CN114335531A - Sulfur-doped hard carbon material and preparation method and application thereof - Google Patents
Sulfur-doped hard carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of potassium ion batteries, and particularly relates to a heteroatom-doped carbon-based material with high reversible capacity and high stability, and further discloses a preparation method and potassium storage application thereof. The heteroatom doped carbon-based negative electrode material with high reversible capacity and high stability is prepared by taking polystyrene as a carbon source and sublimed sulfur as a sulfur source through an in-situ vulcanization method under an inert gas atmosphere. The sulfur-doped hard carbon material is mixed with a binder and a conductive agent according to a certain proportion, and is pyrolyzed at high temperature to prepare the potassium ion battery cathode material. The sulfur-doped hard carbon material overcomes the volume deformation of the conventional potassium ion battery negative electrode material in the charging and discharging processes, and effectively improves the cycle performance of the battery; meanwhile, the doping of sulfur atoms can provide additional active sites for the adsorption of potassium ions, and the specific capacity of the battery is improved. The negative electrode material not only can show higher reversible capacity and stable cycle performance under lower current density, but also can keep the capacity at 95.2% after 1000 cycles, and can keep good stability after 5200 cycles under high current density.
Description
Technical Field
The invention belongs to the technical field of potassium ion battery cathode materials, and particularly relates to a sulfur-doped hard carbon material with high reversible capacity and high stability, and further discloses a preparation method and potassium storage application thereof.
Background
Over the past decades, withThe rapid consumption and rising cost of fossil fuels, as well as the increasing global concern for environmental pollution, the development of renewable, efficient energy storage devices has become critical. Generally, lithium ion batteries have become the dominant technology for portable energy storage and large-scale electrical energy storage, and have considerable application prospects due to their high energy density, long cycle life, and high energy conversion efficiency. However, with the rapid development of portable electronic devices and the increasing demand for energy, Lithium Ion Batteries (LIBs) are increasingly difficult to meet due to resource shortage and uneven distribution. This therefore prompted researchers to look for alternatives to LIBs. Potassium Ion Batteries (PIBs) are considered a promising alternative to LIBs due to their abundant potassium resources, high operating voltages and faster ionic conductivity in electrolytes. In addition, the standard redox potential (-2.93V) of potassium ions is closer to that of lithium ions (-3.04V), and thus PIBs can provide higher energy density compared to LIBs. However, the potassium ion has a large ionic radius
It is easy to cause structural changes of the electrode material during insertion/extraction, thereby adversely affecting the long-cycle stability of the battery. Therefore, the development of PIBs electrode materials having excellent electrochemical properties is urgently required.
For the negative electrodes of PIBs, carbon-based materials are of great interest because of their low cost, abundant resources, high ionic conductivity, and stable physicochemical properties. Previous researches show that by selecting the precursor, the carbon materials such as graphite, hard carbon, soft carbon and the like can be prepared, and ideal potassium storage performance is obtained. Among various precursors, polymers are widely used due to the advantages of high molecular weight, excellent performance, convenient preparation, abundant raw material sources and the like. In 2016, hard carbon microspheres taking sucrose as a precursor are reported to serve as negative electrodes of PIBs for the first time, and the capacity of the negative electrodes is up to 262mA h g under the condition of C/10 current density-1. Some researchers take polyacrylonitrile as a precursor to develop nitrogen-doped porous carbon nanofibers as the negative electrode of the PIBs, and better cycling stability is provided. In addition, researchers have also utilized poly (m-phenylene)Polymers such as diamine, melamine and the like are used as precursors to prepare hollow carbon spheres and carbon nanotubes with hard carbon structures, and the electrochemical performance of the hollow carbon spheres and the carbon nanotubes on PIBs is explored. However, the preparation of these materials is relatively cumbersome, some require hydrothermal or electrospinning methods to prepare the precursors, while others require chemical etching to obtain porous or hollow structures, which makes them difficult to apply to PIBs on a large scale. Compared with other polymers, the Polystyrene (PS) is composed of a main saturated carbon chain and a side conjugated benzene ring, and is a material with low cost, mature preparation method and rich resources. More importantly, the hard carbon material with rigid structure and large interlayer spacing can be obtained by carbonizing the polystyrene. Previous studies have found that PS is easily decomposed into volatile small-molecule organic compounds during pyrolysis, resulting in very low yields of carbonized products. Therefore, there is a need to find an improved method for preparing PS with high yield, simple preparation process and low cost.
