CN109301246B - Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode - Google Patents

Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode Download PDF

Info

Publication number
CN109301246B
CN109301246B CN201811142962.5A CN201811142962A CN109301246B CN 109301246 B CN109301246 B CN 109301246B CN 201811142962 A CN201811142962 A CN 201811142962A CN 109301246 B CN109301246 B CN 109301246B
Authority
CN
China
Prior art keywords
sulfur
carbon material
hard carbon
acid solution
doped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811142962.5A
Other languages
Chinese (zh)
Other versions
CN109301246A (en
Inventor
王庆
王昭雄
罗绍华
王志远
张亚辉
刘延国
郝爱民
高成林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University Qinhuangdao Branch
Original Assignee
Northeastern University Qinhuangdao Branch
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeastern University Qinhuangdao Branch filed Critical Northeastern University Qinhuangdao Branch
Priority to CN201811142962.5A priority Critical patent/CN109301246B/en
Publication of CN109301246A publication Critical patent/CN109301246A/en
Application granted granted Critical
Publication of CN109301246B publication Critical patent/CN109301246B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a sulfur-doped hard carbon material, a preparation method thereof and a potassium ion battery using the same as a negative electrode. The preparation method of the hard carbon material comprises the following steps: (1) pickling high-sulfur coal, and then soaking the high-sulfur coal in alkaline solution to obtain a pre-product; (2) carrying out heat treatment on the pre-product in a protective atmosphere to prepare a hard carbon material; (3) and (3) carrying out acid solution soaking, washing, filtering and drying on the hard carbon material. The invention takes high-sulfur coal as raw material, the pore size of the prepared hard carbon material can meet the requirement of potassium ion intercalation/deintercalation, and meanwhile, sulfur element is self-doped on the surface of the material and in a carbon matrix in situ, so that the material is endowed with new electrochemical activity and more ideal pore channel structure. The sulfur element in the carbon material prepared by the method is distributed more uniformly, and the production cost is lower.

