CN113816425B - MoS 2 Nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material and preparation method thereof - Google Patents
MoS 2 Nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 43
- FKNQFGJONOIPTF-UHFFFAOYSA-N sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 20
- 101700011027 GPKOW Proteins 0.000 title description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N Molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- -1 and meanwhile Chemical compound 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 229910015800 MoS Inorganic materials 0.000 claims abstract 14
- 239000000047 product Substances 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- QGAVSDVURUSLQK-UHFFFAOYSA-N Ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 230000000630 rising Effects 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229940045136 Urea Drugs 0.000 claims description 2
- 229960000539 carbamide Drugs 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 230000002194 synthesizing Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 11
- 101710009221 LD Proteins 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001351 cycling Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011030 bottleneck Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large scale production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001338 necrotic Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The invention discloses a MoS 2 Firstly, active carbon is modified by adopting a nitric acid solution water bath heat treatment method to obtain modified active carbon, then iron phthalocyanine/modified active carbon is synthesized by adopting an in-situ solid phase method, finally, the iron phthalocyanine/modified active carbon and sulfur powder are mixed and then are placed in an inert atmosphere for heat treatment, the iron phthalocyanine/modified active carbon is pyrolyzed into nitrogen-doped carbon/modified active carbon, and meanwhile, molybdenum trioxide which is a byproduct generated in the process of synthesizing the iron phthalocyanine/modified active carbon is reacted with gaseous sulfur at high temperature to grow molybdenum disulfide in situ to obtain MoS 2 The nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material. The method has the characteristics of simple process, good repeatability, high safety and the like, the prepared material has a high specific surface area, and the stability of sodium storage is improved by using the phthalocyanine iron cracking nitrogen-doped carbon as a molybdenum disulfide/modified activated carbon interface.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a MoS 2 A nitrogen-doped carbon/modified activated carbon sodium ion battery cathode material and a preparation method thereof.
Background
The problem of environmental pollution is increasingly prominent, clean energy sources such as wind energy and solar energy are more and more concerned by people, but the energy sources are intermittent and limit the development and wide application of the clean energy sources, and a large-scale energy storage technology is a key technology for solving the bottleneck of efficient utilization of renewable energy sources. The lithium ion battery is an important energy storage technology, is widely applied to portable electronic equipment and new energy automobiles, and is restricted by lithium resource shortage and high price in large-scale development along with the development of electric automobiles and smart power grids. Sodium and lithium have the same main group, similar electronic configuration and chemical properties, abundant sodium reserves and low price, so that the sodium-ion battery is considered as a secondary rechargeable battery which is most easy to replace a lithium-ion battery. The distance between graphite layers is 0.335nm, and the theoretical specific capacity of the graphite layer when the graphite layer is used as the cathode of a lithium ion battery is 372mAh g -1 However, sodium graphite intercalation compounds are difficult to form, with only a small amount of Na + Can be stored in graphite, therefore the reversible capacity is low (35 mAh g) -1 ) And the requirements of the sodium ion battery cannot be met.
Molybdenum disulfide (MoS) 2 ) Is a two-dimensional layered compound with a structure similar to graphite, atoms in the S-Mo-S layer are strongly bonded by covalent bonds, and S-Mo-S layers are bonded by Van der Waals force, the interlayer spacing is up to 0.62 nm, is 1.85 times of the interlayer spacing (0.335nm) of graphite, and is beneficial to repeated intercalation of sodium ions with larger radiusThe theoretical specific capacity reaches 670mAh g -1 Is one of the most potential sodium ion battery cathode materials. However, MoS 2 The lamella is easy to stack in the charging and discharging process, active sites are necrotic, the circulation stability and the rate capability are poor, and MoS 2 Poor conductivity limits its application.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a MoS 2 The preparation method has the advantages of simple process, short period, high repeatability, lower cost, environmental protection and safety, is beneficial to large-scale production, and the prepared MoS 2 the/NC/FAC nano composite material has a stable structure and has excellent cycling stability when being used as a negative electrode material of a sodium-ion battery.
