CN113839019A - Crescent MoS2Oxidized pomace carbon sodium ion battery negative electrode material and preparation method thereof - Google Patents

Crescent MoS2Oxidized pomace carbon sodium ion battery negative electrode material and preparation method thereof Download PDF

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CN113839019A
CN113839019A CN202111084313.6A CN202111084313A CN113839019A CN 113839019 A CN113839019 A CN 113839019A CN 202111084313 A CN202111084313 A CN 202111084313A CN 113839019 A CN113839019 A CN 113839019A
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pomace
carbon
oxidized
crescent
mos
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许占位
王盈
付豪
陆凡宇
王玺
严皓
陈思雨
黄剑锋
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Shaanxi University of Science and Technology
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    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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 discloses a crescent MoS2Oxidized pomace carbon sodium ion battery cathode material and preparation method, the preparation method prepares and oxidizes pomace carbon through the similar Hummers method; placing the oxidized pomace carbon as a carbon source and ammonium molybdate as a molybdenum source in water, stirring and evaporating to dryness to obtain a preform; uniformly mixing the prefabricated body with sulfur powder to perform high-temperature solid-phase reaction, thus preparing the crescent-shaped M supported by the three-dimensional oxidized pomace carbonOS2The cathode material is beneficial to relieving volume expansion and enabling the electrolyte to fully permeate, so that shorter transmission distance of sodium ions and electrons is ensured, and excellent sodium storage performance is shown; the prepared material has high specific capacity and excellent cycling stability. The carbon source used in the invention is oxidized pomace carbon, the pomace is recycled, and the hydrothermal-solid phase methodThe method has the advantages of simple operation, low energy consumption and high repeatability, is suitable for large-scale production and preparation, and has obvious scientific significance in the aspect of application of the sodium-ion battery.

Description

Crescent MoS2Oxidized pomace carbon sodium ion battery negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of electrode materials of sodium-ion batteries, and particularly relates to crescent MoS2Oxide pomace carbon sodium ion battery cathode material and preparation method thereof.
Background
Lithium ion batteries have been widely used in daily life, but large-scale application of lithium ion batteries is limited by a shortage of lithium resources. Compared with lithium, sodium resources are widely distributed, reserves are high, and cost is low, so that the sodium-ion battery is expected to be one of substitutes of lithium-ion batteries. Molybdenum disulfide (MoS)2) Has S-Mo-S sandwich layer structure, weak van der Waals force exists between layers, ion embedding and ion releasing are facilitated, and the theoretical specific capacity is higher (670mAh g)-1) However, MoS2Poor conductivity and MoS in the process of charging and discharging2Easy superposition, poor cycle performance and the like.
Researchers are working on improving MoS2Stability and conductivity of (A), an important measure being to mix MoS2And compounding with conductive carbon material. For example, Luo et al prepared three-dimensional nanoflower MoS by hydrothermal method2Carbon (MoS)2/C NF), Wu et al hydrothermal prepared MoS2The sodium ion battery assembled by the/C microspheres has the advantages of complex preparation process, high cost and environmental friendliness in the related technology, and the prepared material cannot meet the requirements on performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a crescent MoS2The oxidized pomace carbon sodium ion battery cathode material and the preparation method have the advantages of low cost, simplicity in preparation, high repeatability, environmental friendliness and safety, and are beneficial to large-scale production; prepared MOS2The oxidized pomace carbon nano negative electrode material has high performance when being used for a sodium ion batterySpecific capacity and excellent cycling stability.
In order to achieve the purpose, the invention provides a crescent MoS2The preparation method of the oxidized pomace carbon sodium ion battery negative electrode material comprises the following steps:
1) preparing oxidized pomace carbon:
1.1) taking the mass ratio of (2-6): 1, placing the pomace carbon and sodium nitrate into concentrated sulfuric acid for ice bath treatment, slowly adding sufficient potassium permanganate after the ice bath treatment, and stirring for reaction at 10 ℃;
1.2) carrying out constant temperature water bath at 35 ℃ and stirring;
1.3) slowly adding enough water, stirring at 98 ℃, adding a hydrogen peroxide solution, and stirring until bubbles disappear;
1.4) carrying out centrifugal separation while the mixture is hot, and cleaning the residual solid to be neutral and drying to obtain oxidized pomace carbon;
2) dispersing oxidized pomace carbon and ammonium molybdate in sufficient water in a mass ratio of 1 (1-5), heating at 100 ℃ while stirring, evaporating, and performing self-assembly again to prepare an ammonium molybdate/oxidized pomace carbon preform;
3) mixing and grinding an ammonium molybdate/oxidized pomace carbon preform and sulfur powder in a mass ratio of 1 (1-8), heating and preserving heat at 600-800 ℃ in an inert atmosphere, cooling, washing and drying to obtain crescent MoS2Oxide pomace carbon sodium ion battery negative electrode material.