Description

Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode
Technical Field
The invention belongs to the technical field of hard carbon materials, and particularly relates to a sulfur-doped hard carbon material, a preparation method thereof and a potassium ion battery using the sulfur-doped hard carbon material as a negative electrode.
Background
At present, a new generation of secondary batteries has attracted the wide interest of scientific researchers, and lithium ion batteries have the outstanding advantages of high energy density, long cycle life, no pollution and the like, have become the mainstream of the battery market, and are beginning to be applied to driving electric vehicles. However, with the large-scale application of lithium ion batteries, the price and the resource limitation of lithium are worried more and more. In recent years, many new alternative energy storage batteries have been produced and rapidly developed, mainly including secondary batteries of sodium ions, potassium ions, magnesium ions, calcium ions, and the like.
The potassium ion battery has many advantages as a novel alternative energy storage battery, and the potassium source has rich content in the earth crust and low price; the standard reduction potential of the potassium ion battery is closest to that of the lithium ion battery, so that the energy density is high; the electrolyte of the potassium ion battery has high electrochemical activity and is beneficial to the transmission of ions and electrons. The negative electrode materials of the potassium ion batteries reported at present have less research, and the research is focused on carbon materials, however, the carbon negative electrode performance generally used for lithium and sodium ion batteries is poor due to the overlarge radius of potassium ions and the higher chemical activity of potassium.
CN105810914A discloses a sulfur-doped porous carbon material for a sodium ion battery and a preparation method thereof, wherein the sulfur-doped porous carbon material is formed by chemically doping sulfur in the carbon material, and the carbon material has a loose and porous spongy structure. The preparation method comprises the steps of preparing a metal organic framework material from metal inorganic salt and an organic ligand through an in-situ growth method, grinding and mixing the metal organic framework material and sulfur powder, placing the mixture in an inert gas, performing low-temperature heat treatment, performing high-temperature carbonization, and washing and drying a carbonized product to obtain the metal organic framework material. The sulfur-doped porous carbon material prepared by the method has excellent long-cycle stability, good rate performance, high specific capacity and the like when used as the cathode of the sodium ion battery, but the preparation process is complex, the controllability is poor, and the industrial production is difficult.
CN107317015A discloses a method for preparing a potassium ion battery by taking a zinc oxide/carbon composite material as a negative electrode, which is to prepare a potassium ion battery negative electrode material by adopting a high-temperature solid-phase sintering combination method, regulate and control technical parameters in a reaction process in the preparation process to obtain the zinc oxide/carbon composite material, and take the zinc oxide/carbon composite material as the negative electrode material of the potassium ion battery to prepare the potassium ion battery. The synthesis method is simple, the operation steps are controllable, the expanded production is easy, but the performance of the prepared material can not meet the performance requirement of the potassium ion battery.
CN108039464A discloses a self-supporting sodium/potassium ion battery material, a preparation method and an application thereof, wherein the self-supporting sodium/potassium ion battery material is specifically a porous sulfur-doped graphene aerogel, the sulfur content of the aerogel is 2-10 wt%, and the structure is a three-dimensional structure formed by self-assembly of flaky graphene. The graphene oxide aqueous solution is firstly reacted with ammonia water and then is frozen and dried to obtain graphene aerogel, and then the graphene oxide aqueous solution is reacted with sulfur steam at a high temperature to obtain the porous sulfur-doped graphene aerogel. The porous sulfur-doped graphene aerogel can be used for a sodium/potassium ion battery cathode in a self-supporting manner after being compacted. The sodium/potassium ion battery with the porous sulfur-doped graphene aerogel as the negative electrode has excellent cycle performance and rate performance, but the preparation method is complex and industrial production cannot be realized.
