has the grain size of 1-20 mu m, and has the crystal plane interlayer spacingd 002 The value is 0.36-0.4 nm, and the crystallite sizeLa is 1-5 nm, and the alpha is,Lc is the length of 1-5 nm,I D /I G 1-3, specific surface area less than 15 m 2 Per g, pore volume of 0-0.1 cm 3 /g。
The invention also provides a preparation method of the negative electrode plate of the sodium-ion battery, which comprises the following steps:
mixing the biomass hard carbon negative electrode material with conductive carbon black and an adhesive, and uniformly stirring to obtain electrode slurry; the biomass hard carbon negative electrode material is the hard carbon negative electrode material for the sodium ion battery prepared by the preparation method;
and coating the electrode slurry on a current collector, drying and then stamping to obtain the negative electrode plate of the sodium-ion battery.
The invention also provides a sodium ion battery which comprises a negative electrode, a positive electrode, a diaphragm and electrolyte, wherein the negative electrode is the negative electrode plate of the sodium ion battery prepared by the preparation method.
The hard carbon negative electrode material for the sodium ion battery based on the shell biomass has the specific charge capacity of 310-341 mAh/g for the first time and the coulombic efficiency of 83-93% under the condition that the charge-discharge current is 30 mA/g.
The main innovation points of the invention are as follows:
1. through long-term experimental research, the applicant finds that in the prior art, biomass raw materials are generally directly pyrolyzed into biomass charcoal materials and then are applied to the field of negative electrode materials, however, the first specific capacity and the first coulombic efficiency of the biomass charcoal materials prepared in the way are common. Therefore, the applicant has made intensive research and development on this technical problem;
2. according to the technical scheme, before the biomass raw material is pyrolyzed and pyrolyzed, a hydrochloric acid alcohol solution (a mixed solution of dilute hydrochloric acid and ethanol) is adopted to remove ash and ethanol extracts in the biomass raw material; then, the biomass raw material is soaked by concentrated sulfuric acid, the functional group which is easy to oxidize in the biomass raw material is subjected to oxidation modification, the introduced oxygen atom can react with carbon element in situ during subsequent high-temperature carbonization, and closed micropores are left in hard carbon, so that the sodium storage capacity of the hard carbon cathode can be effectively improved while the high first coulombic efficiency is ensured.
Compared with the prior art, the invention has the advantages that:
(1) The hard carbon negative electrode material for the sodium ion battery prepared by the preparation method is high in coulomb efficiency and large in specific capacity for the first time. On one hand, the biomass material can keep natural space morphology in the biomass raw material, such as a large number of micropores, and has larger charge-discharge specific capacity (310-341 mAh/g, such as 341 mAh/g of example 1) than commercial hard carbon (250 mAh/g). Because the biomass carbon negative electrode material for the sodium ion battery has the characteristics of rapid electron transmission and ion diffusion, when the biomass carbon negative electrode material is used as an electrode active material, the migration path of sodium ions is greatly shortened, the sodium ions can rapidly shuttle in the electrode active material, the reversible capacity of the sodium ion battery is improved, and the first coulombic efficiency is high (83-93 percent);
(2) The preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass can eliminate the influence of ash in the biomass raw material, introduces proper oxygen atoms in the process, and obtains hard carbon with small specific surface area (less than 15 m) through high-temperature carbonization 2 The sodium storage position is rich. When used as a negative electrode of a sodium ion battery, excellent characteristics of high coulombic efficiency and high reversible capacity can be achieved. The method has the advantages of simple and easy process, wide and rich raw material sources, environmental protection, regeneration and low cost of the hard carbon cathode material for the sodium ion battery.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a scanning electron microscope image of the hard carbon negative electrode material for a sodium ion battery in example 1 of the present invention.
Fig. 3 is a first charge-discharge curve diagram of the hard carbon negative electrode material for the sodium ion battery in example 1 of the present invention.
Fig. 4 is a graph showing the rate cycle performance of the hard carbon negative electrode material for a sodium ion battery in example 1 of the present invention.
Fig. 5 is an X-ray diffraction pattern of the hard carbon negative electrode material for a sodium ion battery in example 1 of the invention.