To achieve the above object, the present invention provides a MoS 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material comprises the following steps:
1) transferring the activated carbon into a nitric acid solution by adopting a water bath heating method, stirring, heating at 50-100 ℃, and keeping the temperature for 6-30 hours to obtain modified activated carbon;
2) an in-situ solid phase method is adopted, 0.41-1.71 g of phthalic anhydride, 1.02-2.56 g of urea, 0.16-2.48 g of ammonium molybdate and 0.69-2.02 g of ferrous ammonium sulfate hexahydrate are used as raw materials, 0.06-0.41 g of modified activated carbon is used as a substrate, sintering is carried out at 270 ℃, and heat preservation is carried out for 2 hours, so as to synthesize iron phthalocyanine/modified activated carbon;
3) keeping the same mass of iron phthalocyanine/modified activated carbon and sulfur powder at 800-1000 ℃ for 1-2 hours in an inert atmosphere, pyrolyzing the iron phthalocyanine/modified activated carbon and sulfur powder to form nitrogen-doped carbon, and growing molybdenum disulfide in situ to obtain MoS 2 The nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material.
Preferably, the concentration of the nitric acid solution in the step 1) is 1-5 mol/L.
Preferably, after the heat preservation in the step 1) is finished, the product is washed, filtered and dried by water.
Preferably, in the step 2), phthalic anhydride, urea, ammonium molybdate, ammonium ferrous sulfate hexahydrate and modified activated carbon are mixed, ground uniformly and then sintered in a muffle furnace.
Preferably, the sintering in step 2) is performed at 10 ℃ for min -1 The temperature rising rate is increased from room temperature to 270 ℃, the temperature is kept for 2h, the product is naturally cooled to room temperature after the temperature keeping is finished, and the product is purified by ultrapure water and then dried to obtain the iron phthalocyanine/modified activated carbon.
Preferably, in the step 3), the iron phthalocyanine/modified activated carbon and the sulfur powder are mixed and ground uniformly and then placed in a tubular furnace for reaction.
Preferably, the reaction in the step 3) is carried out under an argon atmosphere, and the flow rate of argon is 10-50 sccm.
Preferably, the tubular furnace in the step 3) is used for 10 ℃ min -1 The temperature rising rate is increased from room temperature, the reaction product is naturally cooled to room temperature after the reaction is finished, the product is purified and dried, the purification is that the product is respectively washed for a plurality of times by using ultrapure water and absolute ethyl alcohol, and the drying is that the product is dried in vacuum for 12-36 hours.
The invention also provides a MoS 2 The nitrogen-doped carbon/modified activated carbon sodium ion battery cathode material adopts the MoS 2 The preparation method of the/N-doped carbon/modified activated carbon sodium ion battery cathode material comprises the steps of taking the modified activated carbon as a substrate, taking the N-doped carbon as a transition layer, and preparing MoS 2 The nanosheets are uniformly grown on the substrate and the transition layer at 0.5A g -1 The initial discharge capacity was 831.5mAh g when cycled at a current density of (1) -1 The first coulombic efficiency was 67.3%, and after 100 cycles, the capacity remained 353.1mAh g -1 。
Compared with the prior art, the preparation method of the invention firstly adopts nitric acid solution water-bath heat treatment to modify the active carbon to obtain modified active carbon (FAC) with the surface rich in active functional groups; then, iron phthalocyanine/modified activated carbon (FePc/FAC) is prepared in one step by an in-situ solid-phase method, and finally, the iron phthalocyanine/modified activated carbon and sulfur powder are fully mixed and then subjected to heat treatment, so that on one hand, the iron phthalocyanine/modified activated carbon is cracked into nitrogen-doped carbon, and on the other hand, by using side products generated in the process of synthesizing the iron phthalocyanine/modified activated carbonThe molybdenum trioxide and gaseous sulfur at high temperature act to grow molybdenum disulfide in situ to obtain MoS 2 The nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material. MoS 2 The carbon material is compounded with the carbon material, so that the conductivity can be improved, the volume change in the charging and discharging process is relieved, the stability of the electrode structure is improved, the activated carbon is not easy to adhere, and the carbon material has the advantages of high specific surface area, simple production process, low cost and the like. Wherein, nitric acid modifies the activated carbon to increase the surface active functional groups, which is favorable for MoS 2 Provides nucleation sites and can also significantly inhibit MoS 2 Stacking the sheets; reconstructing a transition layer to further stabilize the structure and improving MoS by regulating and controlling the chemical structure and microstructure 2 The stability and the conductivity of/NC/FAC are realized by adopting nitric acid modified activated carbon (FAC) as a conductive substrate, and the nitric acid modification treatment is favorable for increasing oxygen-containing functional groups on the surface of the FAC so as to increase MoS 2 The interface bonding strength of (2), stability and conductivity are improved. In addition, on the basis of nitric acid modified activated carbon, a carbon transition layer doped with iron phthalocyanine cracking nitrogen is introduced to further regulate and control a molybdenum disulfide/modified activated carbon interface. Through the synergistic effect among three components in the composite structure system, the stability is improved, and the conductivity is improved, so that the high-performance sodium storage is realized. The preparation process is simple and easy to control, low in energy consumption and good in repeatability, and is beneficial to industrial production.