Preferably, 1.40-4.20 g of the pomace carbon and 0.70g of sodium nitrate are taken in the step 1.1) and put into 35-98 mL of concentrated sulfuric acid, and 5.0-17.0 g of potassium permanganate is slowly added after ice bath treatment.
Preferably, the ice bath treatment in the step 1.1) is kept at 0 ℃ for 0.5-2.5 h.
Preferably, 196-531 mL of water are supplemented in the step 1.3).
Preferably, 100-180 mL of 30% hydrogen peroxide solution is added in the step 1.3).
Preferably, in the step 1.4), 50-130 mL of 5% HCl and deionized water are sequentially used for washing for several times until the solution is neutral.
Preferably, 0.50g of the oxidized marc carbon and 0.50-2.50 g of ammonium molybdate are well dispersed in 60mL of water in the step 2).
Preferably, in the step 3), 0.60g of ammonium molybdate/oxidized pomace carbon preform and 0.60-4.80 g of sulfur powder are mixed, mechanically ground and then placed in a tubular heating furnace for heating.
Preferably, the heating in the step 3) is carried out under an argon atmosphere, and the flow rate of argon is 10-50 sccm; the temperature rise rate of the tubular heating furnace is 6-10 ℃ min-1(ii) a Washing is sequentially carried out by using deionized water and absolute ethyl alcohol respectively, and freeze drying is adopted for drying for 10-22 h.
The invention also provides a crescent MoS2The crescent MoS is adopted as the anode material of the oxidized pomace carbon sodium ion battery2Preparation method of oxidized pomace carbon sodium ion battery cathode material, crescent MoS2The nano-sheet grows on a three-dimensional oxidized pomace carbon structure in situ, MoS2The nano-scale particles have a size of 100-150 nm and a current density of 1Ag-1At the lower cycle, the initial reversible capacity is 555.4mAh g-1After 200 cycles, the reversible capacity is maintained at 399.3mAh g-1The coulombic efficiency reaches 99.3 percent.
Compared with the prior art, the preparation method of the invention prepares the oxidized pomace carbon (OAPC) by a Hummers-like method; placing the oxidized pomace carbon as a carbon source and ammonium molybdate as a molybdenum source in water, stirring and evaporating to dryness to obtain a preform; mixing the prefabricated body with sulfur powder to perform high-temperature solid-phase reaction, and thus obtaining the crescent-shaped M supported by the three-dimensional oxidized pomace carbonOS2The negative electrode material is used for carrying out Hummers-like method oxidation treatment on the pomace carbon and increasing surface active functional groups so as to be beneficial to MOS2Nucleation growth, the utilization of a three-dimensional conductive network of oxidized pomace carbon, allows more active sites to be exposed for MOS2In-situ growth to effectively avoid MOS2The structure collapses in the charging and discharging process, a stable structure is maintained, the volume expansion is favorably relieved, the electrolyte is fully permeated, the shorter transmission distance of sodium ions and electrons is ensured, and the excellent sodium storage performance is shown; used in the inventionThe carbon source is oxidized pomace carbon, so that pomace is recycled, the hydrothermal-solid phase method is simple to operate, low in energy consumption and high in repeatability, is suitable for large-scale production and preparation, and has remarkable scientific significance in the aspect of application of sodium ion batteries. The preparation method has the advantages of simple and easily-controlled process, good product consistency, lower cost, high repeatability, environmental protection and safety, and is beneficial to industrial production.