Fig. 6 is a raman chart of the hard carbon negative electrode material for a sodium ion battery in example 1 of the present invention.
FIG. 7 is a first charge-discharge curve diagram of the biomass hard carbon negative electrode material in comparative example 3 of the invention.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples. Unless otherwise specified, the instruments or materials employed in the present invention are commercially available.
As shown in fig. 1, the preparation method of the hard carbon negative electrode material for the sodium ion battery based on shell biomass comprises the following steps:
s1, using a shell biomass material as a biomass raw material, sequentially immersing the biomass raw material into a hydrochloric acid alcohol solution (a mixed solution of dilute hydrochloric acid and ethanol) and a sulfuric acid solution, stirring, removing ash and ethanol extracts in the biomass raw material, and carrying out oxidation modification on functional groups which are easy to oxidize in the biomass raw material to obtain a suspension;
s2, dispersing the suspension obtained in the step S1 in water, filtering and drying to obtain a precursor;
s3, heating the precursor obtained in the step S2 to 450-550 ℃ under the protection of inert gas for pre-carbonization treatment, cooling and then ball-milling to obtain pre-carbon powder;
and S4, heating the pre-carbon powder obtained in the step S3 to 1100-1600 ℃ under the protection of inert gas, carrying out high-temperature carbonization treatment, and cooling to obtain the hard carbon negative electrode material for the sodium ion battery.
The shell biomass materials (oil tea fruit shells, peanut shells, rice hulls and coconut shells) are selected as biomass raw materials, and the raw materials are wide in source, easy to pretreat and high in carbon residue rate after high-temperature carbonization, so that the requirements of low cost, large-scale production and the like can be met. The raw materials selected by the invention have special microstructures, such as developed micropore structure, high lignin content and the like, and the prepared hard carbon has the characteristics of high disorder, large carbon layer spacing, rich micropores and small specific surface area. When the material is used as a negative electrode material of a sodium ion battery, the first coulombic efficiency (83% -95%) is higher than that of hard carbon negative electrodes prepared from other biomasses, the specific capacity is large (341 mAh/g), and the energy density of the sodium ion battery can be greatly improved. One or more of oil tea fruit shell, peanut shell, rice hull and coconut shell is used as a biomass raw material, the biomass raw material is sequentially immersed in a hydrochloric acid alcohol solution (a mixed solution of dilute hydrochloric acid and ethanol) and a sulfuric acid solution and stirred to obtain a suspension, and the suspension is dispersed in water, filtered and dried to obtain a precursor.
The main functions of the step comprise: (1) Impurities such as acidic/ethanol soluble organic matters and inorganic components in the raw materials are removed, and ash content in the prepared biomass hard charcoal is reduced. (2) More importantly, the functional groups which are easy to be oxidized in the raw materials are oxidized and modified, particularly aldehyde groups in lignin are oxidized into carboxyl groups, so that the aim of increasing the content of oxygen elements in a precursor is fulfilled, and the oxygen elements in the precursor can react with carbon elements in situ during high-temperature carbonization and leave micropores in hard carbon, so that the sodium storage capacity of the hard carbon cathode can be effectively improved. The stirring time in the hydrochloric acid alcohol solution and the sulfuric acid solution is 3-6 h, and if the stirring time is too short, the impurity removal effect is reduced; if the stirring time is too long, the impurity removal effect does not continuously increase, and the time cost and energy consumption are also increased. The concentration of the hydrochloric acid is 0.1-1 mol/L, the mass concentration of the ethanol is 20% -70%, in the preferred embodiment of the invention, the concentration of the hydrochloric acid is 0.5 mol/L, and the mass concentration of the ethanol is 30%. The molar concentration of the sulfuric acid solution is 3-6 mol/L, and if the concentration of the sulfuric acid solution is too low (lower than 3 mol/L), the oxidation effect is poor; when the concentration is higher than 6 mol/L, the oxygen content in the precursor is not increased any more, and the production cost is increased. In a preferred embodiment of the invention, stirring is preferably carried out for 6 h in a 6 mol/L sulfuric acid solution.
And heating the precursor to 450-550 ℃ under the protection of inert gas for pre-carbonization treatment, cooling and then ball-milling to obtain pre-carbon powder.
