CN111799467A - MoS for negative electrode of sodium-ion battery2/MoS2Nanocomposite and method for preparing same - Google Patents

MoS for negative electrode of sodium-ion battery2/MoS2Nanocomposite and method for preparing same Download PDF

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CN111799467A
CN111799467A CN202010697152.7A CN202010697152A CN111799467A CN 111799467 A CN111799467 A CN 111799467A CN 202010697152 A CN202010697152 A CN 202010697152A CN 111799467 A CN111799467 A CN 111799467A
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mos
sodium
thiourea
negative electrode
ammonium molybdate
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CN111799467B (en
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许占位
刘鑫悦
黄剑锋
曹丽云
李智
姚恺
任宇川
陈思雨
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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
    • H01M4/58—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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 MoS for a negative electrode of a sodium-ion battery2/MoS2A nano composite material and a preparation method thereof, aiming at solving the problem of MoS caused by the intercalation and deintercalation of sodium ions in the charging and discharging processes in the related technology2Problem of Stacking of lamellae in the preparation method ammonium molybdate and thiourea are first dispersed in deionized water and ultra small MoS is added2Dropwise adding the dispersion liquid into the mixed liquid, stirring and drying the mixed liquid to obtain a precursor MoS2Ammonium molybdate/thiourea, and finally under an inert gas atmospherePrecursor MoS2Heating ammonium molybdate/thiourea, preserving heat and cooling to obtain MoS2/MoS2The nano composite material has simple preparation method and process, low preparation cost and easy realization, and can be prepared into ultra-small MoS2Uniformly fixed on MoS2On the nano-sheets, the sheets are not stacked together, so that enough electrochemical active sites are ensured, the nano-sheets are used as cathode materials of sodium ion batteries, and the cycling stability of the sodium ion batteries is improved.

Description

MoS for negative electrode of sodium-ion battery2/MoS2Nanocomposite and method for preparing same
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a MoS for a cathode of a sodium ion battery2/MoS2A nanocomposite and a method of making the same.
Background
The development of social economy can not avoid the large consumption of non-renewable energy sources such as coal, petroleum, natural gas and the like. The large-scale exploitation and utilization of traditional fossil energy aggravates the exhaustion of the existing energy and is accompanied by serious environmental pollution. Therefore, the adjustment of energy structure becomes a fundamental problem restricting the sustainable development of human society. At present, the traditional fossil energy is changed into renewable clean energy to be a new energy development direction, but new energy such as wind energy, solar energy, tidal energy, geothermal energy, biomass energy and the like are very dependent on the external environment, and have the defects of low energy density, unstable output and easy fluctuation. If the electric energy generated by the generator is directly input into the power grid, the generator has great influence on the power grid. Therefore, in order to meet the requirements of human society for energy, the development of an efficient energy storage system is a problem to be solved urgently.
The lithium ion battery has the advantages of large specific energy, long cycle life, high working voltage, no memory effect, small self-discharge, wide working temperature range, energy density and power, and the like, is regarded as a most promising high-efficiency electrochemical energy storage device, and is widely applied to portable electronic equipment and hybrid power systems. However, the lithium ion battery brings convenience to human beings and consumes a large amount of lithium resources, so that the lithium resources are increasingly in short supply, the expensive cost limits the large-scale use of the lithium ion battery, and the development of the next generation of energy storage system with excellent comprehensive performance becomes a problem to be solved urgently. The sodium element and the lithium element are located in the same main group and have similar electronic configurations. The sodium ion battery and the lithium ion battery are similar in composition and structure and mainly comprise a positive electrode material, a negative electrode material, electrolyte, a diaphragm and a current collector. The energy storage principle of the sodium ion battery is similar to that of the lithium ion battery, and the sodium ion battery is an embedded and detached battery, and the charging process is as follows: in the battery, sodium ions are removed from the anode material and are embedded into the cathode through the electrolyte and the diaphragm; the discharging process is opposite: sodium ions are extracted from the negative electrode and return to the positive electrode through the electrolyte and the diaphragm, and electrons outside the battery move in the same direction with the sodium ions in an external circuit so as to ensure the charge balance of the whole battery system. And the needed metal sodium salt is low in price and rich in crustal content, so that the energy storage system is a promising next-generation large-scale energy storage system.
