CN117263246A - MoS with hollow nanometer microsphere structure 2 Preparation method of potassium ion battery anode material - Google Patents
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- 239000004005 microsphere Substances 0.000 title claims abstract description 53
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 53
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title claims description 16
- 239000007787 solid Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 10
- 239000010406 cathode material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000013543 active substance Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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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- 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
-
- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2006/40—Electric properties
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- 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
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Abstract
The invention relates to a hollow nanometer microsphere structure MoS 2 A preparation method of a potassium ion battery cathode material belongs to the technical field of potassium ion batteries. The invention uses Na 2 MoO 4 、CH 4 N 2 S and SiO 2 Adding the suspension into deionized water, and stirring and uniformly mixing to obtain a mixed solution A; sealing the mixed solution A, then placing the mixed solution A into a hydrothermal reaction at the temperature of 200-240 ℃ for 10-14 h, naturally cooling, carrying out solid-liquid separation to obtain a solid B, washing the solid B by deionized water and ethanol in sequence, and drying to obtain an intermediate product SiO 2 @MoS 2 The method comprises the steps of carrying out a first treatment on the surface of the To intermediate SiO 2 @MoS 2 Adding the mixture into NaOH solution, and reacting at room temperature to remove SiO selectively 2 Solid-liquid separation is carried out to obtain solid C, the solid C is washed by deionized water and ethanol in sequence, and the hollow nanometer microsphere structure MoS is obtained by drying 2 . The invention relates to a hollow nanometer microsphere structure MoS prepared by a template hydrothermal method 2 The material is used as the negative electrode of the potassium ion battery, and has high specific capacity, excellent charge and discharge performance, good rate capability and good cycle stability.
Description
Technical Field
The invention relates to a hollow nanometer microsphere structure MoS 2 A preparation method of a potassium ion battery cathode material belongs to the technical field of high-purity quartz sand purification.
Background
Lithium ion batteries have become the most widely used electrochemical energy storage system with the largest standard mode at present due to the advantages of high energy density, low self-discharge, long service life, high voltage, no memory effect and the like. However, problems of shortage of lithium resources, high cost, easiness in generation of lithium dendrites and the like limit continuous and wide application of the lithium ion battery in an energy storage system, so that searching for a lithium ion battery substitute with better performance has strategic significance. The potassium in the same main group as lithium has similar physical and chemical properties and similar energy storage mechanism of a rocking chair battery, the potassium element content is rich in nature, the aluminum foil with low price can be used for the negative electrode current collector of the potassium ion battery, and the energy density of the potassium ion battery is improved while the cost is reduced. Potassium ion batteries are therefore considered to be one of the most desirable energy storage systems for replacing lithium ion batteries. However, the large radius of potassium ions causes serious problems of volume expansion and slow reaction kinetics of the potassium ion battery during charge and discharge cycles, so that the capacity of the potassium ion battery is rapidly attenuated and the cycle stability of the potassium ion battery is poor, and therefore, the development of an excellent cathode material of the potassium ion battery is important.
At present, graphite is widely used as a negative electrode of a potassium ion battery, and the negative electrode is over 200mAh g -1 Is a reversible capacity of (a). But due to K during charge-discharge cycles + The problems of volume expansion and the like caused by embedding/extracting destroy the structure of an electrode material, so that the capacity attenuation of the potassium ion battery is serious, and the rate capability and the cycle performance are poor.
Disclosure of Invention
Aiming at the technical problems of poor multiplying power performance, poor cycle stability performance and the like in a carbon anode material of a potassium ion battery, the invention provides a MoS with a hollow nano microsphere structure 2 The invention relates to a preparation method of a potassium ion battery cathode material, which adopts a hollow nanometer microsphere structure MoS prepared by a template hydrothermal method 2 Material and hollow nanometer microsphere structure MoS 2 Has high theoretical specific capacity, can provide high specific capacity for potassium ion batteries, moS 2 The nanometer microsphere also has a good ion embedding structure, is favorable for the embedding/taking-off of potassium ions and inhibits the volume expansion in the process, and meanwhile, due to the hollow nanometer microsphere structure MoS 2 The electrolyte has larger specific surface area, and can provide more active sites for electrolyte and active materials, thereby effectively improving the rate capability and the cycle stability of the potassium ion battery.