Specifically, the inert gas protection is used for isolating the precursor from air, so that the precursor is prevented from being burnt and polluted by impurities in the heating process; the inert gas protective flow can also timely take away the moisture volatilized by heating the precursor, the low-boiling organic micromolecules generated by decomposition and the like.
The pre-carbonization time is 1-3h, the pre-carbonization aims at decomposing low-boiling-point organic matters, and a hard carbon material which is highly disordered, has large carbon layer spacing, is rich in micropores and has small specific surface area is conveniently formed in the subsequent high-temperature carbonization process.
The pre-carbonization temperature is preferably 450-550 ℃, if the temperature is too low, the decomposition of low-boiling-point organic matters in the precursor is incomplete, which is not beneficial to forming micropores; if the temperature is too high, the subsequent ball milling process is not favorable for introducing defects into the pre-carbon powder, and a part of regular graphitized structures can be formed in the ball milling process. Because the regular graphitized structure is not beneficial to the storage of sodium in the hard carbon, when the temperature in the pre-carbonization treatment process is too high, the sodium storage capacity of the hard carbon cathode prepared by high-temperature carbonization is reduced.
Powder with uniform particles and the size range of 1-15 mu m can be obtained by ball milling, the coating of the electrode is facilitated, more importantly, partial defects can be introduced into the pre-carbon powder by ball milling, and the defects can form micropores in hard carbon after high-temperature carbonization. Preferably, the rotation speed of the ball milling is 300-700 r/min, and the ball milling time is 0.5-2 h. If the rotating speed is too low, the ball milling time is too short, and powder with uniform particle size cannot be obtained; if the rotating speed is too high and the ball milling time is too long, the hard carbon carbonized at high temperature can form a large amount of graphitized structures, and the sodium storage capacity is reduced. In the preferred embodiment of the invention, the ball milling rotating speed is preferably 400-500 r/min, and the ball milling time is preferably 0.5-1 h.
Specifically, the pre-carbon powder is heated to 1100-1600 ℃ under the protection of inert gas for high-temperature carbonization treatment and is cooled to obtain the hard carbon negative electrode material for the sodium ion battery.
The main function of the high-temperature carbonization treatment is to further remove impurity elements (H, O, N and the like) and functional groups (-OH, -COOH and the like) in the pre-carbonized product to obtain the hard carbon material with high purity and high conductivity. And (3) carrying out high-temperature carbonization treatment on the pre-carbon powder, wherein the carbonization treatment temperature is 1100-1600 ℃, and the treatment time is 1-4 h. Because the biomass hard carbon is difficult to graphitize, when the carbonization temperature is lower than 1100 ℃, impurity elements and functional groups in the hard carbon are not completely removed, the conductivity is low, and proper micropores cannot be formed, so that the irreversible capacity of the hard carbon cathode in the first charge-discharge process is high (mainly due to the increase of irreversible reactions of Na and the impurity elements), and the reversible sodium storage capacity is low. If the carbonization temperature is higher than 1600 ℃, excessive graphitized structures are formed, the distance between carbon layers is reduced, the number of micropores is reduced, the migration and storage of sodium ions in the hard carbon are not facilitated, and the capacity of the obtained hard carbon cathode is reduced.
In some preferred embodiments of the invention, the high temperature carbonization temperature is 1300 ℃, the treatment time is 2 h, and the temperature rise rate is 10 ℃/min. The prepared biomass hard carbon negative electrode has excellent sodium storage performance, the first coulombic efficiency reaches 87.5 percent, and the reversible specific capacity reaches 341 mAh/g. The biomass hard carbon negative electrode also has high specific capacity below 0.1V, and is beneficial to improving the energy density of the sodium ion full battery.
The invention also provides a preparation method of the hard carbon negative plate for the sodium ion battery, which comprises the following specific steps:
E01. mixing the prepared hard carbon negative electrode material with a binder and conductive carbon in proportion, and fully stirring to obtain electrode slurry;
E02. and coating the electrode slurry on a current collector, drying and then stamping to obtain the negative electrode plate of the sodium-ion battery.