The charge-discharge specific capacity, the cycle performance and the rate capability of the positive and negative electrode materials of the sodium ion battery are closely related to the embedding and separating processes of sodium ions in the positive and negative electrode materials in the charge-discharge process. According to literature reports, many studies on positive electrode materials of sodium-ion batteries are carried out, and the positive electrode materials of the sodium-ion batteries mainly comprise four types, namely layered transition metal oxides, tunnel structure oxides, polyanion type positive electrode materials and other novel positive electrode materials such as Prussian blue and the like. The radius of sodium ions (0.102nm) is about 1.4 times the radius of lithium ions (0.076nm), which makes it more difficult for sodium ions to intercalate and deintercalate between the positive and negative electrode materials than for lithium. The main cathode material graphite of the commercial lithium ion battery is used for the cathode of the sodium ion battery and only releases 35mA hg-1The capacity of (c). Therefore, the development of a negative electrode material which is matched with a high-performance positive electrode material and has high specific capacity, excellent cycling stability and excellent rate performance is an urgent problem to be solved.
Molybdenum disulfide (MoS), a typical two-dimensional transition metal sulfide2) Due to the specific S-Mo-S sandwich structure and higher active sulfur content, the material has good development prospect as a negative electrode material of a sodium ion battery. MoS2The interlayer spacing (0.65nm) is about 1.94 times the graphite interlayer spacing (0.335nm)The good diffusion channel of the material is enough to accommodate the rapid transfer of sodium ions in the charging and discharging processes, and the theoretical capacity of the material is up to 670mA h g-1And is a potential negative electrode material of the sodium ion battery. MoS2Sodium storage by "intercalation-conversion" mode:
MoS2+x Na+＝NaxMoS2(1-1)
NaxMoS2+(4-x)Na+＝Mo+2Na2S (1-2)
wherein, the formula (1-1) is intercalation reaction, and the formula (1-2) is conversion reaction.
However, it has low conductivity and electrochemical instability, and is not favorable for exhibiting cycle stability and rate capability. Furthermore, after the first cycle, MoS2The layered structure is rearranged and stacked, larger bulk phase particles are easily formed, and a large number of active sites disappear, so that the active sites can not fully react in the subsequent sodium intercalation/sodium deintercalation process, the capacity of the material is rapidly attenuated within about 30 circles, and the application of the material in an actual battery is influenced. To improve MoS2The unstable structure mainly has the scheme of introducing carbon material as a substrate and other oxides or simple substances as barriers to prevent stacking of sheets, such as: S/MoS2The above scheme effectively ameliorates the problem of material structure instability, but the second component, which is an antiblock agent, fills only the volume of the system and does not contribute to capacity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a MoS for a negative electrode of a sodium-ion battery2/MoS2Nano composite material, preparation method thereof and prepared MoS2/MoS2The nano composite material has stable structure, uniform appearance and high cycle stability, and solves the problem of MoS caused by sodium ion embedding and separating in the charging and discharging processes in the related technology2The problem of stacking sheets, the preparation method has low preparation cost and short period.
In order to achieve the above object, the present invention provides a MoS for a negative electrode of a sodium ion battery2/MoS2A process for preparing a nanocomposite material comprising the steps ofThe method comprises the following steps:
1) mass mAmmonium molybdate0.60 to 1.00g of ammonium molybdate and mThiourea1.80-2.20 g of thiourea is dispersed in 75-95 mL of deionized water to obtain a solution A, and 0.80-0.90 wt% of ultra-small MoS is taken2Dripping 5-20 mL of the dispersion liquid into the solution A to prepare a liquid B;
2) stirring and drying the liquid B to obtain a precursor MoS2Ammonium molybdate/thiourea;
3) under the inert gas atmosphere, the precursor MoS2Heating ammonium molybdate/thiourea at the temperature of 600-800 ℃, preserving heat and cooling to obtain MoS2/MoS2A nanocomposite material.
Further, the ultra-small MoS in the step 1)2The preparation of the dispersion comprises: firstly, MoS2Dispersing in NMP solution, and carrying out ultrasonic treatment in ice water to obtain suspension; then centrifugally separating the suspension, collecting supernatant, centrifugally separating for multiple times until the mixture is colorless and transparent, and obtaining the ultra-small MoS dispersed in NMP2And (3) dispersing the mixture.
Further, in the step 2), the liquid B is magnetically stirred for 10-15 hours, and then the water is dried to obtain a precursor MoS2Ammonium molybdate/thiourea.