Synthetic crescent-shaped M prepared by the inventionOS2/OAPC nanocomposite, crescent MoS2The nano-sheet grows on a three-dimensional oxidized pomace carbon structure in situ, MoS2The nano-scale is about 100-150 nm. MOS2Has obvious synergistic effect with the oxidized pomace carbon, is beneficial to the transfer of reaction electrons, thereby improving MOS2Sodium storage stability of OAPC. MoS2When the/OAPC composite material is used as a negative electrode material of a sodium ion battery, the capacity of the composite material is obviously improved in a long circulation process, the circulation stability is high, and the current density is 1Ag-1At the time of lower cycle, the MoS was measured2The initial reversible capacity of the negative electrode material of the OAPC sodium-ion battery is 555.4mAh g-1The capacity is kept stable along with the charging and discharging process, and the reversible capacity is still kept at 399.3mAh g after 200 cycles-1The coulombic efficiency reaches 99.3 percent. Illustrating the crescent-shaped MoS prepared by the invention2the/OAPC has high specific capacity and excellent cycling stability, and can be widely used as an excellent sodium ion battery cathode material.
Drawings
FIG. 1 shows a crescent-shaped M prepared in example 3 of the present inventionOS2XRD pattern of oxidized pomace carbon sodium ion battery cathode material;
FIG. 2 shows a crescent-shaped M prepared in example 3 of the present inventionOS2SEM image of oxidized pomace carbon sodium ion battery cathode material;
FIG. 3 shows a crescent-shaped M prepared in example 3 of the present inventionOS2Oxidized pomace carbon and M prepared in comparative exampleOS2And (3) comparing the cycle performance of the sodium-ion battery with the negative electrode made of the material.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a crescent MoS2The preparation method of the oxidized pomace carbon sodium ion battery negative electrode material specifically comprises the following steps:
(1) the oxidized pomace carbon is prepared by a Hummers-like method, which comprises the following steps:
(a) weighing the following components in a mass ratio of (2-6): 1, putting 1.40-4.20 g of pomace carbon and 0.70g of sodium nitrate into a 35-98 mL concentrated sulfuric acid beaker, putting the beaker into an ice bath for cooling, keeping the temperature at 0 ℃ for 0.5-2.5 h, slowly adding 5.0-17.0 g of potassium permanganate into the beaker, and stirring and reacting the mixture at 10 ℃ for 1 h;
(b) then transferring the beaker to a constant temperature water bath with the temperature of 35 ℃ and stirring for 2 hours;
(c) slowly adding 196-531 mL of ultrapure water, continuing stirring for 2 hours at 98 ℃, adding 100-180 mL of 30% hydrogen peroxide solution, and stirring until bubbles disappear to remove unreacted potassium permanganate;
(d) centrifuging at 2500rpm while hot, centrifuging the filtrate, decanting the supernatant, sequentially using 50-130 mL of 5% HCl and deionized water to the remaining solid, repeating the step for at least three times, and cleaning to be neutral;
(e) then, drying the material for 12h by adopting a freeze drying method to obtain oxidized pomace carbon;
(2) dispersing oxidized fruit residue carbon and ammonium molybdate in sufficient water according to the mass ratio of 1 (1-5), specifically, mixing 0.50g of oxidized fruit residue carbon with 0.50-2.50 g of ammonium molybdate, fully dispersing in 60mL of aqueous solution, heating at 100 ℃ while magnetically stirring, evaporating to perform self-assembly again, and preparing an ammonium molybdate/oxidized fruit residue carbon preform;
(3) molybdic acid with the mass ratio of 1 (1-8)Mixing and grinding an ammonium/oxidized pomace carbon preform and sulfur powder, specifically, mixing 0.60g of ammonium molybdate/oxidized pomace carbon preform and 0.60-4.80 g of sulfur powder in proportion, mechanically grinding the mixture together, placing the mixture in the rear section of a tubular heating furnace, heating the mixture to 600-800 ℃ in argon atmosphere, and preserving the heat for 2 hours, wherein the flow rate of the argon gas is 10-50 sccm, and the heating rate of the tubular furnace is 6-10 ℃ for min-1Naturally cooling to room temperature, washing the product with deionized water and absolute ethyl alcohol respectively and sequentially, and drying for 10-22 h in a freeze drying mode to obtain the MoS2the/OAPC composite material.