In the step E01, the hard carbon negative electrode material is mixed with the binder and the conductive carbon in a proportion, preferably, the hard carbon negative electrode material accounts for 80 to 97 percent of the total weight of the electrode material, and preferably 85 to 95 percent of the total weight; the content of the adhesive is 0 to 10 percent of the total weight, and preferably 2.5 to 5 percent of the total weight; the proportion of conductive carbon black is 0% to 10% by weight, preferably 2.5% to 5% by weight.
The binder is one of sodium carboxymethylcellulose (CMC), sodium alginate, sodium polyacrylate and polyvinylidene fluoride (PVDF).
In the step E02, the electrode slurry is coated on a copper foil or aluminum foil current collector, and the sodium ion battery negative electrode plate is obtained by drying and stamping. Preferably, the drying temperature is 60-90 ℃, and the drying time is more than 2 hours.
The preparation method of the sodium ion battery cathode electrode plate provided by the invention is simple, is convenient and fast to operate, and is beneficial to industrial preparation and use.
Correspondingly, the invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is prepared by the preparation method.
And (3) dropping organic electrolyte on a diaphragm to assemble the sodium-ion battery by taking the obtained negative electrode plate of the sodium-ion battery as a negative electrode and taking metal sodium as a counter electrode and a reference electrode.
The electrolyte is a mixed solution of electrolyte salt and organic solvent, and comprises conventional organic electrolyte, and the concentration is generally 0.5-5 mol/L, preferably 0.8-1.2 mol/L.
The electrolyte salt can be one or more selected from sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate and sodium fluoro alkyl sulfonate.
The organic solvent is a mixed solution of chain acid ester and cyclic acid ester, wherein the chain acid ester can be at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC), methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds, the cyclic acid ester can be at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), vinylene Carbonate (VC), y-butyl lactone (y-BL), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds, and the alcohol ether can be at least one of diethylene glycol ethyl ether (DGME), triethylene glycol dimethyl ether (TGME) and tetraethylene glycol dimethyl ether (TGEME).
Example 1:
the preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Crushing dried camellia oleifera shells into powder by using a crusher, weighing 10g of camellia oleifera shell powder as a biomass raw material, soaking the biomass raw material into 60 mL of mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 500 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) And ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tube furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1300 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon cathode material for the sodium ion battery.
The hard carbon negative electrode material for the sodium ion battery based on shell biomass prepared in this example is irregular block-shaped as shown in fig. 2 by a scanning electron microscope. When the charging and discharging current is 30 mA/g, the first discharging specific capacity reaches 389.6 mAh/g, the charging specific capacity is 341 mAh/g, and the first coulombic efficiency is 87.5%.
The first charge and discharge performance graph of the hard carbon negative electrode material for the sodium ion battery based on shell biomass prepared in the embodiment is shown in fig. 3, and the hard carbon negative electrode material has excellent first coulombic efficiency and first reversible capacity.
The hard carbon negative electrode material prepared in the embodiment is used for preparing a negative electrode plate of a sodium ion battery, and the specific steps are as follows:
mixing 0.27 g of the hard carbon negative electrode material powder for the sodium ion battery prepared in the embodiment with conductive carbon black, wherein the mass ratio of the hard carbon negative electrode material to the conductive carbon black to the binder is 18: 1, adding the obtained mixture into a CMC (carboxy methyl cellulose) aqueous solution, stirring for 6 hours, and then coating on a carbon-coated aluminum foil to prepare a negative electrode plate; then taking a metal sodium sheet as a counter electrode and NaClO 4 In the electrolyte solution of the EC/DEC (i.e., ethylene carbonate/diethyl carbonate) mixed solution, naClO 4 The concentration of (A) is 1mol/L, the mass ratio of EC to DEC is 1: 1, and a GF/C glass fiber film is used as a diaphragm to assemble a 2016 type button cell.