Further, the precursor MoS is added in the step 3)2Heating ammonium molybdate/thiourea in a tubular atmosphere furnace from room temperature to 600-800 ℃, preserving heat, and cooling to room temperature to obtain MoS2/MoS2A nanocomposite material.
Further, the heat preservation time in the step 3) is 50-100 minutes.
Further, the tubular atmosphere furnace in the step 3) is used for heating at 5-10 ℃ for min-1The temperature rise rate is increased from room temperature to 600-800 ℃.
Further, the precursor MoS in the step 3) is treated2Before heating ammonium molybdate/thiourea, introducing argon with the gas flow of 80-240 sccm into a quartz tube of the tubular atmosphere furnace to exhaust air.
Further, the MoS obtained in the step 3)2/MoS2The nanocomposite was also subjected to deionized water andwashing with absolute ethyl alcohol for 6-10 times respectively, and vacuum drying for 8-12 h. The invention also provides a MoS for the cathode of the sodium-ion battery2/MoS2The nano composite material is prepared by the preparation method.
Further, the MoS2/MoS2The nanocomposite was at 500mA g-1Charging and discharging under the condition, and after 50 complete cycles, the specific discharge capacity is as follows: 315.4-447.6 mA h g-1。
Compared with the prior art, in the preparation method, firstly, ammonium molybdate and thiourea are dispersed in deionized water, and the ultra-small MoS is added2Adding the dispersed liquid into the mixed liquid drop by drop, stirring and drying the mixed liquid to obtain a precursor MoS2Ammonium molybdate/thiourea, and finally, under the inert gas atmosphere, the precursor MoS2Heating ammonium molybdate/thiourea at the temperature of 600-800 ℃, preserving heat and cooling to obtain MoS2/MoS2A nanocomposite material. The preparation method has the advantages of simple process, low preparation cost and short period, and the obtained MoS2/MoS2Nanocomposite, ultra small MoS2Uniformly fixed on MoS2On the nano-chip, the structure is stable, the appearance is uniform, and the MoS is ultra-small2Is filled with MoS2Volume of nanosheet system, MoS during charging and discharging2The nano-sheet has a certain volume expansion, but MoS is ultra-small2As a barrier exists, MoS2The lamella of the nano-sheet can not be stacked together, thereby ensuring enough electrochemical active sites and solving the problem of MoS caused by sodium ion embedding and separating in the charging and discharging process in the related technology2The problem of lamination stacking can be applied to the cathode of the sodium-ion battery, and the cycling stability of the sodium-ion battery is improved.
MoS of the invention2/MoS2Nanocomposites utilizing ultra-small MoS without the introduction of a second component2Plays a role in stabilizing MoS2The MoS is effectively improved by the function of the nano-sheet2The problems of structural collapse, active site disappearance and rapid capacity attenuation of the nano-sheet electrode in the charging and discharging processes are solved2/MoS2The nanocomposite was at 500mA g-1The discharge specific capacity after 50 complete cycles is as follows: 315.4-447.6 mA h g-1And has high cycle stability.
Drawings
FIG. 1 is a MoS prepared according to example III of the present invention2/MoS2Nanocomposite and conventional MoS2Phase characterization contrast diagram of the sodium ion battery negative electrode material;
FIG. 2 is a MoS prepared according to example III of the present invention2/MoS2The morphology and microstructure of the nanocomposite;
FIG. 3 is a MoS prepared according to example III of the present invention2/MoS2Nanocomposite and conventional MoS2And the capacity comparison graph of the sodium ion battery negative electrode material is subjected to charge and discharge tests under different current densities and different current cycle times.
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 for a negative electrode of a sodium-ion battery2/MoS2The preparation method of the nano composite material comprises the following steps:
1) mass mAmmonium molybdate0.60 to 1.00g of ammonium molybdate and mThiourea1.80-2.20 g of thiourea is dispersed in 75-95 mL of deionized water to obtain a solution A, and 5-20 mL of ultra-small MoS2 dispersion liquid with the concentration of 0.80-0.90 wt% is dropwise added into the solution A to obtain a liquid B;
2) stirring and drying the liquid B to obtain a precursor MoS2Ammonium molybdate/thiourea;
3) under the inert gas atmosphere, the precursor MoS2Heating ammonium molybdate/thiourea at 600-800 DEG CCooling after heat preservation to obtain MoS2/MoS2A nanocomposite material.