The invention also provides crescent MoS prepared by the preparation method2Oxide pomace carbon sodium ion battery negative electrode material, namely MoS2Composite material of OAPC, crescent MoS2The nano-sheet grows on a three-dimensional oxidized pomace carbon structure in situ, MoS2The size of the nano-sheet is 100-150 nm, the capacity of the nano-sheet is obviously improved in a long circulation process, the circulation stability is high, and the current density is 1Ag-1At the time of lower cycle, the MoS was measured2The initial reversible capacity of the negative electrode material of the OAPC sodium-ion battery is 555.4mAh g-1The capacity is kept stable along with the charging and discharging process, and the reversible capacity is still kept at 399.3mAh g after 200 cycles-1The coulombic efficiency reaches 99.3 percent.
The present invention will be described in detail with reference to specific examples.
Example 1:
the method comprises the following steps:
(1) the oxidized pomace carbon is prepared by a Hummers-like method, which comprises the following steps:
(a) weighing 1.40g of pomace carbon and 0.70g of sodium nitrate in a 35mL beaker of concentrated sulfuric acid, putting the pomace carbon and the sodium nitrate into an ice bath, cooling the pomace carbon and the sodium nitrate at 0 ℃ for 0.5h, slowly adding 5.0g of potassium permanganate into the beaker, and stirring the mixture at 10 ℃ to react for 1 h;
(b) then transferring the beaker to a constant temperature water bath with the temperature of 35 ℃ and stirring for 2 hours;
(c) slowly adding 196mL of ultrapure water, continuing stirring for 2h at 98 ℃, adding 100mL of 30% hydrogen peroxide, and stirring until bubbles disappear to remove unreacted potassium permanganate;
(d) centrifuging at 2500rpm while hot, centrifuging the filtrate and decanting the supernatant, then repeating the step with 50mL of 5% HCl and deionized water sequentially for at least three times to wash the remaining solid material to neutral;
(e) then, drying the material for 12h by adopting a freeze drying method to obtain oxidized pomace carbon;
(2) fully dispersing 0.50g of oxidized pomace carbon and 0.50g of ammonium molybdate in 60mL of aqueous solution, heating to 100 ℃ while magnetically stirring, evaporating the mixture for self-assembly again, and preparing an ammonium molybdate/oxidized pomace carbon preform;
(3) mixing 0.60g of ammonium molybdate/oxidized pomace carbon preform with 0.60g of sulfur powder, mechanically grinding the mixture together, placing the mixture in the rear section of a tubular heating furnace, and performing heat treatment at 6 ℃ for min under the argon atmosphere of 10sccm-1Heating to 600 ℃, preserving heat for 2h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively and sequentially, and freeze-drying for 10h to obtain MoS2the/OAPC composite material.
Example 2:
the method comprises the following steps:
(1) the oxidized pomace carbon is prepared by a Hummers-like method, which comprises the following steps:
(a) 2.1g of pomace carbon and 0.70g of sodium nitrate are weighed into a 50mL beaker of concentrated sulfuric acid, the mixture is placed into an ice bath to be cooled at 0 ℃ and kept for 1h, 8.0g of potassium permanganate is slowly added into the ice bath, and the mixture is stirred and reacted for 1h at 10 ℃.
(b) Then transferring the beaker to a constant temperature water bath with the temperature of 35 ℃ and stirring for 2 hours;
(c) slowly adding 280mL of ultrapure water, continuing stirring for 2h at 98 ℃, adding 120mL of 30% hydrogen peroxide, and stirring until bubbles disappear so as to remove unreacted potassium permanganate;
(d) centrifuging at 2500rpm while hot, centrifuging the filtrate and decanting the supernatant, then sequentially adding 5% HCl 70mL and deionized water to the remaining solid material, repeating the step at least three times, and washing to neutrality;
(e) then, drying the material for 12h by adopting a freeze drying method to obtain oxidized pomace carbon;
(2) fully dispersing 0.50g of oxidized pomace carbon and 1.0g of ammonium molybdate in 60mL of aqueous solution, heating to 100 ℃ while magnetically stirring, evaporating the mixture to perform self-assembly again, and preparing an ammonium molybdate/oxidized pomace carbon preform;
(3) mixing 0.60g of ammonium molybdate/oxidized pomace carbon preform with 1.20g of sulfur powder, mechanically grinding the mixture together, placing the mixture in the rear section of a tubular heating furnace, and performing heat treatment at 7 ℃ for min under the argon atmosphere of 20sccm-1Heating to 650 ℃, preserving heat for 2h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively and sequentially, and freeze-drying for 13h to obtain MoS2the/OAPC composite material.