Recent research on carbon materials doped with heteroatoms (such as N, O, S and P) shows that the potassium storage performance of the carbon material is remarkably improved by adjusting the electronic structure and chemical properties of the carbon material. Among them, sulfur doping is an effective way to improve the electrochemical performance of LIBs, SIBs and PIBs. Specifically, the difference in electronegativity between the carbon atom and the sulfur atom is beneficial to provide additional reaction sites and to adsorb more metal ions, thereby providing additional reversible storage capacity for the battery. More importantly, the bond between sulfur and carbon can effectively inhibit the loss of the material in the carbonization process, thereby improving the carbonization yield. Therefore, the design idea of the present work is to prepare a high-yield sulfur atom-doped carbonized material by a one-step in-situ sulfidation method without adding any crosslinking agent and catalyst, and to explore its electrochemical performance as a negative electrode of PIBs.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the invention is to provide a preparation method of a potassium ion battery negative electrode material.
The other purpose of the invention is to provide the potassium ion battery cathode material prepared by the method, which is a sulfur-doped hard carbon material.
The present invention also provides the application of the sulfur-doped hard carbon material in a potassium ion battery to solve the problems in the background art.
The above object of the present invention is achieved by the following embodiments:
a preparation method of a sulfur-doped hard carbon material specifically comprises the following steps:
(1) dissolving a dispersion stabilizer in a reaction medium, taking a styrene monomer as a precursor, uniformly reacting with an initiator, heating, reacting, centrifuging, washing, and freeze-drying to obtain the required hard carbon precursor polystyrene;
(2) and (2) under protective gas, mixing the product obtained in the step (1) with a sulfur source and carrying out vulcanization treatment to obtain the sulfur-doped hard carbon material, namely the potassium ion battery cathode material.
Further, in the step (1), the dispersion stabilizer is polyvinylpyrrolidone, and the mass is 0.01 g; the particle size of the polystyrene microspheres is reduced by increasing the amount of polyvinylpyrrolidone.
Further, the reaction medium in the step (1) is any one of a water/ethanol mixed solution and ethanol.
Further, in the step (1), the initiator is any one of ammonium persulfate and potassium persulfate, and the using amount is 1 mmol; the increase of the initiator dosage increases the particle size of the polystyrene microsphere.
Further, the heating reaction in the step (1) is carried out at the temperature of 70 ℃ for 18 h.
Further, the vulcanization treatment in the step (2) is to use a tube furnace at 1-5 ℃ for min-1The temperature rise rate is 500-800 ℃ and the vulcanizing time is 2 h.
Further, the mass ratio of the polystyrene to the sulfur source in the step (2) is 1: 1-5.
A sulfur-doped hard carbon material is prepared by the preparation method.
The application of the sulfur-doped hard carbon material in the preparation of the potassium ion battery comprises the following steps:
adding the sulfur-doped hard carbon material, the conductive agent Ketjen black and the binder sodium carboxymethyl cellulose into a mixed solution of ethanol and water, and stirring to form uniform slurry; then uniformly coating the slurry on a current collector; drying and slicing to obtain the potassium ion battery cathode material.
Further, the sulfur-doped hard carbon material, the conductive agent Ketjen black and the adhesive carboxymethylcellulose sodium are stirred according to the mass ratio of 8:1: 1.
Further, the diameter of the current collector is 12mm, and the current collector is a copper foil current collector.
Further, the drying temperature is 60 ℃, and the drying time is 12 h.
According to the invention, through simple and low-cost scientific design, the sulfur-doped hard carbon material is prepared by in-situ vulcanization of polystyrene and sulfur powder. The obvious innovation of the material is that the preparation process of the sulfur-doped hard carbon material is simple and easy to operate, low in cost and convenient for large-scale application. In the in-situ vulcanization process, the covalent bonding of sulfur and carbon can effectively inhibit the material loss in the carbonization process, and greatly improve the carbonization yield (nearly 100%) of PS. In performance, on one hand, sulfur atoms doped in the carbon matrix provide more active sites for the adsorption of potassium ions, and the reversible capacity of the material is increased. On the other hand, the sulfur-doped hard carbon material has large interlayer distance and specific surface area, is beneficial to the intercalation/deintercalation of potassium ions, and improves the stability of the electrode material. The sulfur-doped hard carbon material can be used at a current density of 100mA g-1Circulating for 1000 times, the capacity is 298.1mAh g-1The capacity retention was about 95.2%. Even at 500mA g-1Is circulated 5200 times at a high current density and still has a g of 220.2mAh-1The reversible specific capacity of (a).