MoS prepared by the invention 2 N-doped carbon/modified activated carbon sodium ion battery negative electrode material (MoS) 2 /NC/FAC)，MoS 2 The nano-sheet grows uniformly on a material with FAC as a substrate and NC as a transition layer, the size distribution is uniform, the size distribution is about 100nm, and MoS 2 The ternary composite material of/NC/FAC is 0.5A g -1 The initial discharge capacity of 831.5mAh g when cycled at a current density of -1 The first coulombic efficiency was 67.3%, and after 100 cycles, the capacity remained 353.1mAh g -1 . The results show that MoS 2 The sodium storage stability of/NC/FAC is higher than that of MoS 2 a/FAC electrode material. The ternary system MoS 2 The negative electrode material of the/NC/FAC sodium-ion battery shows excellent conductivity, cycling stability and high specific discharge capacity, and can be widely used as the negative electrode material of the sodium-ion battery.
Drawings
FIG. 1 shows MoS obtained in example 3 2 XRD pattern of/NC/FAC sodium ion battery cathode material;
FIG. 2 shows MoS obtained in example 3 2 SEM image of/NC/FAC sodium ion battery cathode material;
FIG. 3 shows MoS obtained in example 3 2 Negative electrode material of/NC/FAC sodium ion battery and MoS prepared by comparative example 2 Comparative chart of cycle performance test of negative electrode material of FAC sodium ion battery.
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 discloses a MoS 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material specifically comprises the following steps:
1) transferring the activated carbon into a nitric acid solution with the concentration of 1-5 mol/L by adopting a water bath heating method, stirring, heating and insulating for 6-30 hours at 50-100 ℃, and washing, filtering, and drying a product after the insulation to obtain modified activated carbon;
2) adopting an in-situ solid phase method, taking 0.41-1.71 g of phthalic anhydride, 1.02-2.56 g of urea, 0.16-2.48 g of ammonium molybdate and 0.69-2.02 g of ferrous ammonium sulfate hexahydrate as raw materials, taking 0.06-0.41 g of modified activated carbon as a substrate, uniformly mixing and grinding the raw materials, sintering the mixture in a muffle furnace at 270 ℃ and preserving heat for 2 hours to synthesize iron phthalocyanine/modified activated carbon; preferably, the sintering is performed at 10 ℃ for min -1 The temperature rising rate is increased from room temperature to 270 ℃, the temperature is preserved for 2 hours, the temperature is naturally cooled to room temperature after the temperature preservation is finished, and the product is purified by ultrapure water and then dried;
3) uniformly mixing and grinding the iron phthalocyanine/modified activated carbon and the sulfur powder with equal mass, and then placing the mixture in a tube furnace to keep the temperature at 800-1000 ℃ in an inert atmosphereCracking the mixture at high temperature into nitrogen-doped carbon and growing molybdenum disulfide in situ at the same time for 1-2 hours to obtain MoS 2 and/NC/FAC. Preferably, the reaction is carried out in an argon atmosphere at an argon flow rate of 10-50 sccm and in a tube furnace at 10 ℃ for min -1 The temperature rising rate is increased from room temperature, the reaction product is naturally cooled to room temperature after the reaction is finished, the product is purified and dried, the purification is that the product is respectively washed for a plurality of times by using ultrapure water and absolute ethyl alcohol, and the drying is that the product is dried in vacuum for 12-36 hours.
The invention also provides a MoS 2 The nitrogen-doped carbon/modified activated carbon sodium ion battery cathode material is prepared by the preparation method, namely MoS 2 the/NC/FAC takes modified active carbon as a substrate, nitrogen-doped carbon as a transition layer and MoS 2 The nanosheets are uniformly grown on the substrate and the transition layer at 0.5A g -1 The initial discharge capacity was 831.5mAh g when cycled at a current density of (1) -1 The first coulombic efficiency was 67.3%, and after 100 cycles, the capacity remained 353.1mAh g -1 。
The present invention will be described in detail with reference to specific examples.
