CN111799467B - MoS for negative electrode of sodium-ion battery 2 /MoS 2 Nanocomposite and method for preparing same - Google Patents

MoS for negative electrode of sodium-ion battery 2 /MoS 2 Nanocomposite and method for preparing same Download PDF

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CN111799467B
CN111799467B CN202010697152.7A CN202010697152A CN111799467B CN 111799467 B CN111799467 B CN 111799467B CN 202010697152 A CN202010697152 A CN 202010697152A CN 111799467 B CN111799467 B CN 111799467B
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thiourea
sodium
ammonium molybdate
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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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Abstract

The invention discloses a MoS for a negative electrode of a sodium-ion battery 2 /MoS 2 A nano composite material and a preparation method thereof, which aims to solve the problem of MoS caused by the intercalation and deintercalation of sodium ions in the charge and discharge process in the related technology 2 Problem of Stacking of lamellae in the preparation method ammonium molybdate and thiourea are first dispersed in deionized water and ultra small MoS is added 2 Dropwise adding the dispersion liquid into the mixed liquid, and stirring and drying the mixed liquid to obtain a precursor MoS 2 Ammonium molybdate/thiourea, and finally, the precursor MoS is added in an inert gas atmosphere 2 Heating ammonium molybdate/thiourea, preserving heat and cooling to obtain MoS 2 /MoS 2 The nano composite material has simple preparation method and process, low preparation cost and easy realization, and can be prepared into ultra-small MoS 2 Uniformly fixed on MoS 2 On 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 battery 2 /MoS 2 Nanocomposite and method for preparing same
Technical Field
The invention relates to a sodium ion batteryThe technical field, in particular to a MoS for a sodium ion battery cathode 2 /MoS 2 A 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 in 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, so the lithium ion battery 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 an urgent problem to be solved. 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 discharge process is reversed: 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 process of embedding and separating 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 (0.102 nm) is about 1.4 times the radius of lithium ions (0.076 nm), which makes it more difficult for sodium ions to intercalate and deintercalate between the positive and negative electrode materials than 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 -1 Of the battery. 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 sulfide 2 ) Due to the specific S-Mo-S sandwich structure and the high active sulfur content, the material has good development prospect as a negative electrode material of the sodium-ion battery. MoS 2 The interlayer spacing (0.65 nm) is about 1.94 times of that of graphite, the good diffusion channel is enough to accommodate the rapid transfer of sodium ions in the process of charging and discharging, and the theoretical capacity is up to 670mA h g -1 And the material is a potential negative electrode material of the sodium ion battery. MoS 2 Sodium storage by "intercalation-conversion" mode:
MoS 2 +x Na + ＝Na x MoS 2 (1-1)
Na x MoS 2 +(4-x)Na + ＝Mo+2Na 2 S (1-2)
wherein, the formula (1-1) is intercalation reaction, and the formula (1-2) is conversion reaction.
However, it has low conductivity, is electrochemically unstable, and is not favorable for exhibiting cycle stabilitySexual and rate capability. Furthermore, after the first cycle, moS 2 The 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 MoS 2 The 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/MoS 2 The 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 battery 2 /MoS 2 Nano composite material, preparation method thereof and prepared MoS 2 /MoS 2 The 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 technology 2 The problem of lamination stacking, the preparation cost of the preparation method is low, and the period is short.
In order to achieve the above object, the present invention provides a MoS for a negative electrode of a sodium ion battery 2 /MoS 2 The preparation method of the nano composite material comprises the following steps:
1) Mass m is measured Ammonium molybdate = 0.60-1.00 g ammonium molybdate and mass m Thiourea Dispersing 1.80-2.20 g of thiourea in 75-95 mL of deionized water to obtain a solution A, and taking the ultra-small MoS with the concentration of 0.80-0.90 wt% 2 5-20 mL of dispersion liquid is dripped into the solution A to prepare liquid B;
2) Stirring and drying the liquid B to obtain a precursor MoS 2 Ammonium molybdate/thiourea;
3) Under the inert gas atmosphere, the precursor MoS 2 Heating ammonium molybdate/thiourea at 600-800 ℃ and cooling to obtain MoS 2 /MoS 2 A nanocomposite material.