Compared with the prior art, the invention has the following beneficial effects:
(1) the method takes the polystyrene as a carbon source and the sulfur powder as a sulfur source, generates the sulfur-doped hard carbon material through in-situ vulcanization, has simple preparation method and low cost, and is easy to realize industrial application.
(2) In the sulfur-doped hard carbon material designed by the invention, the sulfur-doped hard carbon material has larger interlayer spacing, and meets the requirements of potassium ion intercalation and deintercalation; the specific surface area is large, the contact area with the electrolyte is increased, and the effective mass transfer of potassium ions is met; abundant active sites increase the adsorption of potassium ions. The lithium ion battery cathode material has high reversible capacity and cycle stability.
(3) The sulfur-doped hard carbon material designed by the invention is used as a potassium ion battery cathode material, and the current density is 100mA g-1Circulating for 1000 times, the capacity is 298.1mAh g-1The capacity retention was about 95.2%. At 500mA g-1Has 220.2mAh g after 5200 cycles-1The reversible specific capacity of (a).
It can be seen that the technical problem to be solved by the present invention is to provide an electrode material with low production cost, simple preparation, high reversible capacity and good stability.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a TEM image of the polystyrene prepared in example 2.
Fig. 2 is a TEM image of a sulfur-doped hard carbon material obtained after in-situ vulcanization of polystyrene and sulfur powder prepared in example 2.
Fig. 3 is a graph showing the cycle performance of the sulfur-doped hard carbon material prepared in example 2 as a negative electrode of a potassium ion battery at a low current density.
Fig. 4 is a graph of the cycle performance of the sulfur-doped hard carbon material prepared in example 2 as a negative electrode of a potassium ion battery at high current density.
Fig. 5 is a graph showing rate performance of the sulfur-doped hard carbon material prepared in example 2 as a negative electrode of a potassium ion battery.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, which are only a part of examples of the present invention, but not all examples.
Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
(1) 0.01g of polyvinylpyrrolidone (PVP, K-30) was dissolved in 25mL of absolute ethanol, and stirred until dissolved. Then 2.2mL of styrene monomer was added to the solution and the reactor was transferred to a 70 ℃ oil bath and magnetic stirring was continued until the mixture was homogeneous. Then, 0.23g of ammonium persulfate was dissolved in 3mL of ultrapure water, and was dropwise added to the above-mentioned reactor after completion of the stirring. Stirring was then continued at 70 ℃ for 18 hours and the reaction was quenched immediately after completion with cold water. The sample was transferred to a centrifuge tube, centrifuged at 3500rpm for 10min, and washed with absolute ethanol and ultrapure water several times, respectively. After freezing in a refrigerator, the resulting product was transferred to a vacuum freeze dryer and dried for 16 hours to obtain Polystyrene Spheres (PS).
(2) Mixing 0.2g PS ball and 0.2g, 0.6g, 1.0g sulfur powder, grinding for 30min, and heating at 5 deg.C for 5 min under nitrogen atmosphere-1And annealing at 600 ℃ for 2h to obtain the sulfur-doped hard carbon material.
(3) 0.08g of the sulfur-doped hard carbon material prepared in the embodiment, 0.01g of Ketjen black and 0.01g of sodium carboxymethylcellulose are mixed and ground, then transferred into a small weighing bottle, 0.8g of ethanol and water mixed solution (1:4) is added for magnetic stirring, the formed uniform slurry is coated on a copper foil current collector, dried at 60 ℃ for 12 hours, sliced into electrode slices of 12mm, and assembled into a CR2032 type button cell in a glove box filled with argon by using a metal potassium block as a counter electrode.
Example 2
(1) 0.01g of polyvinylpyrrolidone (PVP, K-30) was dissolved in 25mL of absolute ethanol, and stirred until dissolved. Then 2.2mL of styrene monomer was added to the solution and the reactor was transferred to a 70 ℃ oil bath and magnetic stirring was continued until the mixture was homogeneous. Then, 0.23g of ammonium persulfate was dissolved in 3mL of ultrapure water, and was dropwise added to the above-mentioned reactor after completion of the stirring. Stirring was then continued at 70 ℃ for 18 hours and the reaction was quenched immediately after completion with cold water. The sample was transferred to a centrifuge tube, centrifuged at 3500rpm for 10min, and washed with absolute ethanol and ultrapure water several times, respectively. After freezing in a refrigerator, the sample was transferred to a vacuum freeze dryer and dried for 16 hours to obtain PS.