Example 3:
the method comprises the following steps:
(1) the oxidized pomace carbon is prepared by a Hummers-like method, which comprises the following steps:
(a) weighing 2.80g of pomace carbon and 0.70g of sodium nitrate in a beaker of 68mL of concentrated sulfuric acid, putting the pomace carbon and the sodium nitrate into an ice bath, cooling the pomace carbon and the sodium nitrate at 0 ℃, keeping the temperature for 1.5h, slowly adding 11.0g of potassium permanganate into the beaker, and stirring the mixture at 10 ℃ to react for 1 h;
(b) then transferring the beaker to a constant temperature water bath with the temperature of 35 ℃ and stirring for 2 hours;
(c) slowly adding 364mL of ultrapure water, continuing stirring for 2h at 98 ℃, adding 140mL of 30% hydrogen peroxide, and stirring until bubbles disappear so as to remove unreacted potassium permanganate;
(d) centrifuging at 2500rpm while hot, centrifuging the filtrate and decanting the supernatant, then sequentially adding 5% HCl 90mL and deionized water to the remaining solid material, repeating the step at least three times, and washing to neutrality;
(e) then, drying the material for 12h by adopting a freeze drying method to obtain oxidized pomace carbon;
(2) fully dispersing 0.50g of oxidized pomace carbon and 1.50g of ammonium molybdate in 60mL of aqueous solution, heating to 100 ℃ while magnetically stirring, evaporating the mixture to perform self-assembly again, and preparing an ammonium molybdate/oxidized pomace carbon preform;
(3) mixing 0.60g of ammonium molybdate/oxidized pomace carbon preform with 2.40g of sulfur powder, mechanically grinding the mixture together, placing the mixture in the rear section of a tubular heating furnace, and performing vacuum distillation at 8 ℃ for min under the argon atmosphere of 30sccm-1Heating to 700 deg.C, keeping the temperature for 2h, naturally cooling to room temperature, and removingRespectively washing the seed water and the absolute ethyl alcohol in sequence, and freeze-drying for 16h to obtain MoS2the/OAPC composite material.
Referring to FIG. 1, it can be seen from FIG. 1 that the product obtained is MOS2OAPC, by contrast with standard card, each diffraction peak in XRD diffraction pattern can be matched with MoS2The diffraction peaks of the standard cards correspond to each other, which shows that the synthesized product is the target product MoS2the/OAPC composite material.
Referring to FIG. 2, it can be seen from the microscopic morphology that the composite material prepared by the invention has the size of nano-scale, crescent MoS2The nano-sheets grow on the three-dimensional oxidized pomace carbon structure in situ, are uniformly distributed and are well dispersed.
Design M as a comparisonOS2Preparation of materials comparative example: mixing ammonium molybdate 0.60g and sulfur powder 2.40g, mechanically grinding, placing in the rear section of tubular heating furnace, and heating at 8 deg.C for min under argon atmosphere of 30sccm-1Heating to 700 ℃ and preserving heat for 2h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively and sequentially, and freeze-drying for 16h to obtain MoS2A material.
As can be seen in fig. 3, with MOS2Material comparison, MoS2When the/OAPC composite material is used as a negative electrode material of a sodium ion battery, the capacity of the composite material is obviously improved in a long circulation process, the circulation stability is high, and the current density is 1Ag-1At the time of lower cycle, the MoS was measured2The initial reversible capacity of the negative electrode material of the OAPC sodium-ion battery is 555.4mAh g-1The capacity is kept stable along with the charging and discharging process, and the reversible capacity is still kept at 399.3mAh g after 200 cycles-1The coulombic efficiency reaches 99.3 percent. Illustrating the crescent-shaped MoS prepared by the invention2the/OAPC can be widely used as an excellent negative electrode material of the sodium-ion battery.