Further, the ultra-small MoS in the step 1) 2 The preparation of the dispersion comprises: firstly, moS is carried out 2 Dispersing 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 NMP 2 And (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 MoS 2 Ammonium molybdate/thiourea.
Further, in the step 3), the precursor MoS is added 2 Heating ammonium molybdate/thiourea from room temperature to 600-800 ℃ in a tubular atmosphere furnace, preserving heat, cooling to room temperature to obtain MoS 2 /MoS 2 A nanocomposite material.
Further, the heat preservation time in the step 3) is 50-100 minutes.
Further, the tube-type atmosphere furnace in the step 3) is used for heating at 5-10 ℃ for min -1 The temperature rising rate is increased from room temperature to 600-800 ℃.
Further, the precursor MoS in the step 3) is treated 2 Before heating ammonium molybdate/thiourea, introducing argon with the gas flow of 80-240 sccm into a quartz tube of the tube type atmosphere furnace to discharge air.
Further, the MoS obtained in the step 3) 2 /MoS 2 The nano composite material is further washed by deionized water and absolute ethyl alcohol for 6 to 10 times respectively, and is dried for 8 to 12 hours in vacuum. The invention also provides a MoS for the cathode of the sodium-ion battery 2 /MoS 2 The nano composite material is prepared by the preparation method.
Further, the MoS 2 /MoS 2 The nano composite material is prepared at 500mA g -1 Charging 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, ammonium molybdate and thiourea are firstly dispersed in deionized water, and ultra-small MoS is added 2 Adding the dispersed liquid drop into the mixed liquidThen stirring and drying the mixed solution to prepare a precursor MoS 2 Ammonium molybdate/thiourea, and finally, the precursor MoS is added in an inert gas atmosphere 2 Heating ammonium molybdate/thiourea at 600-800 ℃ and cooling to obtain MoS 2 /MoS 2 A nanocomposite material. The preparation method has the advantages of simple process, low preparation cost and short period, and the obtained MoS 2 /MoS 2 Nanocomposite, ultra small MoS 2 Uniformly fixed on MoS 2 On the nano-chip, the structure is stable, the appearance is uniform, and the MoS is ultra-small 2 Is filled with MoS 2 Volume of nanosheet system, moS during charging and discharging 2 The nano-sheet has a certain volume expansion, but due to the ultra-small MoS 2 As a barrier exists, moS 2 The lamellar of the nano-sheet can not be stacked together, thereby ensuring enough electrochemical active sites and solving the problem of MoS caused by the intercalation and deintercalation of sodium ions in the charge and discharge process in the related technology 2 The problem of lamination stacking can be applied to the cathode of the sodium-ion battery, and the circulation stability of the sodium-ion battery is improved.
MoS of the invention 2 /MoS 2 Nanocomposites utilize ultra-small MoS without the introduction of a second component 2 Plays a role in stabilizing MoS 2 The MoS is effectively improved by the function of the nano sheet 2 The problems of structural collapse, active site disappearance and rapid capacity attenuation of the nano-sheet electrode in the charging and discharging processes are solved 2 /MoS 2 The nanocomposite was at 500mA g -1 The discharge specific capacity after 50 complete cycles is as follows: 315.4-447.6 mA h g -1 And has high cycle stability.