In this example, ammonium molybdate was decomposed by heating into ammonia gas, molybdenum trioxide and water:
(NH4)6Mo7O24·4H2O→6NH3+7MoO3+7H2O；
the melting point of thiourea is 176-178 ℃, and the thiourea can be decomposed when heated:
NH2CSNH2+H2O→2NH3+H2S+CO2；
at a higher temperature, i.e. 600-800 ℃ in this example, MoO generated by decomposition of ammonium molybdate3H formed by decomposition of thiourea2S is respectively used as a molybdenum source and a sulfur source to react to generate molybdenum disulfide MoS2：
4MoO3+9H2S→4MoS2+SO3+9H2O
And SO formed by the reaction3Is introduced into the tail gas cylinder to generate sulfate ions, the process is simpler, and the pollution to air is less.
Of course, in other embodiments, S powder may be used as the sulfur source instead of thiourea.
In particular, ultra-small MoS in step 1)2The preparation of the dispersion comprises: firstly, MoS2Dispersing in NMP solution, and carrying out ultrasonic treatment in ice water to obtain suspension; then centrifugally separating the suspension, collecting supernatant, centrifugally separating for multiple times until the mixture is colorless and transparent, and obtaining the ultra-small MoS dispersed in NMP2And (3) dispersing the mixture. Ice water is here a mixture of ice and water, at a temperature of 0 ℃ at standard atmospheric pressure.
Preferably, 200mg of commercial MoS is first weighed in step 1) with an analytical balance2Dispersing in a sufficient amount of NMP solution, and carrying out ultrasonic treatment in ice water for 3-6 h, preferably 4h to obtain a suspension;
then centrifuging the suspension at 700-10000 rpm for 20-40 min, preferably 8000rpm, and preferably 30min, and collecting the supernatantCentrifuging the solution for 2-4 times to ensure that the mixture is colorless and transparent, namely the ultra-small MoS dispersed in the NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion is 0.80-0.90 wt%, in this example, the ultra-small MoS2The concentration of the dispersion is preferably 0.85% by weight.
Specifically, in the step 2), the liquid B is magnetically stirred for 10-15 hours, and then the water is dried to obtain a precursor MoS2Ammonium molybdate/thiourea. Preferably, the magnetic stirring time is 12 h.
In this example, the ultra small MoS was made by dispersing the reaction raw materials in deionized water, stirring thoroughly and evaporating the water2Uniformly mixing with a molybdenum source and a sulfur source to prepare a precursor MoS2Ammonium molybdate/thiourea to ensure ultra small MoS2Can be uniformly fixed on MoS2On the nano-chip, the MoS of the embodiment2/MoS2The nano composite material has more uniform appearance.
Specifically, the precursor MoS is added in the step 3)2Heating ammonium molybdate/thiourea in a tubular atmosphere furnace from room temperature to 600-800 ℃, preserving heat, and cooling to room temperature to obtain MoS2/MoS2A nanocomposite material. Herein, room temperature is defined as 25 ℃.
Preferably, the heat preservation time in the step 3) is 50-100 minutes.
Preferably, the tubular atmosphere furnace is used for 5-10 ℃ min-1The temperature rise rate is increased from room temperature to 600-800 ℃.
Preferably, the precursor MoS2Before heating and reacting ammonium molybdate/thiourea in a tubular atmosphere furnace, introducing argon gas with the flow of 80-240 sccm for 40min to ensure that the air in a quartz tube is completely exhausted, and avoiding introducing air in the whole reaction process.
Specifically, MoS obtained in step 4)2/MoS2And washing the nano composite material by deionized water and absolute ethyl alcohol for 6-10 times respectively, and drying for 8-12 h in vacuum.