MoS with hollow nanometer microsphere structure 2 The preparation method of the potassium ion battery anode material comprises the following specific steps:
(1) Na is mixed with 2 MoO 4 、CH 4 N 2 S and SiO 2 Adding the suspension into deionized water, and stirring and uniformly mixing to obtain a mixed solution A;
(2) Sealing the mixed solution A, then placing the mixed solution A into a hydrothermal reaction at the temperature of 200-240 ℃ for 10-14 h, naturally cooling, carrying out solid-liquid separation to obtain a solid B, washing the solid B by deionized water and ethanol in sequence, and drying to obtain an intermediate product SiO 2 @MoS 2 ；
(3) To intermediate SiO 2 @MoS 2 Adding the mixture into NaOH solution, and reacting at room temperature to remove SiO selectively 2 Solid-liquid separation to obtain solid C and solidWashing the hollow microsphere structure MoS by deionized water and ethanol in sequence, and drying to obtain the hollow microsphere structure MoS 2 。
The step (1) SiO 2 The mass concentration of the suspension is 30-50%.
The step (1) Na 2 MoO 4 、CH 4 N 2 S and 40wt% SiO 2 The solid-liquid ratio of the suspension to the deionized water is mmol, wherein the ratio of mmol to mL is 1-5:10-50:1-5:30-70.
The concentration of the NaOH solution in the step (1) is 0.8-1.2 mol/L.
The beneficial effects of the invention are as follows:
(1) The invention relates to a MoS prepared by a template hydrothermal method 2 The material has a hollow nano microsphere structure, uniform appearance, high crystallinity and MoS 2 Has high theoretical specific capacity, can provide high specific capacity for potassium ion batteries, moS 2 The nanometer microsphere also has a good ion embedding structure, is favorable for the embedding/taking-off of potassium ions and inhibits the volume expansion in the process, and meanwhile, due to the hollow nanometer microsphere structure MoS 2 The electrolyte has larger specific surface area, and can provide more active sites for the electrolyte and the active material, thereby effectively improving the rate capability and the cycle stability of the potassium ion battery;
(2) MoS with hollow nano microsphere structure 2 The potassium ion battery cathode has excellent charge and discharge performance, cycle performance and multiplying power performance; at 0.2Ag -1 Under the current density, the first discharge capacity reaches 350mAh g -1 The specific capacity is kept at 250mAh g after 100 circles of circulation -1 The circulating stability is higher;
(3) MoS with hollow nano microsphere structure 2 The potassium ion battery cathode has a stable structure in the charge and discharge process, is not easy to collapse, and the hollow porous structure is beneficial to rapid migration of ions and improves ion mobility.