Example 4:
the method comprises the following steps:
(1) the oxidized pomace carbon is prepared by a Hummers-like method, which comprises the following steps:
(a) the pomace carbon 3.5g and sodium nitrate 0.70g were weighed into a beaker of 83mL concentrated sulfuric acid and placed in an ice bath to cool at 0 ℃ for 2 h. Slowly adding 14.0g of potassium permanganate into the mixture, and stirring the mixture at the temperature of 10 ℃ to react for 1 hour;
(b) then transferring the beaker to a constant temperature water bath with the temperature of 35 ℃ and stirring for 2 hours;
(c) slowly adding 448mL of ultrapure water, continuing stirring for 2h at 98 ℃, adding 160mL of 30% hydrogen peroxide, and stirring until bubbles disappear so as to remove unreacted potassium permanganate;
(d) centrifuging at 2500rpm while hot, centrifuging the filtrate and decanting the supernatant, then sequentially adding the rest solid material into 5% HCl 110mL and deionized water, repeating the step at least three times, and washing to neutrality;
(e) then, drying the material for 12h by adopting a freeze drying method to obtain oxidized pomace carbon;
(2) fully dispersing 0.50g of oxidized pomace carbon and 2.0g of ammonium molybdate in 60mL of aqueous solution, heating to 100 ℃ while magnetically stirring, evaporating the mixture for self-assembly again, and preparing an ammonium molybdate/oxidized pomace carbon preform;
(3) mixing 0.60g of ammonium molybdate/oxidized pomace carbon preform with 3.60g of sulfur powder, mechanically grinding the mixture together, placing the mixture in the rear section of a tubular heating furnace, and performing vacuum distillation at 9 ℃ for min under the argon atmosphere of 40sccm-1Heating to 750 ℃, preserving heat for 2h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively and sequentially, and freeze-drying for 19h to obtain MoS2the/OAPC composite material.
Example 5:
the method comprises the following steps:
(1) the oxidized pomace carbon is prepared by a Hummers-like method, which comprises the following steps:
(a) weighing 4.20g of pomace carbon and 0.70g of sodium nitrate in a beaker of 98mL of concentrated sulfuric acid, putting the beaker into an ice bath, cooling the beaker at 0 ℃ for 2.5 hours, slowly adding 17.0g of potassium permanganate into the beaker, and stirring the beaker at 10 ℃ for reaction for 1 hour;
(b) then transferring the beaker to a constant temperature water bath with the temperature of 35 ℃ and stirring for 2 hours;
(c) adding 531mL of ultrapure water slowly, continuing stirring for 2h at 98 ℃, adding 180mL of 30% hydrogen peroxide, and stirring until bubbles disappear so as to remove unreacted potassium permanganate;
(d) centrifuging at 2500rpm while hot, centrifuging the filtrate and decanting the supernatant, then sequentially adding the rest solid material into 5% HCl 130mL and deionized water, repeating the step at least three times, and washing to neutrality;
(e) then, drying the material for 12h by adopting a freeze drying method to obtain oxidized pomace carbon;
(2) fully dispersing 0.50g of oxidized pomace carbon and 2.50g of ammonium molybdate in 60mL of aqueous solution, heating to 100 ℃ while magnetically stirring, evaporating the mixture for self-assembly again, and preparing an ammonium molybdate/oxidized pomace carbon preform;
(3) mixing 0.60g of ammonium molybdate/oxidized pomace carbon preform with 4.80g of sulfur powder, mechanically grinding the mixture together, placing the mixture in the rear section of a tubular heating furnace, and performing heat treatment at 10 ℃ for 10 min under the argon atmosphere of 50sccm-1Heating to 800 ℃, preserving heat for 2h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively and sequentially, and freeze-drying for 22h to obtain MoS2the/OAPC composite material.