MoS obtained by the preparation method2/MoS2The nano composite material can be applied to the cathode of a sodium ion battery, MoS2/MoS2Microcosmic appearance of nanocompositesIn structure, ultra small MoS2Uniformly fixed on MoS2Nanosheets, ultra-small MoS2Is nanoscale, even up to quantum level, and ultra-small MoS can be observed2Up to about 10nm, stable structure, uniform appearance and ultra-small MoS2Is filled with MoS2Volume of nanosheet system, MoS during charging and discharging2The nano-sheet has a certain volume expansion, but MoS is ultra-small2As a barrier exists, MoS2The sheets of the nano-sheets are not stacked together, so that enough electrochemical active sites are ensured, and the ultra-small MoS is utilized while the second component is not introduced2Plays a role in stabilizing MoS2The MoS is effectively improved by the function of the nano-sheet2The problems of structural collapse, active site disappearance and rapid capacity attenuation of the nano-sheet electrode in the charging and discharging processes are solved, and the problem of MoS caused by sodium ion embedding and releasing in the charging and discharging processes in the related technology is solved2Problem of Stacking of sheets, MoS of the present invention2/MoS2The nanocomposite was at 500mA g-1The discharge specific capacity after 50 complete cycles is as follows: 315.4-447.6 mA h g-1And has high cycle stability.
The first embodiment is as follows:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.80 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate0.60g ammonium molybdate and mThioureaSolution a was obtained by dispersing 1.80g thiourea in 95mL deionized water and ultra small MoS at volume V5 mL2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2Ammonium molybdate/thiourea at 5 ℃ for min in a tubular atmosphere furnace-1The temperature rising rate is increased from room temperature to 600 ℃, the temperature is preserved for 80min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(the gas flow is 80sccm argon for 40min before the reaction to ensure that the air in the quartz tube is completely discharged and the whole reaction process is not ventilated);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 6 times by using deionized water and absolute ethyl alcohol, and drying the sample for 8 hours in vacuum to obtain MoS2/MoS2A nanocomposite material.
Example two:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.82 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate0.70g ammonium molybdate and mThioureaSolution a was obtained by dispersing 1.90g thiourea in 90mL deionized water and ultra small MoS in volume V10 mL2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2Ammonium molybdate/thiourea at 6 ℃ for min in a tubular atmosphere furnace-1The temperature rising rate is increased from room temperature to 650 ℃, the temperature is preserved for 100min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(before the reaction, the gas is introduced with argon gas at a flow rate of 120sccm for 40min to ensure that the air in the quartz tube is completely dischargedNo aeration is carried out in the reaction process);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 7 times by using deionized water and absolute ethyl alcohol, and drying the sample for 9 hours in vacuum to obtain MoS2/MoS2A nanocomposite material.
Example three:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.85 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate0.80g ammonium molybdate and mThiourea2.00g thiourea was dispersed in 85mL deionized water to give solution a, volume V15 mL ultra small MoS2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2Ammonium molybdate/thiourea is put in a tubular atmosphere furnace at 5-10 ℃ for min-1The temperature rising rate is increased from room temperature to 700 ℃, the temperature is preserved for 120min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(argon gas with the flow rate of 160sccm is introduced for 40min before the reaction to ensure that the air in the quartz tube is completely discharged and the whole reaction process is not introduced again);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 8 times by using deionized water and absolute ethyl alcohol, and drying the sample in vacuum for 10 hours to obtain MoS2/MoS2A nanocomposite material.
Example four:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.87 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate0.90g ammonium molybdate and mThiourea2.10g thiourea was dispersed in 80mL deionized water to give solution a, volume V20 mL ultra small MoS2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2Ammonium molybdate/thiourea at 9 ℃ min in a tubular atmosphere furnace-1The temperature rising rate is increased from room temperature to 750 ℃, the temperature is preserved for 140min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(argon gas with the flow rate of 200sccm is introduced for 40min before the reaction to ensure that the air in the quartz tube is completely discharged, and the whole reaction process is not introduced again);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 9 times by using deionized water and absolute ethyl alcohol, and drying the sample for 11 hours in vacuum to obtain MoS2/MoS2A nanocomposite material.
Example five:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.88 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate1.00g ammonium molybdate and mThiourea2.20g thiourea was dispersed in 75mL deionized water to give solution a, volume V20 mL ultra small MoS2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2/Ammonium molybdate/thiourea is put in a tubular atmosphere furnace at 10 ℃ for min-1The temperature rising rate is increased from room temperature to 800 ℃, the temperature is kept for 160min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(the gas flow is 240sccm argon for 40min before the reaction to ensure that the air in the quartz tube is completely exhausted and the whole reaction process is not ventilated);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 10 times by using deionized water and absolute ethyl alcohol, and drying the sample in vacuum for 12 hours to obtain MoS2/MoS2A nanocomposite material.