Drawings
FIG. 1 is a MoS of a hollow nanoparticle structure in example 2 2 XRD pattern of the negative electrode material of the potassium ion battery;
FIG. 2 is a MoS of a hollow nanoparticle structure in example 2 2 SEM image of (2)；
FIG. 3 is a MoS of a hollow nanoparticle structure in example 2 2 A TEM image of (a);
FIG. 4 is a MoS of a hollow nanoparticle structure in example 2 2 Is a CV diagram of (c);
FIG. 5 is a constant current cycle performance curve of the potassium ion battery of example 2;
fig. 6 is a constant current cycle performance curve at different rates of the potassium ion battery of example 2.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: moS with hollow nanometer microsphere structure 2 The preparation method of the potassium ion battery anode material comprises the following specific steps:
(1) 1mmol Na 2 MoO 4 、10mmol CH 4 N 2 S, 1ml of SiO with a concentration of 30wt.% 2 Adding the suspension into 30ml of deionized water, and stirring and uniformly mixing to obtain a mixed solution A;
(2) Transferring the mixed solution A into a 50ml polytetrafluoroethylene lining stainless steel high-pressure reaction kettle, sealing, then placing the mixed solution A into a temperature of 200 ℃ for hydrothermal reaction for 10 hours, naturally cooling, carrying out solid-liquid separation to obtain black solid B, washing the solid B with deionized water for 2 times, washing the solid B with ethanol for 2 times, and drying the solid B at the temperature of 70 ℃ for 10 hours to obtain an intermediate product SiO 2 @MoS 2 ；
(3) To intermediate SiO 2 @MoS 2 Added into 130mL NaOH solution with the concentration of 0.8mol/L, and reacted for 12h at room temperature to selectively remove SiO 2 Solid-liquid separation to obtain solid C, washing solid C with deionized water for 2 times, washing solid C with ethanol for 2 times, and drying at 70deg.C for 10 hr to obtain hollow nanometer microsphere MoS 2 ；
MoS with hollow nano microsphere structure in embodiment 2 The potassium ion battery anode material sample has stronger crystallinity, the hollow structure enables the nano microsphere to have larger specific surface area, and the porous structure provides a fast diffusion channel for ion migration, thereby effectively improving ion diffusionNumber and mobility;
the potassium ion battery assembled in the embodiment comprises a positive electrode and a negative electrode (the active material of the negative electrode is MoS with a hollow nanometer microsphere structure) 2 ) The negative electrode comprises a negative electrode current collector aluminum foil and a negative electrode material layer coated on the surface of the negative electrode current collector, wherein the negative electrode material layer comprises a negative electrode active substance, a conductive agent (carbon black C65) and a binder (CMC), and the negative electrode active substance is of a hollow nanometer microsphere structure MoS 2 A negative electrode material; in mass percent, the negative electrode active material (hollow nanometer microsphere structure MoS) 2 Negative electrode material) accounting for 70%, conductive agent (carbon black C65) accounting for 20%, binder (CMC) accounting for 10%; the coating thickness of the negative electrode material layer is 12mm;
at 0.2Ag -1 At current density, the capacity of the potassium ion battery after 100 times of circulation is about 220mAh g -1 The circulating stability is higher; the hollow nano microsphere structure is not easy to damage in the charge and discharge process, and the hollow porous structure has larger specific surface area to provide more active contact sites, so that the capacity of the potassium ion battery is higher; meanwhile, the porous structure provides a fast diffusion channel for ion migration, so that the ion diffusion quantity and mobility are effectively improved.
Example 2: moS with hollow nanometer microsphere structure 2 The preparation method of the potassium ion battery anode material comprises the following specific steps:
(1) 3mmol of Na 2 MoO 4 、30mmol CH 4 N 2 S, 3ml of SiO with a concentration of 40wt.% 2 Adding the suspension into 50ml of deionized water, and stirring and uniformly mixing to obtain a mixed solution A;
(2) Transferring the mixed solution A into a 100ml polytetrafluoroethylene lining stainless steel high-pressure reaction kettle, sealing, then placing the mixed solution A into a 220 ℃ hydrothermal reaction kettle for 12 hours, naturally cooling, separating solid from liquid to obtain black solid B, washing the solid B with deionized water for 3 times, washing the solid B with ethanol for 3 times, and drying the solid B for 12 hours at 80 ℃ to obtain an intermediate product SiO 2 @MoS 2 ；