It was found that when the charge and discharge current of the hard carbon negative electrode material for the sodium ion battery based on shell biomass in this embodiment was 30 mA/g, the first discharge specific capacity reached 389.6 mAh/g, the charge specific capacity was 341 mAh/g, and the first coulombic efficiency was 87.5%. The rate cycle performance is shown in fig. 4, and can meet the requirements of a sodium ion battery with long service life and high energy density. The amorphous carbon characteristic, interplanar spacing, is exhibited by XRD results shown in FIG. 5d 002 Value of 0.383 nm, crystallite sizeLa is 1.7 nm, and a is,Lc is 1.36 nm. From the Raman results of FIG. 6, it was found thatI D /I G 1.93, the disorder degree of the hard carbon material was large. The specific surface area is 4.94 m 2 G, pore volume 0.006 cm 3 /g。
Example 2:
the preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Weighing 10g of camellia oleifera shell powder as a biomass raw material, soaking the biomass raw material into 60 mL of a mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 500 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) Ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tubular furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1600 ℃ at 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon cathode material for the sodium ion battery.
When the charging and discharging current is 30 mA/g, the first discharging specific capacity of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass reaches 336 mAh/g, the charging specific capacity is 312.5 mAh/g, and the first coulombic efficiency is 93%.
The hard carbon negative electrode material prepared in the embodiment is used for preparing a sodium ion battery negative electrode plate, and the method comprises the following specific steps:
mixing 0.27 g of the hard carbon negative electrode material powder for the sodium ion battery prepared in the embodiment with conductive carbon black, wherein the mass ratio of the hard carbon negative electrode material to the conductive carbon black to the binder PVDF is 18: 1, then dropwise adding N-methyl pyrrolidone into the obtained mixture, stirring for 6 hours, and then coating on a carbon-coated aluminum foil to prepare a negative electrode plate; then a metal sodium sheet is taken as a counter electrode, and 1M NaPF 6 the/DEGDME is used as electrolyte, and the GF/C glass fiber film is used as a diaphragm to assemble the 2016 type button cell. When the charging and discharging current of the hard carbon negative electrode material for the sodium ion battery is 30 mA/g, the first discharging specific capacity is 336 mAh/g, the charging specific capacity is 312.5 mAh/g, and the first coulombic efficiency is 93 percent.
Example 3:
the preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Weighing 10g of camellia oleifera shell powder as a biomass raw material, soaking the biomass raw material into 60 mL of a mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 500 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) Ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tubular furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1400 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon negative electrode material for the sodium ion battery.
The button cell is assembled according to the application method of the embodiment 2, and the first discharge specific capacity of the hard carbon negative electrode material prepared in the embodiment is up to 347.2 mAh/g, the charge specific capacity is 314.2 mAh/g and the first coulombic efficiency is 90.5% under the condition that the charge and discharge current is 30 mA/g.
Example 4:
the preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Weighing 10g of camellia oleifera shell powder as a biomass raw material, soaking the biomass raw material into 60 mL of a mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 500 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) And ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tube furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1100 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon cathode material for the sodium ion battery.
The button battery is assembled according to the application method of the embodiment 2, and the first discharge specific capacity of the hard carbon negative electrode material prepared in the embodiment reaches 377.1 mAh/g, the charge specific capacity is 318.3 mAh/g and the first coulombic efficiency is 84.4% under the condition that the charge and discharge current is 30 mA/g.
Comparative example 1: (only hydrochloric acid alcoholic solution treatment)
When the charge and discharge current of the biomass hard carbon negative electrode material is 30 mA/g, the first discharge specific capacity reaches 320.4 mAh/g, the charge specific capacity is 274.3 mAh/g, and the first coulombic efficiency is 85.6%.
A preparation method of the biomass hard carbon negative electrode material of the comparative example comprises the following steps:
(1) Crushing dried oil tea shells into powder by using a crusher, weighing 10g of oil tea shell powder as a biomass raw material, immersing the biomass raw material into 60 mL of a mixed solution of 1mol/L dilute hydrochloric acid and 50% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extracts in the biomass raw material to obtain brown suspension;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 550 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) And ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tube furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1300 ℃ at 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the biomass hard carbon cathode material.
The button cell is assembled according to the application method of the embodiment 1, and the first discharge specific capacity of the biomass hard carbon negative electrode material of the comparative example is 320.4 mAh/g, the charge specific capacity is 274.3 mAh/g and the first coulombic efficiency is 85.6% when the charge-discharge current is 30 mA/g.