Example six:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.90 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate0.60g ammonium molybdate and mThioureaSolution a was obtained by dispersing 1.80g thiourea in 75mL deionized water and ultra small MoS at volume V5 mL2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2Ammonium molybdate/thioureaIn a tubular atmosphere furnace at 5 deg.C for min-1The temperature rising rate is increased from room temperature to 600 ℃, the temperature is preserved for 50min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(the gas flow is 80sccm argon for 40min before the reaction to ensure that the air in the quartz tube is completely discharged and the whole reaction process is not ventilated);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 6 times by using deionized water and absolute ethyl alcohol, and drying the sample for 8 hours in vacuum to obtain MoS2/MoS2A nanocomposite material.
Example seven:
1. synthesis of ultra-Small MoS2Dispersion liquid:
(1) weighing 200mg of commercial MoS with an analytical balance2Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4h to obtain a suspension;
(2) centrifuging the suspension at 8000rpm for 30min, collecting supernatant, centrifuging for 2-4 times to obtain colorless and transparent mixture, and obtaining ultra-small MoS dispersed in NMP2Dispersion, ultra small MoS obtained2The concentration of the dispersion was 0.83 wt%;
2. synthetic MoS2/MoS2：
(1) Mass mAmmonium molybdate1.00g ammonium molybdate and mThiourea2.20g thiourea was dispersed in 95mL deionized water to give solution a, volume V20 mL ultra small MoS2Dropping the dispersed liquid into the solution A to prepare liquid B;
(2) the liquid B is stirred by magnetic force for 15 hours until the moisture is dried to obtain a precursor MoS2Ammonium molybdate/thiourea;
(3) the precursor MoS2/Ammonium molybdate/thiourea is put in a tubular atmosphere furnace at 10 ℃ for min-1The temperature rising rate is increased from room temperature to 800 ℃, the temperature is kept for 100min, and finally the temperature is cooled to room temperature to generate MoS2/MoS2(the gas flow is 240sccm argon for 40min before the reaction to ensure that the air in the quartz tube is completely exhausted and the whole reaction process is not ventilated);
(4) after the reaction is finished, taking out a sample, respectively washing the sample for 10 times by using deionized water and absolute ethyl alcohol, and drying the sample in vacuum for 12 hours to obtain MoS2/MoS2A nanocomposite material.
To verify the MoS prepared according to the invention2/MoS2Properties of the nanocomposites MoS prepared in EXAMPLE III2/MoS2Nanocomposite and conventional MoS2Phase characterization of the sodium ion battery negative electrode material was compared, as shown in FIG. 1, MoS2Nanosheets and MoS prepared according to example three2/MoS2The diffraction peaks of the nano composite material are well corresponding to standard cards, and prove that two MoS with different sizes of the same phase2Successful composition of (2), and conventional MoS2MoS of negative electrode material of sodium-ion battery2The diffraction peak of the nanosheet is sharper due to the simple MoS2The nano-sheet crystal grains are relatively large and are more sharp on the diffraction peak, while the MoS prepared in the third embodiment2/MoS2Nanocomposites due to the presence of ultra-small MoS2The diffraction peaks are relatively slightly different, so that the MoS prepared in example III can be proved2/MoS2Presence of ultra-small MoS in nanocomposites2。
MoS with high rate capability prepared for example three2/MoS2Analysis of the morphology and microstructure of the composite material, as shown in FIG. 2, MoS was observed2Uniform distribution and ultra-small MoS2And MoS2Two different-size MoS nanosheets2All the visualized lattice spacings of 0.64nm are consistent with the lattice spacings corresponding to the crystal planes of FIG. 1(002) in the phase analysis, and the ultra-small MoS at the circle in the figure is observed2Ultra small MoS2Uniformly fixed on MoS2On the nano-chip, all prove MoS2/MoS2The composite material is successfully designed and prepared.
MoS prepared for example III2/MoS2Nanocomposite and conventional MoS2The sodium ion battery negative electrode material is subjected to charge and discharge tests under different current densities and different current cycle times respectively, and data analysis in the figure shows that the charge and discharge test result is 100mAg-1At current density of (c), MoS prepared in example III2/MoS2Nano meterThe first discharge capacity of the composite material is 798.5mAhg-1After five cycles of small current circulation, the high current density is changed to 500mA g-1Charge and discharge tests were performed and after 50 complete cycles, the capacity remained at 447.6mAh g-1MoS prepared in example III at high Current Density2/MoS2The nano composite material has good circulation stability and capacity retention rate, and the MoS prepared in the third embodiment2/MoS2The nanocomposite has high cycle stability.