Therefore, the carbon negative electrode material for the potassium ion battery needs to be developed in the field, so that the carbon negative electrode material has a stable structure, a proper electrochemical potassium-intercalation platform and a large specific capacity, and is suitable for industrial production.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a sulfur-doped hard carbon material having a porous structure with sulfur atoms at least partially distributed within the hard carbon material.
The porous carbon material designed by the invention can match the requirements of a potassium ion battery on a negative electrode material, and the doping of sulfur atoms can increase the interlayer spacing of the carbon material and obtain a more ideal pore channel structure, thereby meeting the requirements of potassium ion embedding/removing.
In the sulfur-doped carbon material provided by the invention, sulfur atoms can replace carbon sites in a carbon matrix, and because the electronegativity of the sulfur atoms is similar to that of the carbon atoms, but the radius of the sulfur atoms is larger than that of the carbon atoms, the sulfur atoms doped in the hard carbon material can break the original balance structure of the hard carbon material, endow the material with new electrochemical activity and a more ideal pore channel structure, and are more favorable for the migration and diffusion process of potassium ions. The existence of the sulfur atom can improve the specific capacity of the material on one hand and can endow the hard carbon material with new electrochemical activity on the other hand.
The sulfur atoms are at least partially distributed in the hard carbon material, namely the sulfur atoms are distributed on the surface and in the hard carbon material or the sulfur atoms are completely distributed in the hard carbon material.
Preferably, the sulfur content in the hard carbon material of the present invention is 2 to 10 wt%, for example, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, etc.
Preferably, the hard carbon material has a hierarchical pore structure.
Further preferably, the hard carbon material has micropores, mesopores and macropores distributed therein.
Micropores are called with the aperture less than 2nm, mesopores are called with the aperture of 2-50 nm, and macropores are called with the aperture of more than 50 nm.
Preferably, the hard carbon material has a pore size distribution of 0.5nm to 2 μm, such as 1nm, 2nm, 10nm, 20nm, 500nm, 200nm, 500nm, 1 μm, and the like.
The hard carbon material has too small aperture, which causes difficult potassium ion embedding/removing in the charging and discharging process; the hard carbon material has too large pore diameter, few active sites and easily collapsed structure.
Preferably, the specific surface area of the hard carbon material is 280-1189 m2G, e.g. 300m2/g、400m2/g、500m2/g、600m2/g、700m2/g、800m2/g、1000m2And/g, etc.
The hard carbon material has too small a surface area to provide more storage active sites.
The invention also aims to provide a preparation method of the sulfur-doped hard carbon material, which comprises the following steps:
(1) pickling high-sulfur coal, and then soaking the high-sulfur coal in alkaline solution to obtain a pre-product;
(2) and (3) carrying out heat treatment on the pre-product in a protective atmosphere to obtain the hard carbon material.
The invention adopts high-sulfur coal (the sulfur content is more than or equal to 3 wt%) as a raw material, prepares the sulfur-doped hard carbon material by in-situ self-doping, and prepares a graded porous structure suitable for a potassium ion battery by utilizing the graded tubular cellular structure of the high-sulfur coal, and simultaneously, the sulfur element in the high-sulfur coal can improve the specific capacity and the electrochemical activity of the material.
The in-situ autodoping can ensure that sulfur atoms not only exist on the surface of the material, but also a part of the sulfur atoms exist in the carbon matrix, thereby breaking the original balance structure of the hard carbon material and endowing the material with new electrochemical activity and a more ideal pore channel structure.
Preferably, the sulfur content of the high-sulfur coal of the present invention is 3 to 8 wt%, for example, 4 wt%, 5 wt%, 6 wt%, 7 wt%, etc.
Preferably, the pickling process in step (1) comprises: and (3) crushing the high-sulfur coal, soaking the crushed high-sulfur coal in an acid solution, filtering and drying.
Preferably, the acid solution comprises a hydrochloric acid solution and/or a hydrofluoric acid solution.
Preferably, the concentration of the hydrochloric acid solution is 0.5-5 mol/L, such as 1mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L and the like.