Comparative example 2: (sulfuric acid solution treatment only)
When the charging and discharging current is 30 mA/g, the first discharging specific capacity of the biomass hard carbon negative electrode material of the comparative example reaches 346 mAh/g, the charging specific capacity is 296.6 mAh/g, and the first coulombic efficiency is 85.7 percent.
A preparation method of the biomass hard carbon negative electrode material of the comparative example comprises the following steps:
(1) Crushing dried oil tea fruit shells into powder by using a crusher, weighing 10g of oil tea fruit shell powder as a biomass raw material, adding the raw material into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 h at room temperature to remove ash and introduce oxygen atoms, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 450 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) Ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tubular furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1300 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the biomass hard carbon negative electrode material.
The button cell is assembled according to the application method of the embodiment 1, and the first discharge specific capacity of the biomass hard carbon negative electrode material of the comparative example is 346 mAh/g, the charge specific capacity is 296.6 mAh/g and the first coulombic efficiency is 85.7% when the charge and discharge current is 30 mA/g.
Example 5:
the preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Crushing dried rice hulls into powder by using a crusher, weighing 10g of rice hull powder as a biomass raw material, soaking the rice hull powder into 60 mL of mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 500 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) Ball-milling the obtained pre-carbonized material for 30 min at 500 revolutions per minute, putting the pre-carbonized material into a tube furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1300 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon cathode material for the sodium ion battery.
The button battery is assembled according to the application method of the embodiment 1, under the condition that the charging and discharging current is 30 mA/g, the first discharging specific capacity reaches 344.3 mAh/g, the charging specific capacity is 310.9 mAh/g, and the first coulombic efficiency is 90.3%.
Example 6:
when the charge and discharge current of the hard carbon negative electrode material for the sodium ion battery based on shell biomass is 30 mA/g, the first discharge specific capacity reaches 385.6 mAh/g, the charge specific capacity is 332.8 mAh/g, and the first coulombic efficiency is 86.3%.
The preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Crushing the dried peanut shells into powder by using a crusher, weighing 10g of peanut shell powder as a biomass raw material, soaking the peanut shell powder into 60 mL of a mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 hours at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 550 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) And ball-milling the obtained pre-carbonized material for 60 min at 500 revolutions per minute, putting the pre-carbonized material into a tube furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1300 ℃ at 3 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon cathode material for the sodium ion battery.
The button cell is assembled according to the application method of the embodiment 1, the first discharge specific capacity reaches 385.6 mAh/g under the condition that the charge-discharge current is 30 mA/g, the charge specific capacity is 332.8 mAh/g, and the first coulombic efficiency is 86.3%.
Example 7:
when the charge and discharge current is 30 mA/g, the first discharge specific capacity of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass in the embodiment reaches 376.3 mAh/g, the charge specific capacity is 334.9 mAh/g, and the first coulombic efficiency is 89%.
The preparation method of the hard carbon negative electrode material for the sodium ion battery based on the shell biomass comprises the following specific steps:
(1) Crushing dried coconut shells into powder by using a crusher, weighing 10g of coconut shell powder as a biomass raw material, soaking the biomass raw material into 60 mL of a mixed solution of 0.5 mol/L dilute hydrochloric acid and 30% ethanol, stirring for 6 h at room temperature, and removing ash and ethanol extract in the biomass raw material; filtering, adding the filtrate into 60 mL of sulfuric acid with the molar concentration of 6 mol/L, stirring for 6 hours at room temperature, carrying out oxidation modification, and obtaining brown suspension after the reaction is finished;
(2) Ultrasonically dispersing the obtained brown suspension in water for 30 min, filtering and drying to obtain a precursor, putting the precursor into a tubular furnace filled with argon for pre-pyrolysis carbonization, heating to 500 ℃ at a speed of 10 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain a pre-carbonized material;
(3) And ball-milling the obtained pre-carbonized material for 10 min at 500 revolutions per minute, putting the pre-carbonized material into a tubular furnace filled with argon for high-temperature pyrolysis carbonization, heating to 1300 ℃ at the speed of 5 ℃/min, preserving the temperature for 2 h, and cooling to room temperature to obtain the hard carbon negative electrode material for the sodium ion battery.