MoS prepared by the invention2/MoS2The nano composite material is used as a sodium ion battery cathode material, has stable structure and uniform appearance and exists ultra-small MoS2The battery has excellent cycle performance, improves the cycle stability of the sodium ion battery, and solves the problem of MoS caused by the intercalation and deintercalation of sodium ions in the charge and discharge processes in the related technology2The problem of stacking of plies. The preparation method of the invention has low preparation cost and is easy to realize.

Claims (10)

1. MoS for negative electrode of sodium-ion battery2/MoS2The preparation method of the nano composite material is characterized by comprising the following steps:
1) mass mAmmonium molybdate0.60 to 1.00g of ammonium molybdate and mThiourea1.80-2.20 g of thiourea is dispersed in 75-95 mL of deionized water to obtain a solution A, and 0.80-0.90 wt% of ultra-small MoS is taken2Dripping 5-20 mL of the dispersion liquid into the solution A to prepare a liquid B;
2) stirring and drying the liquid B to obtain a precursor MoS2Ammonium molybdate/thiourea;
3) under the inert gas atmosphere, the precursor MoS2Heating ammonium molybdate/thiourea at the temperature of 600-800 ℃, preserving heat and cooling to obtain MoS2/MoS2A nanocomposite material.
2. MoS for sodium-ion battery negative electrode according to claim 12/MoS2The preparation method of the nano composite material is characterized in that the ultra-small MoS in the step 1)2Of dispersionsThe preparation method comprises the following steps: firstly, MoS2Dispersing in NMP solution, and carrying out ultrasonic treatment in ice water to obtain suspension; then centrifugally separating the suspension, collecting supernatant, centrifugally separating for multiple times until the mixture is colorless and transparent, and obtaining the ultra-small MoS dispersed in NMP2And (3) dispersing the mixture.
3. MoS for sodium-ion battery negative electrode according to claim 12/MoS2The preparation method of the nano composite material is characterized in that in the step 2), the liquid B is magnetically stirred for 10-15 hours and then dried to obtain a precursor MoS2Ammonium molybdate/thiourea.
4. MoS for sodium-ion battery negative electrode according to claim 12/MoS2The preparation method of the nano composite material is characterized in that the precursor MoS is added in the step 3)2Heating ammonium molybdate/thiourea in a tubular atmosphere furnace from room temperature to 600-800 ℃, preserving heat, and cooling to room temperature to obtain MoS2/MoS2A nanocomposite material.
5. MoS for sodium-ion battery negative electrode according to claim 42/MoS2The preparation method of the nano composite material is characterized in that the heat preservation time in the step 3) is 50-100 minutes.
6. MoS for sodium-ion battery negative electrode according to claim 42/MoS2The preparation method of the nano composite material is characterized in that the tubular atmosphere furnace in the step 3) is used for 5-10 ℃ min-1The temperature rise rate is increased from room temperature to 600-800 ℃.
7. MoS for sodium-ion battery negative electrode according to claim 42/MoS2The preparation method of the nano composite material is characterized in that the precursor MoS in the step 3) is added2Introducing gas flow into a quartz tube of a tube-type atmosphere furnace before heating ammonium molybdate/thioureaAnd discharging air by using argon gas with the amount of 80-240 sccm.
8. MoS for the negative electrode of sodium-ion batteries according to claim 1, 4, 5, 6 or 72/MoS2The preparation method of the nano composite material is characterized in that the MoS obtained in the step 3)2/MoS2And washing the nano composite material by deionized water and absolute ethyl alcohol for 6-10 times respectively, and drying for 8-12 h in vacuum.
9. MoS for negative electrode of sodium-ion battery2/MoS2Nanocomposite material, characterized in that a MoS for a negative electrode of a sodium ion battery according to any of claims 1 to 8 is used2/MoS2The nano composite material is prepared by the preparation method.
10. MoS for the negative electrode of a sodium-ion battery according to claim 92/MoS2Nanocomposite characterized in that said MoS2/MoS2The nanocomposite was at 500mA g-1Charging and discharging under the condition, and after 50 complete cycles, the specific discharge capacity is as follows: 315.4-447.6 mA h g-1。
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