Preferably, the concentration of the hydrofluoric acid solution is 0.1-1 mol/L, such as 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, and the like.
Preferably, the acid washing time is 12-28 h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h and the like.
The acid wash can remove ash (minerals) from the high sulfur coal, avoiding its effect on the electrochemical performance of the hard carbon material.
Preferably, the mass ratio of the solute to the acid-washed high-sulfur coal in the alkaline solution in the step (1) is 0.5:1 to 4:1, such as 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, and the like.
The mass ratio of solute in the alkaline solution to the high-sulfur coal after acid washing is less than 0.5:1, the content of the activating agent is too small, and a large specific surface area is difficult to generate; the mass ratio of the solute in the alkaline solution to the high-sulfur coal after acid washing is more than 4:1, a large number of micropores are generated, and further the pore structure is damaged, and the mechanical strength is reduced.
Preferably, the alkaline solution comprises a KOH solution and/or a NaOH solution.
Preferably, the time for immersing in the alkaline solution is 12-28 h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, and the like.
Preferably, the drying process is freeze drying.
Preferably, the heat treatment temperature in the step (2) of the present invention is 600 to 900 ℃, for example, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, etc.
The heat treatment temperature is higher than 900 ℃, which may cause the graphitization degree of the carbon material to be increased, reduce the interlayer spacing and influence the intercalation and deintercalation of potassium ions; the heat treatment temperature is lower than 600 ℃, which may cause the conversion of coal to carbon and incomplete pore forming of the activating agent, thereby affecting the potassium storage performance.
Preferably, the heating rate of the heat treatment is 0.5-5 ℃/min, such as 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, and the like.
Preferably, the time of the heat treatment is 1-6 h, such as 2h, 3h, 4h, 5h and the like.
Preferably, the protective atmosphere comprises an inert atmosphere, preferably comprising any one or a combination of at least two of a nitrogen atmosphere, an argon atmosphere and a helium atmosphere, such as an argon atmosphere, a nitrogen atmosphere and the like.
Preferably, step (2) of the present invention is followed by step (3): and (3) carrying out acid solution soaking, washing, filtering and drying on the hard carbon material.
Preferably, the acid solution comprises a hydrochloric acid solution and/or a hydrofluoric acid solution.
Further preferably, the acid solution is a hydrochloric acid solution.
Preferably, the concentration of the acid solution is 0.5-5 mol/L, such as 1mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, and the like.
Preferably, the acid washing time is 6-24 h, such as 7h, 8h, 9h, 10h, 11h, 12h, 13h, 15h, 17h, 19h, 21h, 23h and the like.
Preferably, the washing comprises a deionized water washing.
Preferably, the drying temperature is 80-120 ℃, such as 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ and the like.
As a preferred technical scheme, the preparation method of the sulfur-doped hard carbon material comprises the following steps:
(1) pickling high-sulfur coal with 3-8% of sulfur in an acid solution for 12-28 h, soaking in an alkaline solution for 12-28 h, wherein the mass ratio of the solute of the alkaline solution to the pickled high-sulfur coal is 0.5: 1-4: 1, and freeze-drying to obtain a pre-product;
(2) carrying out heat treatment on the pre-product at the temperature of 600-900 ℃ at the heating rate of 0.5-5 ℃/min, and preserving heat for 1-6 h to obtain a hard carbon material;
(3) soaking the hard carbon material in 0.5-5 mol/L hydrochloric acid solution for 6-24 h, washing with deionized water, filtering and drying at 80-120 ℃.
It is a further object of the present invention to provide the use of a sulfur-doped hard carbon material as described in one of the objects for use in the field of batteries, preferably in the field of potassium ion batteries.
Preferably, the hard carbon material is used as an anode material of a potassium ion battery.
It is a fourth object of the present invention to provide a potassium ion battery comprising a purposeful one of said sulfur-doped hard carbon materials.
Preferably, the negative electrode material of the potassium ion battery comprises a sulfur-doped hard carbon material according to one of the purposes.