Example 1:
the method comprises the following steps:
1) adding activated carbon into a nitric acid solution with the concentration of 1mol/L, heating to 100 ℃ while magnetically stirring, preserving heat for 6 hours, washing, filtering, and drying after the heat preservation is finished to obtain nitric acid modified activated carbon (FAC);
2) weighing 0.41g of phthalic anhydride, 1.02g of urea, 0.16g of ammonium molybdate, 0.69g of ammonium ferrous sulfate hexahydrate and 0.06g of FAC, grinding uniformly in a glass mortar, and placing in a muffle furnace at 10 ℃ for min -1 The heating rate is increased from room temperature to 270 ℃, the temperature is maintained for 2 hours, the temperature is naturally cooled to room temperature after the temperature is maintained, and the FePc/FAC is obtained after the temperature is purified by ultrapure water and then dried;
3) 0.38g of FePc/FAC and 0.38g of sulfur powder are mixed and ground uniformly, and the mixture is transferred into a tube furnace in the argon atmosphere and is heated for 10 min -1 The temperature rising rate is increased from room temperature to 1000 ℃, the temperature is kept for 1h, and the mixture is naturally cooled;
4) collecting the above products, washing with deionized water and anhydrous ethanol for 3 times respectively, vacuum drying for 36h,obtaining MoS 2 The negative electrode material of the/NC/FAC sodium-ion battery.
Example 2:
the method comprises the following steps:
1) adding activated carbon into a nitric acid solution with the concentration of 2mol/L, heating to 60 ℃ while magnetically stirring, preserving heat for 12 hours, washing, filtering and drying after the heat preservation is finished to obtain nitric acid modified activated carbon (FAC);
2) weighing 0.73g of phthalic anhydride, 1.42g of urea, 0.31g of ammonium molybdate, 1.05g of ammonium ferrous sulfate hexahydrate and 0.13g of FAC, grinding uniformly in a glass mortar, and placing in a muffle furnace at 10 ℃ for min -1 Raising the temperature from room temperature to 270 ℃ at the temperature raising rate, preserving the heat for 2 hours, naturally cooling to room temperature after the heat preservation is finished, purifying with ultrapure water, and drying to obtain FePc/FAC;
3) 0.38g of FePc/FAC and 0.38g of sulfur powder are mixed and ground uniformly, and the mixture is transferred into a tube furnace in the argon atmosphere and is heated for 10 min -1 The temperature rising rate is increased from room temperature to 950 ℃, the temperature is kept for 1h, and the mixture is naturally cooled;
4) collecting the above products, washing with deionized water and anhydrous ethanol for 3 times respectively, and vacuum drying for 24h to obtain MoS 2 The negative electrode material of the/NC/FAC sodium-ion battery.
Example 3:
the method comprises the following steps:
1) adding activated carbon into a nitric acid solution with the concentration of 3mol/L, heating to 80 ℃ while magnetically stirring, preserving heat for 18 hours, washing, filtering and drying after the heat preservation is finished to obtain nitric acid modified activated carbon (FAC);
2) weighing 1.05g of phthalic anhydride, 1.81g of urea, 0.62g of ammonium molybdate, 1.38g of ammonium ferrous sulfate hexahydrate and 0.23g of FAC, grinding uniformly in a glass mortar, and placing in a muffle furnace at 10 ℃ for min -1 Raising the temperature from room temperature to 270 ℃ at the temperature raising rate, preserving the heat for 2 hours, naturally cooling to room temperature after the heat preservation is finished, purifying with ultrapure water, and drying to obtain FePc/FAC;
3) 0.38g of FePc/FAC and 0.38g of sulfur powder are mixed and ground uniformly, and the mixture is transferred into a tube furnace in the argon atmosphere and is heated for 10 min -1 The temperature rising rate is increased from room temperature to 900 ℃, the temperature is kept for 2h, and the product is naturally cooled;
4) collecting the above products, washing with deionized water and anhydrous ethanol for 3 times respectively, and vacuum drying for 12h to obtain MoS 2 The negative electrode material of the/NC/FAC sodium-ion battery.
Referring to FIG. 1, it can be seen from FIG. 1 that the product produced is MoS 2 Comparing with standard PDF card, the NC/FAC shows that the peak position of diffraction peak is basically completely matched, which indicates that the prepared product is the target product MoS 2 /NC/FAC。
See FIG. 2, by MoS 2 MoS can be found in a topographic map of/NC/FAC 2 The nano-sheet grows uniformly on a material which takes FAC as a substrate and NC as a transition layer, and the size distribution is uniform and about 100 nm.