(3) To intermediate SiO 2 @MoS 2 Added to 150mL of the mixture with the concentration of 1mol/LIn NaOH solution, reacting for 14h at room temperature to selectively remove SiO 2 Solid-liquid separation to obtain solid C, washing solid C with deionized water for 3 times, washing solid C with ethanol for 3 times, and drying at 80deg.C for 10 hr to obtain hollow nanometer microsphere MoS 2 ；
MoS of the present embodiment 2 XRD patterns of the anode material of the potassium ion battery are shown in figure 1, and as can be seen from figure 1, the hollow nanometer microsphere structure MoS 2 The crystallinity of the negative material sample of the potassium ion battery is strong;
MoS with hollow nano microsphere structure 2 See FIG. 2 for an SEM image of (2), from FIG. 2, moS 2 The microsphere is a flower cluster microsphere structure consisting of uniform nano sheets, the size is about 200-240 nm, the microsphere structure is regular, and the morphology and the dispersion are uniform;
MoS with hollow nano microsphere structure 2 The TEM image of (A) is shown in FIG. 3, and from FIG. 3, moS 2 The nano-sheets grow on the surfaces of the microspheres, the nano-microspheres are in a hollow structure, the nano-sheet layers and the hollow structure enable the nano-microspheres to have larger specific surface area, and the porous structure provides a fast diffusion channel for ion migration, so that the ion diffusion quantity and mobility are effectively improved;
MoS with hollow nano microsphere structure 2 As can be seen from fig. 4, the oxidation peak appears at 1.73V during the first charge and the reduction peaks appear at 0.01V and 1.11V during the discharge; oxidation peaks appear at 1.73V during charge 2 and reduction peaks appear at 0.01V and 0.40V during discharge; oxidation peaks appear at 1.73V during charge 3 and reduction peaks appear at 0.01V and 0.40V during discharge; in the fourth and fifth charging and discharging processes, the positions of the oxidation peak and the reduction peak are overlapped with the positions of the oxidation-reduction peak in the third charging and discharging process;
the constant current cycle performance curve of the potassium ion battery of this example is shown in FIG. 5, and as can be seen from FIG. 5, the constant current cycle performance curve is shown in 0.2Ag -1 At current density, the capacity of the potassium ion battery after 100 times of circulation is about 240mAh g -1 The coulombic efficiency is about 100%. In the process of 100 cycles, the capacity of the potassium ion battery is seriously lost for the first time, which results inThe reason for the capacity loss is irreversible structural change and generation of an SEI film; the capacity loss of the battery gradually decreases during the 2 nd to 10 th cycles, and the structure of the battery tends to be stable; the battery capacity was about 290mAh g during the 10 th to 60 th cycles -1 Almost unchanged, the battery structure is stable; during cycles 70 to 100, the battery capacity begins to decrease again, from about 290mAh g -1 To 240mAh g -1 ；
The potassium ion battery comprises a positive electrode and a negative electrode (the active material of the negative electrode is MoS with a hollow nanometer microsphere structure) 2 ) Separator (glass fiber) and electrolyte (1M KFSI EC: DMC (1:1)), wherein the anode comprises an anode current collector aluminum foil and an anode material layer coated on the surface of the anode current collector, the anode material layer comprises an anode active substance, a conductive agent (carbon black C65) and a binder (CMC), and the anode active substance is a hollow nanometer microsphere structure MoS 2 A negative electrode material; in percentage by mass, the negative electrode active material (hollow nanometer microsphere structure MoS2 negative electrode material) in the negative electrode material layer accounts for 70%, the conductive agent (carbon black C65) accounts for 20%, and the binder (CMC) accounts for 10%; the coating thickness of the negative electrode material layer is 12mm;
the constant current cycle performance curves of the potassium ion battery under different multiplying powers are shown in fig. 6, and it can be seen from fig. 6 that the cycle tests are respectively carried out at 0.05C, 0.1C, 0.2C, 0.5C, 1C and 2C, and the corresponding specific capacity is 300 mAh.g -1 、280mAh·g -1 、270mAh·g -1 、190mAh·g -1 、100mAh·g -1 And 50 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the When the temperature is recovered from 2C to 0.05C, the specific capacity can be almost recovered, which shows that the rate performance, the cycle stability and the reversibility of the potassium ion battery are better.