The button cell is assembled according to the application method of the embodiment 1, under the condition that the charging and discharging current is 30 mA/g, the first discharging specific capacity reaches 376.3 mAh/g, the charging specific capacity is 334.9 mAh/g, and the first coulombic efficiency is 89%.
Comparative example 3 (one-step carbonization treatment)
The preparation method of the biomass hard carbon negative electrode material comprises the following steps:
pulverizing dried oil tea shell into powder by a pulverizer, weighing 10g of oil tea shell powder, putting the oil tea shell powder into a tube furnace filled with argon for pyrolysis and carbonization, heating to 1300 ℃ at a speed of 10 ℃/min, and preserving heat for 2 h. And after pyrolysis and carbonization, cooling to room temperature, and ball-milling the obtained carbon material for 30 min at the speed of 500 revolutions per minute to obtain the biomass hard carbon negative electrode material. The button cells were assembled according to the application method of example 1.
The specific discharge capacity of the biomass hard carbon negative electrode material prepared in the comparative example reaches 285.5 mAh/g for the first time under the condition of charging and discharging current of 30 mA/g, and the specific charge capacity is 231.4 mAh/g and is lower than that of other examples. The first charge-discharge curve is shown in fig. 7.
Comparative example 4 (one-step carbonization treatment)
The preparation method of the biomass hard carbon negative electrode material comprises the following steps:
and (2) beating the dried rice hulls into powder by using a grinder, weighing 10g of rice hull powder, putting the rice hull powder into a tubular furnace filled with argon for pyrolysis carbonization, heating to 1300 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours. And cooling to room temperature after pyrolysis and carbonization, and ball-milling the obtained carbon material for 30 min at 500 revolutions per minute to obtain the biomass carbon cathode material. The button cells were assembled according to the application method of example 1.
The first discharge specific capacity of the biomass hard carbon negative electrode material prepared by the comparative example is 186.2 mAh/g under the condition of the charge and discharge current of 30 mA/g, and the charge specific capacity is 137.4 mAh/g which is lower than that of other examples.
The comparative example 1 and the comparative example 2 are typical biomass hard carbon negative electrode materials in the prior art, and in order to ensure that the subsequent negative electrode materials can be smoothly smeared on a current collector, the conventional technical means is to perform a ball milling step after high-temperature pyrolysis carbonization, different from the comparative example 1, the pyrolysis carbonization process is divided into two steps, namely, pre-carbonization is performed under the low-temperature condition (400-600 ℃), high-temperature pyrolysis carbonization is performed under the high-temperature condition (1100-1600 ℃), a ball milling step is performed between the pre-carbonization and the high-temperature pyrolysis carbonization, a precursor with uniform particle size and a proper amount of defects is obtained through the low-temperature pre-carbonization and ball milling steps, micropores of the hard carbon negative electrode are increased, and the sodium storage capacity of the hard carbon negative electrode is improved on the premise of ensuring the first coulombic efficiency. By controlling the high-temperature carbonization temperature, the prepared hard carbon cathode has proper micropore and carbon layer spacing, high conductivity, small specific surface area, excellent sodium storage performance, obviously improved first discharge specific capacity and first coulombic efficiency, and has outstanding advantages compared with the prior art.
TABLE 1 comparison of properties of examples and comparative examples of the present application
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed solution, or modify equivalent embodiments using the teachings disclosed above, without departing from the scope of the solution. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall fall within the protection scope of the technical solution of the present invention, unless the technical essence of the present invention departs from the content of the technical solution of the present invention.
Claims (10)
1. A preparation method of a hard carbon negative electrode material for a sodium ion battery based on shell biomass is characterized in that the shell biomass material is used as a biomass raw material, and the preparation steps are as follows:
s1, sequentially immersing a biomass raw material into a hydrochloric acid alcohol solution and a sulfuric acid solution, stirring, removing ash and ethanol extracts in the biomass raw material, and carrying out oxidation modification on functional groups which are easy to oxidize in the biomass raw material to obtain a suspension; the molar concentration of the sulfuric acid solution is 3-6 mol/L;
s2, dispersing the suspension obtained in the step S1 in water, filtering and drying to obtain a precursor;
s3, heating the precursor obtained in the step S2 to 450-550 ℃ under the protection of inert gas for pre-carbonization treatment, cooling and then ball-milling to obtain pre-carbon powder;
and S4, heating the pre-carbon powder obtained in the step S3 to 1100-1600 ℃ under the protection of inert gas, carrying out high-temperature carbonization treatment, and cooling to obtain the hard carbon negative electrode material for the sodium ion battery.