For comparison, design M O S 2 Comparative example prepared by FAC: mixing ammonium molybdate 1.05g, sulfur powder 2.03g and modified active carbon 0.12g, grinding uniformly, transferring into a tube furnace at 10 deg.C for 10 min -1 The heating rate is increased from room temperature to 750 ℃, the temperature is kept for 2h, the mixture is naturally cooled to room temperature, and the mixture is washed for 3 times by deionized water and absolute ethyl alcohol and then is dried for 12h in vacuum, so that MoS is obtained 2 A negative electrode material of FAC sodium ion battery.
Referring to FIG. 3, MoS can be seen from FIG. 3 2 When the/NC/FAC nano composite material is used as the cathode material of the sodium-ion battery, compared with the M prepared by the comparative example O S 2 /FAC with significant capacity increase and improved cycling stability, MoS 2 (NC/FAC at 0.5A g -1 The initial discharge capacity of 831.5mAh g when cycled at a current density of -1 The first coulombic efficiency was 67.3%, and after 100 cycles, the capacity remained 353.1mAh g -1 . The results show that MoS 2 The sodium storage stability of/NC/FAC is higher than that of MoS 2 a/FAC electrode material.
Example 4:
the method comprises the following steps:
1) adding activated carbon into a nitric acid solution with the concentration of 4mol/L, heating to 50 ℃ while magnetically stirring, preserving heat for 24 hours, washing, filtering and drying after the heat preservation is finished to obtain nitric acid modified activated carbon (FAC);
2) balance1.37g of phthalic anhydride, 2.21g of urea, 1.24g of ammonium molybdate, 1.71g of ammonium ferrous sulfate hexahydrate and 0.32g of FAC are taken, ground uniformly in a glass mortar and then placed in a muffle furnace for 10 ℃ min -1 The heating rate is increased from room temperature to 270 ℃, the temperature is maintained for 2 hours, the temperature is naturally cooled to room temperature after the temperature is maintained, and the FePc/FAC is obtained after the temperature is purified by ultrapure water and then dried;
3) 0.38g of FePc/FAC and 0.38g of sulfur powder are mixed and ground uniformly, and the mixture is transferred into a tube furnace in the argon atmosphere and is heated for 10 min -1 The temperature rising rate is increased from room temperature to 900 ℃, the temperature is kept for 2h, and the product is naturally cooled;
4) collecting the above products, washing with deionized water and anhydrous ethanol for 3 times respectively, and vacuum drying for 20h to obtain MoS 2 The negative electrode material of the/NC/FAC sodium-ion battery.
Example 5:
the method comprises the following steps:
1) adding activated carbon into a nitric acid solution with the concentration of 5mol/L, heating to 70 ℃ while magnetically stirring, preserving heat for 30 hours, washing, filtering, and drying after the heat preservation is finished to obtain nitric acid modified activated carbon (FAC);
2) weighing 1.71g of phthalic anhydride, 2.56g of urea, 2.48g of ammonium molybdate, 2.02g of ammonium ferrous sulfate hexahydrate and 0.41g of FAC, grinding uniformly in a glass mortar, and placing in a muffle furnace at 10 ℃ for min -1 Raising the temperature from room temperature to 270 ℃ at the temperature raising rate, preserving the heat for 2 hours, naturally cooling to room temperature after the heat preservation is finished, purifying with ultrapure water, and drying to obtain FePc/FAC;
3) 0.38g of FePc/FAC and 0.38g of sulfur powder are mixed and ground uniformly, and the mixture is transferred into a tube furnace in the argon atmosphere and is heated for 10 min -1 The temperature rising rate is increased from room temperature to 800 ℃, the temperature is kept for 1h, and the mixture is naturally cooled;
4) collecting the above products, washing with deionized water and anhydrous ethanol for 3 times respectively, and vacuum drying for 30h to obtain MoS 2 The negative electrode material of the/NC/FAC sodium-ion battery.