Preferably, the negative electrode material of the potassium ion battery is the sulfur-doped hard carbon material.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the sulfur-doped hard carbon material designed by the invention, the doping of sulfur atoms can increase the interlayer spacing of the carbon material and obtain a more ideal pore channel structure, so that the potassium ion intercalation/deintercalation requirement is met, and the sulfur-doped hard carbon material has excellent electrochemical performance as a negative electrode material of a potassium ion battery.
(2) The invention takes high-sulfur coal as a raw material, sulfur element exists in a material matrix, and no external sulfur source is needed to be introduced.
(3) The sulfur-doped hard carbon material is prepared by in-situ autodoping, so that sulfur atoms can be present on the surface of the material, and a part of the sulfur atoms are present in the carbon matrix, thereby breaking the original balance structure of the hard carbon material and endowing the material with new electrochemical activity and a more ideal pore channel structure.
Drawings
FIG. 1 is an SEM image of a sulfur-doped hard carbon material obtained in example 1;
FIG. 2 is an XRD pattern of the sulfur-doped hard carbon material obtained in example 1;
FIG. 3 is an SEM image of the sulfur-doped hard carbon material obtained in example 11;
fig. 4 is the XRD pattern of the sulfur-doped hard carbon material obtained in example 11.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) Pickling high-sulfur coal with 4.27 percent of sulfur in 1mol/L hydrochloric acid solution for 24 hours, soaking in NaOH solution for 24 hours, wherein the mass ratio of the solute of the NaOH solution to the pickled high-sulfur coal is 1:1, and freeze-drying to obtain a pre-product;
(2) carrying out heat treatment on the pre-product at the temperature of 800 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 2h to prepare a hard carbon material;
(3) the method comprises the steps of soaking a hard carbon material in a 2mol/L hydrochloric acid solution for 12 hours, washing with deionized water, filtering and drying at 100 ℃ to obtain a sulfur-doped hard carbon material with the sulfur content of 3.75% and the pore size distribution of 0.5 nm-2 mu m, wherein figure 1 is an SEM (scanning electron microscope) diagram of the hard carbon material, carbon can be seen to be in a honeycomb structure, figure 2 is an XRD (X-ray diffraction) diagram of the hard carbon material, and the hard carbon material can be seen to be amorphous hard carbon.
Example 2
The difference from example 1 is that the sulfur content of the sulfur coal in step (1) was 3%, resulting in a sulfur-doped hard carbon material having a sulfur content of 2.79%.
Example 3
The difference from example 1 is that the sulfur content of the sulfur coal in step (1) was 8%, resulting in a sulfur-doped hard carbon material having a sulfur content of 7.49%.
Example 4
The difference from example 1 is that the sulfur content of the sulfur coal in step (1) was 2.5%, resulting in a sulfur-doped hard carbon material having a sulfur content of 2%.
Example 5
The difference from the example 1 is that the mass ratio of the alkali solution solute to the acid-washed high-sulfur coal in the step (1) is 0.5:1, and the sulfur-doped hard carbon material with the sulfur content of 4.02 percent is obtained.
Example 6
The difference from the example 1 is that the mass ratio of the alkali solution solute to the acid-washed high-sulfur coal in the step (1) is 4:1, and the sulfur-doped hard carbon material with the sulfur content of 3.58% is obtained.
Example 7
The difference from the example 1 is that the mass ratio of the alkali solution solute to the acid-washed high-sulfur coal in the step (1) is 0.3:1, and the sulfur-doped hard carbon material with the sulfur content of 4.03% is obtained.
Example 8
The difference from the example 1 is that the mass ratio of the alkali solution solute to the acid-washed high-sulfur coal in the step (1) is 5:1, and the sulfur-doped hard carbon material with the sulfur content of 3.31% is obtained.
Example 9
The difference from example 1 is that the heat treatment temperature in step (2) was 600 deg.c, resulting in a sulfur-doped hard carbon material having a sulfur content of 3.82%.
Example 10
The difference from example 1 is that the heat treatment temperature in step (2) was 900 deg.c, resulting in a sulfur-doped hard carbon material having a sulfur content of 3.68%.
Example 11
(1) Pickling high-sulfur coal with 3.75 percent of sulfur in a mixed solution of 1mol/L hydrochloric acid solution and 0.2mol/L hydrofluoric acid solution for 24 hours, then soaking in an alkaline solution for 18 hours, wherein the mass ratio of the solute of the alkaline solution to the pickled high-sulfur coal is 2:1, and freezing and drying to obtain a pre-product;