(2) Mixing and grinding 0.2g PS balls and 0.6g sulfur powder for 30min, and heating at 5 deg.C for 5 min under nitrogen atmosphere-1And annealing at 600 ℃ for 2h to obtain the sulfur-doped hard carbon material.
(3) The assembled CR2032 type button cell was produced in the same manner as in example 1.
Example 3
(1) 0.01g of polyvinylpyrrolidone (PVP, K-30) was dissolved in 25mL of absolute ethanol, and stirred until dissolved. Then 2.2mL of styrene monomer was added to the solution and the reactor was transferred to a 70 ℃ oil bath and magnetic stirring was continued until the mixture was homogeneous. Then, 0.23g of ammonium persulfate was dissolved in 3mL of ultrapure water, and was dropwise added to the above-mentioned reactor after completion of the stirring. Stirring was then continued at 70 ℃ for 18 hours and the reaction was quenched immediately after completion with cold water. The sample was transferred to a centrifuge tube, centrifuged at 3500rpm for 10min, and washed with absolute ethanol and ultrapure water several times, respectively. After freezing in a refrigerator, the sample was transferred to a vacuum freeze dryer and dried for 16 hours to obtain PS.
(2) Mixing and grinding 0.2g PS balls and 1.0g sulfur powder for 30min, and heating at 5 deg.C for 5 min under nitrogen atmosphere-1And annealing at 600 ℃ for 2h to obtain the sulfur-doped hard carbon material.
(3) The assembled CR2032 type button cell was produced in the same manner as in example 1.
Example 4
0.01g of polyvinylpyrrolidone (PVP, K-30) was dissolved in 25mL of absolute ethanol, and stirred until dissolved. Then 2.2mL of styrene monomer was added to the solution and the reactor was transferred to a 70 ℃ oil bath and magnetic stirring was continued until the mixture was homogeneous. Then, 0.23g of ammonium persulfate was dissolved in 3mL of ultrapure water, and was dropwise added to the above-mentioned reactor after completion of the stirring. Stirring was then continued at 70 ℃ for 18 hours and the reaction was quenched immediately after completion with cold water. The sample was transferred to a centrifuge tube, centrifuged at 3500rpm for 10min, and washed with absolute ethanol and ultrapure water several times, respectively. After freezing in a refrigerator, the sample was transferred to a vacuum freeze dryer and dried for 16 hours to obtain PS.
(2) 0.2g of PS beads and 06g of sulfur powder was mixed and ground for 30min at 5 ℃ in a nitrogen atmosphere-1And annealing at 500 ℃ for 2h to obtain the sulfur-doped hard carbon material.
(3) The assembled CR2032 type button cell was produced in the same manner as in example 1.
Example 5
0.01g of polyvinylpyrrolidone (PVP, K-30) was dissolved in 25mL of absolute ethanol, and stirred until dissolved. Then 2.2mL of styrene monomer was added to the solution and the reactor was transferred to a 70 ℃ oil bath and magnetic stirring was continued until the mixture was homogeneous. Then, 0.23g of ammonium persulfate was dissolved in 3mL of ultrapure water, and was dropwise added to the above-mentioned reactor after completion of the stirring. Stirring was then continued at 70 ℃ for 18 hours and the reaction was quenched immediately after completion with cold water. The sample was transferred to a centrifuge tube, centrifuged at 3500rpm for 10min, and washed with absolute ethanol and ultrapure water several times, respectively. After freezing in a refrigerator, the sample was transferred to a vacuum freeze dryer and dried for 16 hours to obtain PS.
(2) Mixing and grinding 0.2g PS balls and 0.6g sulfur powder for 30min, and heating at 5 deg.C for 5 min under nitrogen atmosphere-1And annealing at 700 ℃ for 2h to obtain the sulfur-doped hard carbon material.
(3) The assembled CR2032 type button cell was produced in the same manner as in example 1.
Comparative example 1
The difference from example 1 is that 0.2g of PS are directly introduced under a nitrogen atmosphere at 5 ℃ for min-1And annealing at 600 ℃ for 2h to obtain the hard carbon material.
Comparative example 2
The difference from example 1 is that 0.2g of commercial activated carbon and 0.6g of sulfur powder were mixed and ground for 30min at 5 ℃ for 5 min under a nitrogen atmosphere-1And annealing at 600 ℃ for 2h to obtain the sulfur-doped activated carbon material.