The preparation method comprises the steps of firstly modifying the activated carbon by adopting a nitric acid solution water bath heat treatment method to obtain modified activated carbon (FAC), then synthesizing iron phthalocyanine/FAC (FePc/FAC) by adopting an in-situ solid phase method, and finally uniformly mixing the FePc/FAC and sulfur powderUniformly placing the mixture in an argon atmosphere, pyrolyzing FePc/FAC to nitrogen-doped carbon/FAC, and simultaneously growing MoS in situ by using the action of molybdenum trioxide and sulfur powder which are byproducts of FePc synthesis 2 Obtaining MoS 2 The method has novel design thought, and the MoS is prepared by adopting a high-temperature heat treatment process 2 a/NC/FAC nanocomposite material, thereby avoiding M O S 2 The cyclic stability of the material is improved. The method adopted by the invention has the characteristics of simple process, good repeatability, high safety and the like. MoS prepared by the invention 2 The/nitrogen-doped carbon/modified activated carbon ternary nano composite material has a high specific surface area, and can be used as an excellent sodium ion battery cathode material by using the phthalocyanine iron cracking nitrogen-doped carbon as a molybdenum disulfide/modified activated carbon interface to improve the sodium storage stability.
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 (9)
1. MoS 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material is characterized by comprising the following steps of:
1) transferring the activated carbon into a nitric acid solution by adopting a water bath heating method, stirring, heating at 50-100 ℃, and keeping the temperature for 6-30 hours to obtain modified activated carbon;
2) an in-situ solid phase method is adopted, 0.41-1.71 g of phthalic anhydride, 1.02-2.56 g of urea, 0.16-2.48 g of ammonium molybdate and 0.69-2.02 g of ferrous ammonium sulfate hexahydrate are used as raw materials, 0.06-0.41 g of modified activated carbon is used as a substrate, sintering is carried out at 270 ℃, and heat preservation is carried out for 2 hours, so as to synthesize iron phthalocyanine/modified activated carbon;
3) keeping the same mass of iron phthalocyanine/modified activated carbon and sulfur powder at 800-1000 ℃ for 1-2 hours in an inert atmosphere, pyrolyzing the iron phthalocyanine/modified activated carbon and sulfur powder to form nitrogen-doped carbon, and growing molybdenum disulfide in situ to obtain MoS 2 The nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material.
2. A MoS according to claim 1 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material is characterized in that the concentration of a nitric acid solution in the step 1) is 1-5 mol/L.
3. A MoS according to claim 1 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery cathode material is characterized in that a product is washed, filtered and dried by water after the heat preservation in the step 1) is finished.
4. A MoS according to claim 1 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery cathode material is characterized in that phthalic anhydride, urea, ammonium molybdate, ammonium ferrous sulfate hexahydrate and modified activated carbon in the step 2) are mixed, ground uniformly and then sintered in a muffle furnace.
5. A MoS according to claim 4 2 The preparation method of the/N-doped carbon/modified activated carbon sodium ion battery cathode material is characterized in that the sintering in the step 2) is carried out for 10 min -1 The temperature rising rate is increased from room temperature to 270 ℃, the temperature is kept for 2h, the product is naturally cooled to room temperature after the temperature keeping is finished, and the product is purified by ultrapure water and then dried to obtain the iron phthalocyanine/modified activated carbon.
6. A MoS according to claim 1 2 The preparation method of the/N-doped carbon/modified activated carbon sodium ion battery cathode material is characterized in that in the step 3), the iron phthalocyanine/modified activated carbon and the sulfur powder are mixed, ground uniformly and then placed in a tubular furnace for reaction.
7. A MoS according to claim 6 2 The preparation method of the/nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material is characterized in that the reaction in the step 3) is carried out in an argon atmosphere, and the flow rate of argon is 10-50 sccm.
8. A MoS according to claim 6 2 The preparation method of the/N-doped carbon/modified activated carbon sodium ion battery cathode material is characterized in that the tubular furnace in the step 3) is used for 10 ℃ min -1 The temperature rising rate is increased from room temperature, the reaction product is naturally cooled to room temperature after the reaction is finished, the product is purified and dried, the purification is that the product is respectively washed for a plurality of times by using ultrapure water and absolute ethyl alcohol, and the drying is that the product is dried in vacuum for 12-36 hours.
9. MoS 2 A/N-doped carbon/modified activated carbon sodium ion battery negative electrode material, characterized in that the MoS of any one of claims 1 to 8 is adopted 2 The preparation method of the/N-doped carbon/modified activated carbon sodium ion battery cathode material comprises the steps of taking the modified activated carbon as a substrate, taking the N-doped carbon as a transition layer, and preparing MoS 2 The nanosheets are uniformly grown on the substrate and the transition layer at 0.5A g -1 The initial discharge capacity was 831.5mAh g when cycled at a current density of (1) -1 The first coulombic efficiency was 67.3%, and after 100 cycles, the capacity remained 353.1mAh g -1 。
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