In conclusion, the method is ingenious in design, the pomace carbon carbonized by pomace is oxidized, so that waste is turned into wealth, resource utilization is maximized, the pomace carbon is oxidized by a Hummers-like method, and a large number of functional groups on the oxidized pomace are used for MoS2The growth of the strain plays a role in inducing and promoting and stabilizing MoS2Meanwhile, the conductivity is improved. The three-dimensional structure is beneficial to electrolyte permeation and charge transmission, so that the reversible capacity and the cycling stability of the battery are improved. The method is simple and easy to control, has low cost and high repeatability, and is favorable for industrial production. The crescent-shaped M prepared by the methodOS2The oxidized pomace carbon can be used as an excellent sodium ion battery negative electrode material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. Crescent MoS2The preparation method of the oxidized pomace carbon sodium ion battery negative electrode material is characterized by comprising the following steps of:
1) preparing oxidized pomace carbon:
1.1) taking the mass ratio of (2-6): 1, placing the pomace carbon and sodium nitrate into concentrated sulfuric acid for ice bath treatment, slowly adding sufficient potassium permanganate after the ice bath treatment, and stirring for reaction at 10 ℃;
1.2) carrying out constant temperature water bath at 35 ℃ and stirring;
1.3) slowly adding enough water, stirring at 98 ℃, adding a hydrogen peroxide solution, and stirring until bubbles disappear;
1.4) carrying out centrifugal separation while the mixture is hot, and cleaning the residual solid to be neutral and drying to obtain oxidized pomace carbon;
2) dispersing oxidized pomace carbon and ammonium molybdate in sufficient water in a mass ratio of 1 (1-5), heating at 100 ℃ while stirring, evaporating, and performing self-assembly again to prepare an ammonium molybdate/oxidized pomace carbon preform;
3) mixing and grinding an ammonium molybdate/oxidized pomace carbon preform and sulfur powder in a mass ratio of 1 (1-8), heating and preserving heat at 600-800 ℃ in an inert atmosphere, cooling, washing and drying to obtain crescent MoS2Oxide pomace carbon sodium ion battery negative electrode material.
2. The crescent MoS of claim 12The preparation method of the oxidized pomace carbon sodium ion battery cathode material is characterized in that 1.1) 1.40-4.20 g of pomace carbon and 0.70g of sodium nitrate are taken and put into 35-98 mL of concentrated sulfuric acid, and 5.0-17.0 g of potassium permanganate is slowly added after ice bath treatment.
3. The crescent MoS of claim 22A preparation method of an oxidized pomace carbon sodium ion battery cathode material is characterized in thatIn the step 1.1), the ice-bath treatment is kept at 0 ℃ for 0.5 to 2.5 hours.
4. The crescent MoS of claim 22The preparation method of the oxidized pomace carbon sodium ion battery cathode material is characterized in that 196-531 mL of water is supplemented in the step 1.3).
5. A crescent-shaped MoS according to claim 42The preparation method of the oxidized pomace carbon sodium ion battery cathode material is characterized in that 100-180 mL of 30% hydrogen peroxide solution is added in the step 1.3).
6. A crescent-shaped MoS according to claim 52The preparation method of the oxidized pomace carbon sodium ion battery cathode material is characterized in that 50-130 mL of 5% HCl and deionized water are sequentially used for cleaning for several times in the step 1.4) until the materials are neutral.
7. The crescent MoS of claim 12The preparation method of the oxidized pomace carbon sodium ion battery negative electrode material is characterized in that 0.50g of oxidized pomace carbon and 0.50-2.50 g of ammonium molybdate are fully dispersed in 60mL of water in the step 2).
8. The crescent MoS of claim 12The preparation method of the oxidized pomace carbon sodium ion battery cathode material is characterized in that in the step 3), 0.60g of ammonium molybdate/oxidized pomace carbon preform and 0.60-4.80 g of sulfur powder are mixed, mechanically ground and then placed in a tubular heating furnace for heating.
9. The crescent MoS of claim 82The preparation method of the oxidized pomace carbon sodium ion battery negative electrode material is characterized in that in the step 3), the material is heated in an argon atmosphere, and the flow rate of argon is 10-50 sccm; the temperature rise rate of the tubular heating furnace is 6-10 ℃ min-1(ii) a Washing with deionized water and anhydrous ethanol respectivelyAnd sequentially washing, wherein freeze drying is adopted for 10-22 h.
10. Crescent MoS2Oxide pomace carbon sodium ion battery negative electrode material, characterized in that the crescent MoS of any one of claims 1 to 9 is adopted2Preparation method of oxidized pomace carbon sodium ion battery cathode material, crescent MoS2The nano-sheet grows on a three-dimensional oxidized pomace carbon structure in situ, MoS2The nano-sheet has a size of 100-150 nm and a current density of 1A g-1At the lower cycle, the initial reversible capacity is 555.4mAh g-1After 200 cycles, the reversible capacity is maintained at 399.3mAh g-1The coulombic efficiency reaches 99.3 percent.
CN202111084313.6A 2021-09-16 2021-09-16 Crescent MoS2Oxidized pomace carbon sodium ion battery negative electrode material and preparation method thereof Pending CN113839019A (en)

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