Comparative example 3
The difference from example 1 is that 0.2g of commercial carbon nanotubes and 0.6g of sulfur powder were mixed and ground for 30min at 5 ℃ for min under a nitrogen atmosphere-1And annealing at 600 ℃ for 2h to obtain the sulfur-doped carbon nanotube material.
Comparative example 4
The difference from example 1 is that 0.2g of commercial graphene and 0.6g of sulfur powder were mixed and ground for 30min at 5 ℃ for min under a nitrogen atmosphere-1And annealing at 600 ℃ for 2h to obtain the sulfur-doped graphene material.
Performance testing
The sulfur-doped hard carbon material prepared in the above embodiment is subjected to a performance test, and the specific method is as follows:
(1) the materials prepared in the above examples were characterized by X-ray diffraction (XRD), Raman spectroscopy (Raman), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), BET specific surface area measurement, thermogravimetric analysis (TGA), and the like. The morphology, structure and specific surface area of the material are analyzed.
(2) And (3) testing the electrochemical performance of the potassium ion battery: the prepared sulfur-doped hard carbon material is assembled into a button cell, a Newwei cell test system is adopted to carry out constant current charge and discharge test at room temperature, and the current density of the cell test is 100mA g-1. It was subjected to Cyclic Voltammetry (CV) and ac impedance testing using an electrochemical workstation.
TABLE 1
The invention provides a sulfur-doped hard carbon material as a negative electrode material of a potassium ion battery, and an electrode material with the best performance is found by changing the doping amount and pyrolysis temperature of sulfur. By comparing 5 examples and 4 comparative examples, it is found that the sulfur-doped hard carbon material prepared in example 2, namely the PS/sulfur doping mass ratio is 1:3, and the heat treatment temperature is 600 ℃, has better electrochemical performance as the cathode material of the potassium ion battery, and can be used as 100mA g-1298.1mAh g is kept after 1000 cycles of circulation under current density-1The reversible capacity of (a).
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The sulfur-doped hard carbon negative electrode material of the potassium ion battery is characterized in that the sulfur-doped hard carbon material has a large interlayer spacing of 0.372-0.382 nm; the specific surface area is 69-193m2/g；
The sulfur-doped hard carbon material is prepared by the following method, and the method comprises the following steps:
(1) dissolving a dispersion stabilizer in a reaction medium, taking a styrene monomer as a precursor, uniformly reacting with an initiator, heating, reacting, centrifuging, washing, and freeze-drying to obtain the required hard carbon precursor polystyrene;
(2) and (2) under protective gas, mixing the product obtained in the step (1) with sulfur powder and carrying out vulcanization treatment to obtain the sulfur-doped hard carbon material, namely the potassium ion battery cathode material.
2. The method for preparing a sulfur-doped hard carbon material according to claim 1, wherein the dispersion stabilizer in the step (1) is polyvinylpyrrolidone; the reaction medium is at least one of water/ethanol mixed solution and ethanol.
3. The method for preparing the sulfur-doped hard carbon material according to claim 1, wherein the initiator in the step (1) is at least one of ammonium persulfate and potassium persulfate.
4. The method for preparing sulfur-doped hard carbon material as claimed in claim 1, wherein the sulfidation treatment in step (2) is carried out by heating the tube furnace to 800 ℃ at a heating rate of 1-5 ℃/min and then maintaining the temperature for 2 h.
5. The method for preparing the sulfur-doped hard carbon material according to claim 1, wherein the mass ratio of the polystyrene to the sulfur source in the step (2) is 1: 1-5.
6. A sulfur-doped hard carbon material having a high reversible capacity and a high stability, which is produced by the production method according to any one of claims 1 to 5.
7. The sulfur-doped hard carbon material with high reversible capacity and high stability for the potassium ion battery according to claim 6, comprising the following steps:
adding the sulfur-doped hard carbon material, the conductive agent Ketjen black and the binder sodium carboxymethyl cellulose into a mixed solution of ethanol and water, and stirring to form uniform slurry; then uniformly coating the slurry on a current collector; drying and slicing to obtain the potassium ion battery cathode material.
8. The use according to claim 7, wherein the sulfur-doped hard carbon material, the conductive agent Ketjen black, and the binder carboxymethylcellulose sodium are stirred in a mass ratio of 8:1: 1; the diameter of the current collector is 12mm, and the current collector is a copper foil current collector; the drying temperature is 60 ℃, and the drying time is 12 h.
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