(2) carrying out heat treatment on the pre-product at the temperature of 700 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 3h to prepare a hard carbon material;
(3) the hard carbon material is soaked in 1mol/L hydrochloric acid solution for 24 hours, washed by deionized water, filtered and dried at 100 ℃ to obtain the sulfur-doped hard carbon material with the sulfur content of 3.28 percent, fig. 3 is an SEM picture of the hard carbon material, carbon can be seen to be in a tubular cellular structure from the SEM picture, fig. 4 is an XRD (X-ray diffraction) spectrum of the hard carbon material, and the hard carbon material can be seen to be amorphous hard carbon from the XRD spectrum.
Example 12
(1) Pickling high-sulfur coal with 4.27% of sulfur content in 1mol/L hydrochloric acid solution for 12 hours, soaking in alkaline solution for 12 hours, wherein the mass ratio of alkaline solution solute to the pickled high-sulfur coal is 1:1, and freeze-drying to obtain a pre-product;
(2) carrying out heat treatment on the pre-product at the temperature of 800 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 6h to prepare a hard carbon material;
(3) soaking the hard carbon material in 5mol/L hydrochloric acid solution for 6h, washing with deionized water, filtering and drying at 80 ℃ to obtain the sulfur-doped hard carbon material with the sulfur content of 3.88%.
Example 13
(1) Pickling high-sulfur coal with 4.27% of sulfur content in 1mol/L hydrochloric acid solution for 28h, soaking in alkaline solution for 28h, wherein the mass ratio of alkaline solution solute to the pickled high-sulfur coal is 1:1, and freeze-drying to obtain a pre-product;
(2) carrying out heat treatment on the pre-product at the temperature of 800 ℃ at the heating rate of 0.5 ℃/min, and keeping the temperature for 1h to prepare a hard carbon material;
(3) soaking the hard carbon material in 0.5mol/L hydrochloric acid solution for 24h, washing with deionized water, filtering and drying at 120 ℃ to obtain the sulfur-doped hard carbon material with the sulfur content of 3.98%.
Comparative example 1
The difference from example 1 is that the high sulfur coal was replaced with sulfur-free coal.
Comparative example 2
The difference from example 1 is that high-sulfur coal was replaced with sulfur-free coal, and the prepared pre-product was mixed with sulfur powder and heat-treated.
And (3) performance testing:
the prepared nitrogen-doped hard carbon material is subjected to the following performance tests:
(1) and (3) testing the charge and discharge performance, namely assembling the prepared nitrogen-doped hard carbon material into a button cell, and testing the performance of the cell by adopting blue electricity under the current density of 0.1A/g.
(2) And testing the specific surface area of the Bet by adopting a Beschard specific surface area tester.
TABLE 1
Figure BDA0001816211140000111
As can be seen from table 1, the potassium ion batteries of examples 1 to 13 all had excellent cycle performance, and the 200 th coulombic efficiency was 99% or more.
As can be seen from table 1, the electrochemical performance of example 4 is inferior to that of example 1, probably because the electrochemical activity of the prepared sulfur-doped hard carbon material is low due to the low sulfur content of the prepared material, so the prepared material has poor electrochemical performance.
As can be seen from Table 1, the electrochemical performance of example 7 is inferior to that of example 1, probably because the electrochemical performance of the prepared material is inferior due to the low NaOH content and the difficulty in generating large specific surface area.
As can be seen from Table 1, the electrochemical performance of the material prepared in example 8 is poor compared with that of example 1, probably because the content of NaOH is high, the micropores of the material prepared are too many, the pore structure is damaged, the mechanical strength is reduced, and the electrode is easy to be pulverized in the charging and discharging processes, so that the electrochemical performance of the material prepared is poor.
As can be seen from table 1, the electrochemical performance of comparative example 1 is inferior to that of example 1, probably because the electrochemical activity of the material prepared in comparative example 1 is low because the material contains no sulfur.
As can be seen from Table 1, the electrochemical performance of comparative example 2 is inferior to that of example 1, probably because the comparative example 2 adopts the mode of adding sulfur powder to dope sulfur, the sulfur element is distributed unevenly and is easy to agglomerate to block the pore channels, and the electrochemical performance of the prepared material is inferior.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (32)