2. The preparation method according to claim 1, wherein the hull biomass material is one or more of oil tea camellia husk, peanut hull, rice hull and coconut hull.
3. The method according to claim 1, wherein in step S1, the biomass raw material is stirred in the hydrochloric acid alcoholic solution for 3-6 hours; the hydrochloric acid alcohol solution is a mixed solution of dilute hydrochloric acid and ethanol, the molar concentration of the dilute hydrochloric acid is 0.1-1 mol/L, and the mass concentration of the ethanol is 20% -70%; the volume ratio of the mass of the biomass raw material to the sulfuric acid solution is 10-60 g: 60 And (mL).
4. The method according to claim 1, wherein in the step S2, the dispersion is ultrasonic dispersion, and the time of ultrasonic dispersion is 30 to 60 min.
5. The production method according to claim 1, wherein in step S3, the temperature increase rate of the temperature increase is 5 to 10 ℃/min; the temperature of the pre-carbonization treatment is 450-550 ℃; the time of the pre-carbonization treatment is 1-3h.
6. The preparation method of claim 1, wherein in the step S3, the rotation speed of the ball mill is 300-700 r/min, and the ball milling time is 0.5-2 h.
7. The preparation method according to claim 1, wherein in step S4, the temperature rise rate of the temperature rise is 3-10 ℃/min, and the time of the high-temperature carbonization treatment is 1-4 h.
8. The hard carbon negative electrode material for the sodium ion battery prepared by the preparation method of any one of claims 1 to 7 is characterized by being amorphous carbon, the particle size of the amorphous carbon is 1-20 mu m, and the interplanar spacing d 002 The value is 0.36-0.4 nm, the crystallite size L a is 1-5 nm, L c is 1-5 nm, I D /I G 1-3, specific surface area less than 15 m 2 Per g, pore volume of 0-0.1 cm 3 /g。
9. A preparation method of a negative electrode plate of a sodium ion battery is characterized by comprising the following specific steps:
mixing the hard carbon negative electrode material for the sodium ion battery, conductive carbon black and a binder, and uniformly stirring to obtain electrode slurry;
and coating the electrode slurry on a current collector, drying and then stamping to obtain the negative electrode plate of the sodium-ion battery.
10. A sodium-ion battery, which comprises a negative electrode, a positive electrode, a diaphragm and electrolyte, and is characterized in that the negative electrode is the negative electrode plate of the sodium-ion battery prepared by the preparation method according to claim 9.
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| CN115418749A (en) * | 2022-09-13 | 2022-12-02 | 陕西科技大学 | Preparation method and application of microcrystalline graphite fiber negative electrode material |
| CN115231548B (en) * | 2022-09-20 | 2023-01-13 | 中国科学院山西煤炭化学研究所 | High-capacity modified natural polymer-based hard carbon material and preparation and application thereof |
| CN115650202B (en) * | 2022-10-18 | 2023-06-16 | 仲恺农业工程学院 | Durian shell-based hard carbon negative electrode material and preparation method thereof |
| CN116040605A (en) * | 2022-12-22 | 2023-05-02 | 广东容钠新能源科技有限公司 | High-performance hard carbon negative electrode material for high-temperature sodium ion battery and preparation method thereof |
| CN116443845A (en) * | 2023-03-09 | 2023-07-18 | 河南克能新能源科技有限公司 | Preparation method of low-cost sodium ion battery anode material and battery thereof |
| CN116979064B (en) * | 2023-09-25 | 2024-02-06 | 宁德时代新能源科技股份有限公司 | Carbon material and preparation method thereof, negative electrode plate, secondary battery and power utilization device |
| CN117228658B (en) * | 2023-11-10 | 2024-01-30 | 赣州立探新能源科技有限公司 | Deashing hard carbon material and preparation method and application thereof |
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