Drawings
FIG. 1 is a MoS prepared according to example III of the present invention 2 /MoS 2 Nanocomposite and conventional MoS 2 A phase characterization comparison diagram of the sodium ion battery negative electrode material;
FIG. 2 is a MoS prepared according to example III of the present invention 2 /MoS 2 The morphology and microstructure of the nanocomposite;
FIG. 3 shows an embodiment of the present inventionMoS prepared in example III 2 /MoS 2 Nanocomposite and conventional MoS 2 And 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 obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The invention discloses a MoS for a negative electrode of a sodium-ion battery 2 /MoS 2 The preparation method of the nano composite material comprises the following steps:
1) Mass m Ammonium molybdate = 0.60-1.00 g of ammonium molybdate and mass m Thiourea Dispersing 1.80-2.20 g of thiourea in 75-95 mL of deionized water to obtain a solution A, and dropwise adding 5-20 mL of ultra-small MoS2 dispersion liquid with the concentration of 0.80-0.90 wt% into the solution A to obtain a liquid B;
2) Stirring and drying the liquid B to obtain a precursor MoS 2 Ammonium molybdate/thiourea;
3) Under the inert gas atmosphere, the precursor MoS 2 Heating ammonium molybdate/thiourea at 600-800 ℃ and cooling to obtain MoS 2 /MoS 2 A nanocomposite material.
In this example, ammonium molybdate is decomposed by heating into ammonia gas, molybdenum trioxide and water:
(NH 4 ) 6 Mo 7 O 24 ·4H 2 O→6NH 3 +7MoO 3 +7H 2 O；
thiourea has a melting point of 176 to 178 ℃ and decomposes when heated:
NH 2 CSNH 2 +H 2 O→2NH 3 +H 2 S+CO 2 ；
at higher temperatures, i.e. 600-800 ℃ in this exampleMoO generated by decomposition of ammonium molybdate 3 H formed by decomposition of thiourea 2 S is respectively used as a molybdenum source and a sulfur source to react to generate molybdenum disulfide MoS 2 ：
4MoO 3 +9H 2 S→4MoS 2 +SO 3 +9H 2 O
And SO formed by the reaction 3 Is 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) 2 The preparation of the dispersion comprises: firstly, moS 2 Dispersing 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 NMP 2 And (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 balance 2 Dispersing in sufficient NMP solution, and carrying out ultrasonic treatment in ice water for 3-6 h, preferably 4h to obtain suspension;
then centrifuging the suspension at 700-10000 rpm for 20-40 min, preferably 8000rpm, and preferably 30min for centrifugal separation, collecting the supernatant, centrifuging for 2-4 times, and allowing the mixture to be colorless and transparent to obtain ultra-small MoS dispersed in NMP 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.80 to 0.90wt%, in this example, ultra small MoS 2 The concentration of the dispersion is preferably 0.85% by weight.
Specifically, in the step 2), the liquid B is magnetically stirred for 10-15 h, and then the water is dried to obtain a precursor MoS 2 Ammonium molybdate/thiourea. Preferably, the magnetic stirring time is 12h.
In this example, the ultra-small MoS was produced by dispersing the reaction raw materials in deionized water, stirring thoroughly and evaporating the water 2 Mixing with molybdenum source and sulfur source, and making into capsuleObtaining a precursor MoS 2 Ammonium molybdate/thiourea to ensure ultra small MoS 2 Can be uniformly fixed on MoS 2 On the nano-chip, the MoS of the embodiment 2 /MoS 2 The nano composite material has more uniform appearance.
Specifically, the precursor MoS is added in the step 3) 2 Heating ammonium molybdate/thiourea in a tubular atmosphere furnace from room temperature to 600-800 ℃, preserving heat, cooling to room temperature to obtain MoS 2 /MoS 2 A nanocomposite material. Herein, room temperature is defined as 25 ℃.
Preferably, the temperature keeping time in the step 3) is 50 to 100 minutes.
Preferably, the tube-type atmosphere furnace is used for 5-10 ℃ min -1 The temperature rising rate is increased from room temperature to 600-800 ℃.
Preferably, the precursor MoS 2 Before heating and reacting ammonium molybdate/thiourea in a tubular atmosphere furnace, introducing argon gas with the gas flow of 80-240 sccm for 40min to ensure that the air in a quartz tube is exhausted completely, and avoiding introducing gas in the whole reaction process.
Specifically, moS obtained in step 4) 2 /MoS 2 The nano composite material is further washed by deionized water and absolute ethyl alcohol for 6 to 10 times respectively, and is dried for 8 to 12 hours in vacuum.
MoS obtained by the preparation method 2 /MoS 2 The nano composite material can be applied to the cathode of a sodium ion battery, moS 2 /MoS 2 In the microstructure of the nanocomposite, ultra-small MoS 2 Uniformly fixed on MoS 2 Nanosheets, ultra-small MoS 2 Is nanoscale, even up to quantum level, and ultra-small MoS can be observed 2 Up to about 10nm, stable structure, uniform appearance and ultra-small MoS 2 Is filled with MoS 2 Volume of nanosheet system, moS during charging and discharging 2 The nano-sheet has a certain volume expansion, but MoS is ultra-small 2 As a barrier exists, moS 2 The 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 introduced 2 Plays a role in stabilizing MoS 2 Mo is effectively improved by the function of the nano-sheetsS 2 The 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 solved 2 Problem of Stacking of sheets, moS of the present invention 2 /MoS 2 The nanocomposite was at 500mA g -1 The discharge specific capacity after 50 complete cycles is as follows: 315.4-447.6 mA h g -1 And has high cycle stability.
The first embodiment is as follows:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) Weighing 200mg of commercial MoS with an analytical balance 2 Dispersing 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 NMP 2 Dispersion, ultra-small MoS obtained 2 The concentration of the dispersion was 0.80wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m Ammonium molybdate =0.60g ammonium molybdate and m Thiourea =1.80g thiourea dispersed in 95mL deionized water to give solution a ultra small MoS volume V =5mL 2 Dropping 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 MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS is added 2 Ammonium molybdate/thiourea at 5 ℃ for min in a tubular atmosphere furnace -1 The 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 MoS 2 /MoS 2 (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 MoS 2 /MoS 2 A nanocomposite material.
Example two:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) Weighing 200mg of commercial MoS with an analytical balance 2 Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4 hours to obtain 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 NMP 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.82wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m Ammonium molybdate =0.70g ammonium molybdate and m Thiourea =1.90g thiourea dispersed in 90mL deionized water to obtain solution a, ultra small MoS volume V =10mL 2 Dropping 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 MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS is added 2 Ammonium molybdate/thiourea at 6 ℃ for min in a tubular atmosphere furnace -1 The heating rate is increased from room temperature to 650 ℃, the temperature is kept for 100min, and finally the temperature is cooled to room temperature to generate MoS 2 /MoS 2 (before the reaction, the gas is introduced with 120sccm of argon for 40min to ensure that the air in the quartz tube is exhausted completely, and the whole reaction process is not introduced any more);
(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 MoS 2 /MoS 2 A nanocomposite material.
Example three:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) Weighing 200mg of commercial MoS by using an analytical balance 2 Dispersing 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 mixtureIn a colorless transparent state, ultra-small MoS dispersed in NMP is obtained 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.85wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m is measured Ammonium molybdate =0.80g ammonium molybdate and m Thiourea =2.00g thiourea dispersed in 85mL deionized water to solution a, ultra small MoS volume V =15mL 2 Dropping 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 MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS is added 2 Ammonium molybdate/thiourea is put in a tubular atmosphere furnace at 5-10 ℃ for min -1 The 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 MoS 2 /MoS 2 (the gas flow is 160sccm argon for 40min before the reaction to ensure that the air in the quartz tube is exhausted completely and the whole reaction process is not ventilated);
(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 carrying out vacuum drying for 10 hours to obtain MoS 2 /MoS 2 A nanocomposite material.
Example four:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) Weighing 200mg of commercial MoS with an analytical balance 2 Dispersing 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 NMP 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.87wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m Ammonium molybdate =0.90g ammonium molybdate and m Thiourea =2.10g thiourea dispersed in 80mL deionized water to give solution a ultra small MoS volume V =20mL 2 Dropping the dispersion into the solutionPreparing liquid B in A;
(2) The liquid B is stirred by magnetic force for 12 hours until the moisture is dried to obtain a precursor MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS 2 Ammonium molybdate/thiourea at 9 ℃ min in a tubular atmosphere furnace -1 The 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 MoS 2 /MoS 2 (before the reaction, the gas is introduced with the flow rate of 200sccm of argon for 40min to ensure that the air in the quartz tube is exhausted completely, and the whole reaction process is not introduced any more);
(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 carrying out vacuum drying for 11 hours to obtain MoS 2 /MoS 2 A nanocomposite material.
Example five:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) Weighing 200mg of commercial MoS by using an analytical balance 2 Dispersing 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 NMP 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.88wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m Ammonium molybdate =1.00g ammonium molybdate and m Thiourea =2.20g thiourea dispersed in 75mL deionized water to solution a, ultra small MoS volume V =20mL 2 Dropping 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 MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS 2/ Ammonium molybdate/thiourea is put in a tubular atmosphere furnace at 10 ℃ for min -1 The heating 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 MoS 2 /MoS 2 (argon gas flow rate 240sccm before reaction)Air is used for 40min to ensure that the air in the quartz tube is completely discharged, and the whole reaction process is not aerated);
(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 MoS 2 /MoS 2 A nanocomposite material.
Example six:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) Weighing 200mg of commercial MoS with an analytical balance 2 Dispersing in sufficient NMP solution, and performing ultrasonic treatment in ice water for 4 hours to obtain 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 NMP 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.90wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m Ammonium molybdate =0.60g ammonium molybdate and m Thiourea =1.80g thiourea dispersed in 75mL deionized water to solution a, ultra small MoS volume V =5mL 2 Dropping 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 MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS 2 Ammonium molybdate/thiourea at 5 ℃ for min in a tube atmosphere furnace -1 The 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 MoS 2 /MoS 2 (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 MoS 2 /MoS 2 A nanocomposite material.
Example seven:
1. synthesis of ultra-Small MoS 2 Dispersion liquid:
(1) By using minuteAnalytical balance weighing 200mg commercial MoS 2 Dispersing 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 NMP 2 Dispersion, ultra small MoS obtained 2 The concentration of the dispersion was 0.83wt%;
2. synthetic MoS 2 /MoS 2 ：
(1) Mass m is measured Ammonium molybdate =1.00g ammonium molybdate and m Thiourea =2.20g thiourea dispersed in 95mL deionized water to solution a volume V =20mL ultra small MoS 2 Dropping 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 MoS 2 Ammonium molybdate/thiourea;
(3) The precursor MoS 2/ Ammonium molybdate/thiourea is put in a tubular atmosphere furnace at 10 ℃ for min -1 The heating 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 MoS 2 /MoS 2 (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 MoS 2 /MoS 2 A nanocomposite material.
To verify the MoS prepared according to the invention 2 /MoS 2 Properties of the nanocomposites MoS prepared in EXAMPLE III 2 /MoS 2 Nanocomposite and conventional MoS 2 Phase characterization of the sodium ion battery negative electrode material was compared, as shown in FIG. 1, moS 2 Nanosheets and MoS prepared according to example three 2 /MoS 2 The diffraction peaks of the nano composite material are well corresponding to standard cards, and prove that two MoS with different sizes of the same phase 2 Successful composition of (2), and conventional MoS 2 MoS of negative electrode material of sodium ion battery 2 The diffraction peak of the nano-sheet is sharperIs due to simple MoS 2 The nano-sheet crystal grains are relatively large and are more sharp on the diffraction peak, while the MoS prepared in the third embodiment 2 /MoS 2 Nanocomposites due to the presence of ultra-small MoS 2 The diffraction peaks are relatively different, so that the MoS prepared in example III can be proved 2 /MoS 2 Presence of ultra-small MoS in nanocomposites 2 。
MoS with high Rate Performance prepared for example three 2 /MoS 2 Analysis of the morphology and microstructure of the composite material, as shown in FIG. 2, moS was observed 2 Uniform distribution and ultra-small MoS 2 And MoS 2 Two different-size MoS nanosheets 2 All of the visualized lattice spacings of (2) were 0.64nm, which coincided with the lattice spacing corresponding to the crystal plane of FIG. 1 (002) in the phase analysis, and ultra-small MoS was observed at the circle in the figure 2 Ultra small MoS 2 Uniformly fixed on MoS 2 All on the nano-chip prove MoS 2 /MoS 2 The composite material was successfully designed and prepared.
MoS prepared for example three 2 /MoS 2 Nanocomposite and conventional MoS 2 The 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 -1 At current density of (c), moS prepared in example III 2 /MoS 2 The first discharge capacity of the nano composite material is 798.5mAhg -1 After five cycles of small current circulation, the high current density is changed to 500mA g -1 Charge and discharge tests were performed and after 50 complete cycles, the capacity remained 447.6mAh g -1 MoS prepared in example III at high Current Density 2 /MoS 2 The nano composite material has good circulation stability and capacity retention rate, and the MoS prepared in the third embodiment 2 /MoS 2 The nanocomposite has high cycle stability.
MoS prepared by the invention 2 /MoS 2 The nano composite material is used as a sodium ion battery cathode material, has stable structure and uniform appearance and exists ultra-small MoS 2 The 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 technology 2 The problem of stacking of plies. The preparation method has low preparation cost and is easy to realize.

Claims (7)

1. MoS for negative electrode of sodium-ion battery 2 /MoS 2 The preparation method of the nano composite material is characterized by comprising the following steps:
1) Mass m is measured Ammonium molybdate = 0.60-1.00 g of ammonium molybdate and mass m Thiourea Dispersing 1.80-2.20 g of thiourea in 75-95 mL of deionized water to obtain a solution A, and taking the ultra-small MoS with the concentration of 0.80-0.90 wt% 2 5-20 mL of dispersion liquid is dripped into the solution A to prepare liquid B;
2) Stirring and drying the liquid B to obtain a precursor MoS 2 Ammonium molybdate/thiourea;
3) Under the inert gas atmosphere, the precursor MoS 2 Heating ammonium molybdate/thiourea at 600-800 ℃ and cooling to obtain MoS 2 /MoS 2 A nanocomposite material of ultra-small MoS 2 Uniformly fixed on MoS 2 On a nano-chip, wherein the ultra-small MoS 2 Reaching about 10 nm;
ultra-small MoS in the step 1) 2 The preparation of the dispersion comprises: firstly, moS 2 Dispersing 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 NMP 2 A dispersion liquid;
magnetically stirring the liquid B for 10-15 h in the step 2), and drying to obtain a precursor MoS 2 Ammonium molybdate/thiourea.
2. MoS for sodium-ion battery negative electrode according to claim 1 2 /MoS 2 The preparation method of the nano composite material is characterized in that the precursor MoS is added in the step 3) 2 Ammonium molybdate/thiourea in tubeHeating the mixture in an atmosphere furnace from room temperature to 600-800 ℃, preserving the heat, and cooling the mixture to room temperature to obtain the MoS 2 /MoS 2 A nanocomposite material.
3. MoS for sodium-ion battery negative electrode according to claim 2 2 /MoS 2 The preparation method of the nano composite material is characterized in that the heat preservation time in the step 3) is 50-100 minutes.
4. MoS for sodium-ion battery negative electrode according to claim 2 2 /MoS 2 The 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 -1 The temperature rise rate is increased from room temperature to 600-800 ℃.
5. MoS for sodium-ion battery negative electrode according to claim 2 2 /MoS 2 The preparation method of the nano composite material is characterized in that the precursor MoS in the step 3) is added 2 Before heating ammonium molybdate/thiourea, introducing argon with the gas flow of 80-240 sccm into a quartz tube of the tube type atmosphere furnace to discharge air.
6. MoS for the negative electrode of sodium-ion batteries according to claim 1 or 2 or 3 or 4 or 5 2 /MoS 2 The preparation method of the nano composite material is characterized in that the MoS obtained in the step 3) 2 /MoS 2 The nano composite material is further washed by deionized water and absolute ethyl alcohol for 6 to 10 times respectively, and is dried for 8 to 12 hours in vacuum.
7. MoS for negative electrode of sodium-ion battery 2 /MoS 2 Nanocomposite material, characterized in that a MoS for a negative electrode of a sodium ion battery according to any of claims 1 to 6 is used 2 /MoS 2 The nano composite material is prepared by the preparation method.
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