Example 3: moS with hollow nanometer microsphere structure 2 The preparation method of the potassium ion battery anode material comprises the following specific steps:
(1) 5mmol of Na 2 MoO 4 、50mmol CH 4 N 2 S, 5ml of SiO with a concentration of 50wt.% 2 Adding the suspension into 70ml of deionized water, and stirring and uniformly mixing to obtain a mixed solution A;
(2) Transfer the mixed solution A to 250ml polytetrafluoroethylene lining stainless steel high pressure reactorSealing in a kettle, performing hydrothermal reaction at 240 ℃ for 14 hours, naturally cooling, performing solid-liquid separation to obtain black solid B, washing the solid B with deionized water for 4 times, washing with ethanol for 4 times, and drying at 90 ℃ for 10 hours to obtain an intermediate product SiO 2 @MoS 2 ；
(3) To intermediate SiO 2 @MoS 2 Added into 170mL of NaOH solution with the concentration of 1.2mol/L, and reacted for 15 hours at room temperature to selectively remove SiO 2 Solid-liquid separation to obtain solid C, washing solid C with deionized water for 4 times, washing solid C with ethanol for 3 times, and drying at 90deg.C for 8 hr to obtain hollow nanometer microsphere MoS 2 ；
MoS with hollow nano microsphere structure in embodiment 2 The potassium ion battery anode material sample has stronger crystallinity, the hollow structure enables the nano microsphere to have larger specific surface area, and the porous structure provides a fast diffusion channel for ion migration, so that the ion diffusion quantity and mobility are effectively improved;
the potassium ion battery assembled in the embodiment comprises a positive electrode and a negative electrode (the active material of the negative electrode is MoS with a hollow nanometer microsphere structure) 2 ) The negative electrode comprises a negative electrode current collector aluminum foil and a negative electrode material layer coated on the surface of the negative electrode current collector, wherein the negative electrode material layer comprises a negative electrode active substance, a conductive agent (carbon black C65) and a binder (CMC), and the negative electrode active substance is of a hollow nanometer microsphere structure MoS 2 A negative electrode material; in mass percent, the negative electrode active material (hollow nanometer microsphere structure MoS) 2 Negative electrode material) accounting for 70%, conductive agent (carbon black C65) accounting for 20%, binder (CMC) accounting for 10%; the coating thickness of the negative electrode material layer is 12mm;
at 0.2 A.g -1 At current density, the capacity of the potassium ion battery after 100 times of circulation is about 210 mAh.g -1 The circulating stability is higher; the hollow nano microsphere structure is not easy to damage in the charge and discharge process, and the hollow porous structure has larger specific surface area to provide more active contact sites, so that the capacity of the potassium ion battery is higher; while the porous structure provides a fast diffusion path for ion migration, withThe ion diffusion quantity and mobility are effectively improved.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (4)
1. MoS with hollow nanometer microsphere structure 2 The preparation method of the potassium ion battery anode material is characterized by comprising the following specific steps:
(1) Na is mixed with 2 MoO 4 、CH 4 N 2 S and SiO 2 Adding the suspension into deionized water, and stirring and uniformly mixing to obtain a mixed solution A;
(2) Sealing the mixed solution A, then placing the mixed solution A into a hydrothermal reaction at the temperature of 200-240 ℃ for 10-14 h, naturally cooling, carrying out solid-liquid separation to obtain a solid B, washing the solid B by deionized water and ethanol in sequence, and drying to obtain an intermediate product SiO 2 @MoS 2 ；
(3) To intermediate SiO 2 @MoS 2 Adding the mixture into NaOH solution, and reacting at room temperature to remove SiO selectively 2 Solid-liquid separation is carried out to obtain solid C, the solid C is washed by deionized water and ethanol in sequence, and the hollow nanometer microsphere structure MoS is obtained by drying 2 。
2. Hollow nanoparticle structure MoS according to claim 1 2 The preparation method of the potassium ion battery anode material is characterized by comprising the following steps: step (1) SiO 2 The mass concentration of the suspension is 30-50%.
3. Hollow nanoparticle structure MoS according to claim 1 2 The preparation method of the potassium ion battery anode material is characterized by comprising the following steps: step (1) Na 2 MoO 4 、CH 4 N 2 S and 40wt% SiO 2 The solid-liquid ratio of the suspension to the deionized water is mmol, wherein the ratio of mmol to mL is 1-5:10-50:1-5:30-70.
4. According to claim1 the hollow nanometer microsphere structure MoS 2 The preparation method of the potassium ion battery anode material is characterized by comprising the following steps: the concentration of the NaOH solution in the step (1) is 0.8-1.2 mol/L.
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