1. A sulfur-doped hard carbon material, characterized in that the hard carbon material has a porous structure, the sulfur atoms being at least partially distributed inside the hard carbon material;
the hard carbon material has a hierarchical pore structure, and micropores, mesopores and macropores are distributed in the hard carbon material; the pore size distribution is 0.5 nm-2 mu m; the specific surface area is 280-1189 m2/g；
The hard carbon material is prepared by the following method, and the method comprises the following steps:
(1) pickling high-sulfur coal, and then soaking the high-sulfur coal in alkaline solution to obtain a pre-product;
(2) and (3) carrying out heat treatment on the pre-product in a protective atmosphere to obtain the hard carbon material.
2. The sulfur-doped hard carbon material according to claim 1, wherein the sulfur content in the hard carbon material is 2 to 10 wt%.
3. A method for preparing a sulfur-doped hard carbon material according to claim 1 or 2, comprising the steps of:
(1) pickling high-sulfur coal, and then soaking the high-sulfur coal in alkaline solution to obtain a pre-product;
(2) and (3) carrying out heat treatment on the pre-product in a protective atmosphere to obtain the hard carbon material.
4. The method according to claim 3, wherein the sulfur content of the high-sulfur coal is 3 to 8 wt%.
5. The method of claim 3, wherein the acid washing in step (1) comprises: and (3) crushing the high-sulfur coal, soaking the crushed high-sulfur coal in an acid solution, filtering and drying.
6. The method according to claim 5, wherein the acid solution comprises a hydrochloric acid solution and/or a hydrofluoric acid solution.
7. The method according to claim 6, wherein the concentration of the hydrochloric acid solution is 0.5 to 5 mol/L.
8. The method according to claim 6, wherein the hydrofluoric acid solution has a concentration of 0.1 to 1 mol/L.
9. The preparation method according to claim 3, wherein the acid washing time is 12-28 hours.
10. The preparation method according to claim 3, wherein the mass ratio of the solute in the alkaline solution in the step (1) to the high-sulfur coal after acid washing is 0.5:1 to 4: 1.
11. The method of claim 3, wherein the alkaline solution comprises KOH solution and/or NaOH solution.
12. The method according to claim 3, wherein the immersion in the alkaline solution is carried out for 12 to 28 hours.
13. The method of claim 5, wherein the drying process is freeze-drying.
14. The method according to claim 3, wherein the heat treatment temperature in the step (2) is 600 to 900 ℃.
15. The method according to claim 3, wherein the heat treatment is performed at a temperature increase rate of 0.5 to 5 ℃/min.
16. The method according to claim 3, wherein the heat treatment time is 1 to 6 hours.
17. The method of claim 3, wherein the protective atmosphere comprises an inert atmosphere.
18. The method of claim 17, wherein the protective atmosphere comprises any one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere, or a combination of at least two thereof.
19. The production method according to claim 3, wherein step (2) is followed by step (3): and (3) carrying out acid solution soaking, washing, filtering and drying on the hard carbon material.
20. The method of claim 19, wherein the acid solution comprises a hydrochloric acid solution and/or a hydrofluoric acid solution.
21. The method of claim 20, wherein the acid solution is a hydrochloric acid solution.
22. The method according to claim 19, wherein the concentration of the acid solution is 0.5 to 5 mol/L.
23. The method of claim 19, wherein the acid wash time is 6 to 24 hours.
24. The method of claim 19, wherein the washing comprises a deionized water wash.
25. The method of claim 19, wherein the drying temperature is 80-120 ℃.
26. The method of preparing a sulfur-doped hard carbon material of claim 3, comprising the steps of:
(1) pickling high-sulfur coal with 3-8% of sulfur in an acid solution for 12-28 h, soaking in an alkaline solution for 12-28 h, wherein the mass ratio of the solute of the alkaline solution to the pickled high-sulfur coal is 0.5: 1-4: 1, and freeze-drying to obtain a pre-product;
(2) carrying out heat treatment on the pre-product at the temperature of 600-900 ℃ at the heating rate of 0.5-5 ℃/min, and preserving heat for 1-6 h to obtain a hard carbon material;
(3) soaking the hard carbon material in 0.5-5 mol/L hydrochloric acid solution for 6-24 h, washing with deionized water, filtering and drying at 80-120 ℃.
27. Use of the sulfur-doped hard carbon material according to claim 1 or 2 in the field of batteries.
28. Use according to claim 27, wherein the hard carbon material is used in the field of potassium ion batteries.
29. Use according to claim 28, wherein the hard carbon material is used as a negative electrode material for potassium ion batteries.
30. A potassium ion battery comprising the sulfur-doped hard carbon material of claim 1 or 2.
31. The potassium ion battery of claim 30, wherein the negative electrode material of the potassium ion battery comprises the sulfur-doped hard carbon material of claim 1 or 2.
32. The potassium ion battery of claim 31, wherein the negative electrode material of the potassium ion battery is the sulfur-doped hard carbon material of claim 1 or 2.
CN201811142962.5A 2018-09-28 2018-09-28 Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode Active CN109301246B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811142962.5A CN109301246B (en) 2018-09-28 2018-09-28 Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811142962.5A CN109301246B (en) 2018-09-28 2018-09-28 Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode

Publications (2)

Publication Number Publication Date
CN109301246A CN109301246A (en) 2019-02-01
CN109301246B true CN109301246B (en) 2021-07-02

Family

ID=65164897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811142962.5A Active CN109301246B (en) 2018-09-28 2018-09-28 Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode

Country Status (1)

Country Link
CN (1) CN109301246B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110706934A (en) * 2019-09-12 2020-01-17 东北大学秦皇岛分校 Sulfur self-doped hard carbon supercapacitor electrode material and preparation method thereof
CN113451557B (en) * 2021-06-25 2022-04-15 安徽工业大学 Preparation method of lithium-sulfur battery positive-grade material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103339770A (en) * 2010-11-09 2013-10-02 康奈尔大学 Sulfur containing nanoporous materials, nanoparticles, methods and applications
CN105810914A (en) * 2016-05-13 2016-07-27 中南大学 Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material
CN106229519A (en) * 2016-07-29 2016-12-14 辽宁科技大学 A kind of method utilizing coal to prepare auto-dope difunctional oxygen reaction eelctro-catalyst
CN107887602A (en) * 2017-09-27 2018-04-06 北京化工大学 A kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope and its preparation method and application
CN108455555A (en) * 2018-01-18 2018-08-28 新疆大学 High-volume and capacity ratio coal based super capacitor electrode material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9806334B2 (en) * 2012-11-02 2017-10-31 Semiconductor Energy Laboratory Co., Ltd. Power storage device electrode, method for forming the same, power storage device, and electrical device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103339770A (en) * 2010-11-09 2013-10-02 康奈尔大学 Sulfur containing nanoporous materials, nanoparticles, methods and applications
CN105810914A (en) * 2016-05-13 2016-07-27 中南大学 Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material
CN106229519A (en) * 2016-07-29 2016-12-14 辽宁科技大学 A kind of method utilizing coal to prepare auto-dope difunctional oxygen reaction eelctro-catalyst
CN107887602A (en) * 2017-09-27 2018-04-06 北京化工大学 A kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope and its preparation method and application
CN108455555A (en) * 2018-01-18 2018-08-28 新疆大学 High-volume and capacity ratio coal based super capacitor electrode material and preparation method thereof

Also Published As

Publication number Publication date
CN109301246A (en) 2019-02-01

Similar Documents

Publication Publication Date Title
Zheng et al. Robust erythrocyte-like Fe2O3@ carbon with yolk-shell structures as high-performance anode for lithium ion batteries
CN107732203B (en) Preparation method of nano cerium dioxide/graphene/sulfur composite material
CN107579250B (en) Composite carbon material conductive agent
CN112794324B (en) High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof
CN114956037A (en) Carbon material for sodium ion battery negative electrode, preparation method of carbon material, sodium ion battery negative electrode piece and sodium ion battery
CN113948681B (en) Biomass-based hard carbon compound composite material and preparation method and application thereof
CN106299344B (en) A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof
CN110600682B (en) Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof
Gong et al. Anchoring high-mass iodine to nanoporous carbon with large-volume micropores and rich pyridine-N sites for high-energy-density and long-life Zn-I2 aqueous battery
CN111048324A (en) Manganese dioxide-porous carbon composite material and preparation method and application thereof
CN109301246B (en) Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode
JIN et al. Cobalt-doped hollow carbon framework as sulfur host for the cathode of lithium sulfur battery
Zhang et al. Porous nitrogen-doped FeP/C nanofibers as promising anode for potassium-ion batteries
CN110600710B (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN110783542A (en) Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery
CN106972171B (en) Three-dimensional network structure material, preparation method and application thereof
CN112820866B (en) Capsule-shaped nickel ferrite composite carbon skeleton lithium ion battery cathode material and preparation method and application thereof
CN112750627B (en) Carbon nano tube and preparation method and application thereof
CN111180745B (en) CeO (CeO)xPreparation method and application of/MC nanosheet material
Wang et al. A novel three-dimensional hierarchical porous lead-carbon composite prepared from corn stover for high-performance lead-carbon batteries
CN113782713A (en) MoS2Nano-sheet vertically embedded biological carbon nano composite material and preparation method and application thereof
CN110589795A (en) Manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network and preparation method and application thereof
CN110061216A (en) A kind of preparation method of the lithium sulfur battery anode material based on biomass seaweed
CN113113604B (en) Micron open-cell cage-shaped defect MnO @ Ni material and preparation method and application thereof
CN117163946B (en) Nitrogen-oxygen doped porous carbon and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant