CN115332518A - Quantum dot tin oxide loaded multi-walled carbon nanotube composite material and preparation method and application thereof - Google Patents
Quantum dot tin oxide loaded multi-walled carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion secondary batteries, and discloses a quantum dot tin oxide loaded multi-walled carbon nanotube composite material, and a preparation method and application thereof. The method comprises the following steps: 1) Dissolving tin salt in water to obtain a tin salt solution; 2) Uniformly mixing the multi-walled carbon nanotube with a tin salt solution to obtain a suspension A; 3) Placing the suspension A in a gas-liquid discharge plasma reaction device, and carrying out discharge reaction under the atmosphere of argon plasma to obtain suspension B; performing subsequent treatment to obtain the quantum dot tin oxide loaded multi-walled carbon nanotube composite material; the dosage of the multi-wall carbon nano tube meets the following requirements: the mass ratio of the tin ions to the multi-walled carbon nanotubes is (0.04-0.8): 1. the method disclosed by the invention is efficient, simple to operate and low in cost, and can realize large-scale production of the quantum dot tin oxide carbon composite material. The material of the invention is used for lithium ion batteries, can obviously improve the cycle stability of electrode materials and has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of nano functional materials and lithium ion secondary batteries, and particularly relates to a quantum dot tin oxide loaded multi-wall carbon nanotube material prepared by a gas-liquid phase plasma discharge reduction technology, and a preparation method and application thereof.
Background
Lithium-ion Batteries (LIBs) are composed of negative (also called anode) and positive (cathode) materials through which Li ions (Li) pass + ) A rechargeable energy storage device that achieves electrical energy storage by reciprocating insertion and removal movement between an anode and a cathode. During discharge, li ions will be transported from the anode to the cathode through the non-aqueous electrolyte and the separator; during charging, the process proceeds in the opposite direction.
LIBs have the advantages of high energy density (high specific capacity), light weight, long life, no memory effect, etc. The specific capacity of a lithium ion battery is mainly determined by the materials of the positive electrode and the negative electrode. However, the theoretical capacity (372 mAh g) of the negative electrode material graphite used in the commercial lithium ion battery at present -1 ) And discharge potential (-0.1V vs. Li) + Li, which is easily overcharged, particularly causes lithium dendrite deposition at low temperature, pierces a separator to form a short circuit, and causes a safety accident), is relatively low, so it cannot satisfy the demand of people for the next generation of lithium ion batteries (higher capacity, longer life, and safety in a wide temperature range). Therefore, there is a need to develop alternative anode materials with high specific capacity, moderate discharge potential and good cycling performance. Among various negative electrode materials, tin oxide has a high theoretical specific capacity (1490 mAh g) -1 Nearly 4 times of graphite) and moderate discharge potential (0.6V vs. Li) + /Li), easy preparation, low cost and environmental protection, etc. and is greatly concerned. However, compared to graphite anodes with low capacity but very stable cycling, tin oxideThe negative electrode has many challenges which are not negligible, firstly, when the conversion reaction and the alloying reaction completely occur, the volume of the negative electrode can be caused to expand greatly (about 300%), and the negative electrode material is easy to be pulverized and fall off due to the large change of the volume in the charging and discharging process; secondly, in the charging/discharging process, the formed lithium oxide with poor conductivity can block the internal alloy reaction on the tin surface, so that the reaction reversibility is reduced, and the cycle performance is unstable; in addition, because tin has a low recrystallization temperature (-71 ℃), tin particles formed by dealloying reaction are easy to aggregate and grow at normal temperature, so that the electrochemical reaction kinetics is reduced, and the cycle reversibility is further reduced.
In order to solve the above problems, some studies have been made. For example, chinese patent application CN201811493527.7 provides a method for preparing a quantum dot tin oxide/fluorinated graphene composite material, which includes dissolving a tin-containing salt in deionized water, adding a surfactant, fully stirring at 20-70 ℃ for 1-5 hours to obtain a tin-containing solution, mixing the tin-containing solution with an ultrasonic monolayer fluorinated graphene dispersion solution, carrying out a solvothermal reaction at 150-210 ℃ for 5-30 hours, and carrying out centrifugal drying to obtain the tin oxide quantum dot/fluorinated graphene composite negative electrode material. The quantum dot tin oxide prepared by the method is uniformly dispersed among the layers of the fluorinated graphene, and can show better performance when being applied to a sodium ion battery. However, the method has the disadvantages of long experiment time, high energy consumption and complex preparation process, and cannot achieve the short-process technology required by large-scale production. Chinese invention patent CN201610048028.1 utilizes SnCl 2 ·2H 2 Introducing thiourea as catalyst and stabilizer for hydrolysis of O, and stirring at normal temperature for 12-24 hr to obtain yellow, clear and transparent SnO 2 And mixing the quantum dot solution with the carbon nano tube, stirring for a period of time, filtering and drying to obtain the quantum dot tin oxide/carbon nano tube composite material. The method has the advantages of no need of high-temperature reaction in the preparation process, low energy consumption and simple and convenient experimental operation, and can show better electrochemical performance when being applied to the cathode of the lithium ion battery. However, the quantum dot tin oxide prepared by the method has too high proportion and very dense particle distribution, so that the quantum dot particles are easy to aggregate and grow and are not easy to growIs favorable for the stability of circulation. In spite of the fact that most of the existing methods for preparing quantum dot tin oxide composite materials cannot realize controllable preparation of uniform nano small-size tin oxide on the premise of simple, efficient and clean production, the method greatly limits the scale production and application and popularization of quantum dot tin oxide composite material cathodes in practice.
Disclosure of Invention
In order to overcome the defects of the existing quantum dot tin oxide carbon composite material, the invention aims to provide a quantum dot tin oxide loaded multi-walled carbon nanotube composite material and an efficient preparation method thereof. The method utilizes solvated electrons with strong reducibility in the gas-liquid plasma, can induce quantum dot tin oxide particles (5 nm) with uniform size to be loaded on multi-walled carbon nanotubes (MWCNTs) in a short time (5-30 minutes), has the characteristics of simple and convenient operation, low preparation cost, high efficiency and reliability and the like, and is easy to realize large-scale production. In the lithium ion battery, the extremely small size (about 5 nm) of tin oxide can obviously increase the reaction area so as to effectively shorten Li + The diffusion distance is matched with the stable structure of the composite carbon material, so that not only can the agglomeration of nano particles be prevented, but also the volume change caused in the charge and discharge process of the material can be obviously relieved, and the electrode dynamics and the cycle performance are improved.
The invention also aims to provide application of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material in a lithium ion battery cathode. Compared with a common tin oxide negative electrode, the quantum dot tin oxide loaded multi-walled carbon nanotube composite material has higher cycling stability, can achieve higher specific capacity and coulombic efficiency compared with the multi-walled carbon nanotube, and better meets the requirement of the multi-walled carbon nanotube as a lithium ion battery negative electrode material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a quantum dot tin oxide loaded multi-walled carbon nanotube composite material comprises the following steps:
(1) Dissolving tin salt in water to obtain a tin salt solution;
(2) Uniformly mixing the multi-walled carbon nanotube with a tin salt solution to obtain a suspension A;
(3) Placing the suspension A obtained in the step (2) in a gas-liquid discharge plasma reaction device, and carrying out discharge reaction in an argon plasma atmosphere to obtain a suspension B; and performing subsequent treatment to obtain the quantum dot tin oxide loaded multi-walled carbon nanotube composite material.
The tin salt in the step (1) comprises more than one of tin chloride (more than or equal to 98 percent) containing crystal water or no crystal water (more than or equal to 98 percent) of analytically pure AR, tin sulfate (more than or equal to 98 percent) of AR and tin sulfate (more than or equal to 98 percent) of AR.
The mass ratio of the tin salt to the water is (10-200 mg): 30ml.
The addition amount of the multi-walled carbon nano-tube in the step (2) meets the condition that the mass ratio of tin ions in the tin salt to the multi-walled carbon nano-tube is (0.04-0.8): 1.
the uniform mixing refers to stirring uniformly; the stirring speed is 100-400 r/min, and the stirring time is 1-6 h.
The discharge reaction conditions in the step (3) are as follows: the input voltage is controlled to be 20-80V, the output high voltage is 1-10 kV, the discharge frequency is 10-100 kHz, and the discharge treatment time is 5-30 minutes.
The gas-liquid discharge plasma reaction device comprises a needle-shaped hollow electrode, a reactor main body and a disc electrode. The reactor main body is a cavity with openings at two ends, the bottom of the reactor main body is sealed by a disc electrode, and the needle-shaped hollow electrode is arranged in the cavity of the reactor main body through an opening at the upper end of the reactor main body. The needle-shaped hollow electrode is provided with an air inlet. One end of the needle-shaped hollow electrode, which is provided with the air inlet, is connected with the negative electrode output end of the rectifier, and one end of the air outlet is arranged in the reactor main body; the disc electrode is connected with the positive electrode output end of the rectifier; the air outlet of the needle-shaped hollow electrode is connected with the air storage device; the rectifier is connected with a power supply.
The reactor main body is a cylindrical reactor and is made of polytetrafluoroethylene; the needle-shaped hollow electrode is made of stainless steel, and the disc electrode is a graphite electrode; the depth of the reactor main body is 50 mm, and the diameter of the inner wall is 60 mm. After the suspension A is added, the depth of the suspension A is 25-35 mm, and the distance between the liquid surface of the suspension A and the lower end of the needle-shaped hollow electrode is 2-5 mm.
In the step (3), the flow rate of argon gas in the needle-shaped hollow electrode is 5-20 mL/min, and the purity is 99.999%.
The plasma discharge of the present invention is a pulsed dc discharge.
The subsequent treatment refers to filtration and drying. The drying is vacuum drying, the vacuum degree is 5000-10000 Pa, the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
The quantum dot tin oxide loaded multi-walled carbon nanotube composite material realizes that nano-scale tin oxide particles are uniformly loaded on the multi-walled carbon nanotube, wherein the loading amount is 15-30%, the size of the loaded particles is about 5nm, and the phenomenon of metal particle aggregation caused by over reduction does not occur.
The quantum dot tin oxide-loaded multi-walled carbon nanotube composite material prepared by plasma reduction is applied to lithium ion batteries.
The principle of the invention is as follows: firstly, dissolving tin salt in water to obtain a tin ion solution, adding the multi-walled carbon nano-tube, and continuously stirring to uniformly disperse tin ions around the multi-walled carbon nano-tube. The solvated electrons with strong reducibility generated by plasma discharge reduce the tin ions adsorbed on the multi-walled carbon nanotubes into tin metal simple substance particles, and the tin metal simple substance particles are easily and rapidly oxidized into tin oxide particles by oxygen in water due to extremely small particle size and are adsorbed on the multi-walled carbon nanotubes.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts a liquid phase discharge plasma system, generates a large amount of solvated electrons with strong reducibility under the action of plasma and liquid phase, and can quickly and efficiently reduce most tin ions in the solution and adsorb the tin ions on the surface of the multi-wall carbon nanotube material.
(2) The method can reduce metallic tin and quickly oxidize the metallic tin into tin oxide to be loaded on the surface of the multi-wall carbon nanotube material by a simple one-step liquid phase discharge plasma treatment method, has the advantages of controllable discharge reaction time within 30 minutes, simple and convenient operation, short process flow, high efficiency and reliability, low preparation cost and easy realization of large-scale production.
(3) The quantum dot tin oxide loaded multi-walled carbon nanotube composite material prepared by the invention has excellent electrochemical performance when applied to a lithium ion battery cathode, can have higher cycling stability compared with a commercial tin oxide material cathode, and can achieve higher specific capacity and coulombic efficiency compared with a multi-walled carbon nanotube.
Drawings
FIG. 1 is a schematic view of a gas-liquid discharge plasma reaction apparatus;
fig. 2 is an XRD diffractogram of quantum dot tin oxide supported multi-walled carbon nanotubes in example 1, which includes standard PDF cards of multi-walled carbon nanotubes and tin oxide;
FIG. 3 is a TEM image of quantum dot tin oxide-supported multi-walled carbon nanotubes in example 1;
FIG. 4 is a thermogravimetric plot of quantum dot tin oxide loaded multi-walled carbon nanotubes in example 1;
FIG. 5 shows that in example 1, the quantum dot tin oxide-loaded multi-walled carbon nanotube is applied to a half-cell of a lithium ion battery as an electrode at a low current density (0.1 Ag) -1 ) The following cycle performance is compared with that of the multi-wall carbon nano tube;
FIG. 6 shows that in example 1, the quantum dot tin oxide-loaded multi-walled carbon nanotube is applied to a half-cell of a lithium ion battery as an electrode at a low current density (0.1A g) -1 ) Coulombic efficiency profile of the lower cycle, versus the coulombic efficiency of the multi-walled carbon nanotubes;
FIG. 7 is a TEM image of quantum dot tin oxide supported multi-walled carbon nanotubes of example 2;
FIG. 8 is a TEM image of quantum dot tin oxide loaded multi-walled carbon nanotubes of example 3.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to the following examples and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
As shown in fig. 1, the gas-liquid discharge plasma reaction apparatus used in the present invention comprises a voltage device, a reaction device and a gas transmission device, wherein the voltage device comprises a common power supply 1 and a rectifier 2, and the reaction device comprises a needle-shaped hollow electrode 3, a reactor main body 4 and a disc electrode 5. The reactor main body is a cavity with openings at two ends, the bottom of the reactor main body is sealed by a disc electrode, and the needle-shaped hollow electrode is arranged in the cavity of the reactor main body through the opening at the upper end of the reactor main body. The needle-shaped hollow electrode is provided with an air inlet. One end of the needle-shaped hollow electrode, which is provided with the air inlet, is connected with the negative electrode output end of the rectifier, and one end of the air outlet is arranged in the reactor main body; the disc electrode is connected with the positive electrode output end of the rectifier; the air outlet of the needle-shaped hollow electrode is connected with an air conveying device; the rectifier is connected with a power supply. The needle-shaped hollow electrode 3 and the disc electrode 5 are respectively made of stainless steel and graphite; the reactor main body is made of polytetrafluoroethylene, the depth of the reactor main body is 50 mm, and the diameter of the inner wall of the reactor main body is 60 mm; the gas transmission device comprises an argon gas bottle 6 and a gas pipe 7 which connects the argon gas bottle and the needle-shaped hollow electrode.
When the reaction occurs, the depth of the suspension A added into the reactor main body for reaction is 5-30 mm, the distance between the liquid surface of the suspension and the lower end of the needle-shaped hollow electrode is 2-5 mm, and the distance is the discharge distance or the discharge gap. The flow rate of argon gas in the needle-shaped hollow electrode is 5-20 ml/min, and the purity is more than 99.999%.
The plasma power supply used by the invention is prepared by Nanjing Suman plasma technology Limited company, and has the model of CTP-2000K; meanwhile, in order to utilize the characteristic of direct current discharge as much as possible, the output signal of the plasma power supply is changed into a pulse direct current signal by using a rectifier.
Example 1
(1) 98% analytically pure SnCl 2 ·2H 2 Dissolving O (48 mg) in deionized water (30 mL), and stirring for 10 minutes under the condition of magnetic stirring at 300 revolutions per minute to obtain a solution A;
(2) Adding 150mg of high-purity multi-wall carbon nano tubes (purchased from Kaina carbon new material Co., ltd., purity is more than 97%, tube diameter is 3-15 mu m, tube length is 15-30 mu m), and continuously stirring for 1h to obtain black suspension B;
(3) Transferring the black suspension B obtained in the step (2) into a gas-liquid discharge plasma cylindrical reactor main body, controlling the distance between the liquid level of the suspension and the lower end of the needle-shaped hollow electrode to be 3 mm, controlling high-purity argon (10 ml/min, purity 99.999%) to directly blow the liquid level through the needle-shaped hollow electrode, switching on a plasma power supply, and continuously and stably reacting for 10 minutes under the conditions that the input voltage is 40V, the output high voltage is 5 kV, and the discharge frequency is 34.5 kHz to obtain a black suspension C;
(4) Filtering the black suspension C obtained in the step (3) to wash impurities and separate solid and liquid, and then drying the cleaned and separated solid black product in vacuum at 70 ℃ for 12h under the vacuum degree of 10000Pa to obtain the quantum dot tin oxide metal loaded multi-walled carbon nanotube composite material with the size of about 5nm, which is marked as 1-QDSnO 2 /MWCNTs。
The XRD diffractogram of the quantum dot tin oxide metal loaded multi-walled carbon nanotube composite of this example is shown in fig. 2. Compared with the XRD of the original multi-walled carbon nanotube, the XRD of the quantum dot tin oxide metal loaded multi-walled carbon nanotube composite material has the advantages that the existence of a carbon peak is eliminated, a tin oxide peak with higher intensity appears at 26.5 degrees, so that an amorphous carbon peak at 26.2 degrees is covered, and in addition, an amorphous peak at 33.5 degrees and an obvious peak at 52 degrees correspond to the tin oxide peak, which indicates that the tin oxide loaded multi-walled carbon nanotube composite material is successfully prepared through plasma discharge.
A TEM image of the quantum dot tin oxide metal-loaded multi-walled carbon nanotube composite material of this embodiment is shown in fig. 3, and it can be clearly seen that particles with a size of about 5nm are loaded on a single multi-walled carbon nanotube, wherein the apparent lattice fringes of the nano-sized particles are measured to be 0.34nm and correspond to the (1 0) plane of tin oxide, which proves that the particles are tin oxide quantum dots, and in addition, the lattice fringes with clear edges of the multi-walled carbon nanotube correspond to the (0 2) plane of the multi-walled carbon nanotube. The results further illustrate the successful synthesis of quantum dot tin oxide metal-loaded multi-walled carbon nanotubes. In addition, under the test condition of air atmosphere at 25-650 ℃,1-QDSnO 2 the/MWCNTs thermogravimetric plot is shown in FIG. 4, calculated to have a tin oxide loading of 22%.
In a glove box (H) 2 O＜0.1％，O 2 Less than 0.1 percent) by taking the prepared quantum dot tin oxide loaded multi-walled carbon nanotube composite material as an anode, calgard 2025 as a diaphragm, a metal lithium sheet as a cathode, and lithium hexafluorophosphate as electrolyte salt (the solvent is EC: DEC =2: 1) And pressing the pole piece into a pole piece with the diameter of 12mm, and assembling the pole piece and the CR2016 button battery case into a half battery. And (3) carrying out charge and discharge performance test on the prepared half battery in a LAND battery test system, wherein the specific parameters are as follows: as shown in FIG. 5, when the current density is 0.1 ag -1 When the charging and discharging voltage range is 0.01V-3V, the capacity of the negative electrode made of the hydrothermal synthesized micron-sized tin oxide and the commercial tin oxide is attenuated rapidly, compared with 1-QDSnO 2 the/MWCNTs have higher capacity in the early period than the former two periods, but show excellent cycling stability as much as the MWCNTs, and the capacity is higher than that of hydrothermally synthesized micron-sized tin oxide and commercial tin oxide after about 30 cycles, and after 50 cycles, 1-QDSnO 2 The specific capacities of the MWCNTs and the MWCNTs are 525mA h g respectively -1 And 365mA g -1 Hydrothermally synthesized micron-sized tin oxide and commercial SnO 2 The attenuation is 403mA h g respectively -1 And 411mA h g -1 . In addition, it is worth noting that in the coulombic efficiency comparison under the low current density of fig. 6, the coulombic efficiency of the quantum dot tin oxide loaded multi-walled carbon nanotube is greatly improved, which indicates that compared with the original multi-walled carbon nanotube, the multi-walled carbon nanotube generates an unstable SEI film due to a large specific surface area, and the SEI film of the quantum dot tin oxide loaded material is more stable.
FIG. 5 shows that the quantum dot tin oxide-loaded multi-walled carbon nanotube applied as an electrode in a half-cell of a lithium ion battery in example 1 has a low current density (0.1 Ag) -1 ) The following cycle performance is compared with that of the multi-wall carbon nano tube;
FIG. 6 shows that the quantum dot tin oxide loaded multi-walled carbon nanotube applied as an electrode in a half-cell of a lithium ion battery in example 1 has a low current density (0.1 Ag) -1 ) Coulombic efficiency of the lower cycle, compared to that of multi-walled carbon nanotubes.
Example 2
(1) Will be provided with98% analytically pure SnCl 4 ·5H 2 Dissolving O (75 mg) in deionized water (30 mL), and stirring for 8 minutes under the condition of magnetic stirring at 100 revolutions per minute to obtain a solution A;
(2) Adding 150mg of high-purity multi-wall carbon nano tubes (purchased from Kenner carbon new material Co., ltd., purity of more than 97%, tube diameter of 3-15 μm and tube length of 15-30 μm) into the solution A obtained in the step (1), and continuously stirring for 3h to obtain a black suspension B;
(3) Transferring the black suspension B obtained in the step (2) into a gas-liquid discharge plasma cylindrical reactor main body, controlling the distance between the liquid level of the suspension and the lower end of the needle-shaped hollow electrode to be 2mm, controlling high-purity argon (20 ml/min, purity 99.999%) to directly blow the liquid level through the needle-shaped hollow electrode, switching on a plasma power supply, and continuously and stably reacting for 30 minutes under the conditions of input voltage of 80V, output high voltage of 10 kV and discharge frequency of 65 kHz to obtain black suspension C;
(4) Filtering the black suspension C obtained in the step (3) to wash impurities and separate solid and liquid, and then drying the cleaned and separated solid black product for 8 hours at 80 ℃ under the vacuum degree of 5000Pa to obtain the quantum dot tin oxide metal-loaded multi-walled carbon nanotube composite material with the size of about 5nm, which is recorded as 2-QDSnO 2 /MWCNTs。
The reaction product is also quantum dot tin oxide particles of about 5nm in size loaded on multi-walled carbon nanotubes (shown in fig. 7). Fig. 7 is a TEM image of quantum dot tin oxide supported multi-walled carbon nanotubes of example 2.
2-QDSnO prepared in this example 2 The MWCNTs material is used as the lithium ion battery cathode, the cycling stability of the tin oxide composite cathode can be effectively improved, the capacity of the original multi-walled carbon nanotube can be greatly improved and a more stable SEI film can be formed due to the addition of the tin oxide, and the test result is similar to that of the example 1.
Example 3
(1) 98% analytically pure SnSO 4 (48 mg) was dissolved in deionized water (30 mL) and stirred for 5 minutes at 400 rpm under magnetic stirring to give solution A;
(2) Adding 150mg of high-purity multi-wall carbon nano tubes (purchased from Kenner carbon new material Co., ltd., purity of more than 97%, tube diameter of 3-15 μm and tube length of 15-30 μm) into the solution A obtained in the step (1), and continuously stirring for 2h to obtain a suspension B;
(3) Transferring the black suspension B obtained in the step (2) into a gas-liquid discharge plasma cylindrical reactor, controlling the distance between the liquid level of the suspension and the lower end of the needle-shaped hollow electrode to be 3 mm, controlling high-purity argon (15 ml/min, purity 99.999%) to directly blow the liquid level through the needle-shaped hollow electrode, switching on a plasma power supply, and continuously and stably reacting for 20 minutes under the conditions of input voltage of 20V, output high voltage of 1 kV and discharge frequency of 30 kHz to obtain black suspension C;
(4) Filtering the black suspension C obtained in the step (3) to wash impurities and separate solid and liquid, and then drying the cleaned and separated solid black product D in vacuum at 60 ℃ for 12h under 8000Pa of vacuum degree to obtain the quantum dot tin oxide metal-loaded multi-walled carbon nanotube composite material with the size of about 5nm, wherein the label is 3-QDSnO 2 /MWCNTs。
The reaction product is also quantum dot tin oxide particles of about 5nm size loaded on multi-walled carbon nanotubes (shown in fig. 8).
FIG. 8 is a TEM image of quantum dot tin oxide loaded multi-walled carbon nanotubes of example 3.
The 3-QDSnO prepared in this example 2 The MWCNTs material is used as the lithium ion battery cathode, the cycling stability of the tin oxide composite cathode can be effectively improved, the capacity of the original multi-walled carbon nanotube can be greatly improved and a more stable SEI film can be formed due to the existence of tin oxide, and the test result is similar to that of the example 1.
Example 4
(1) 98% analytically pure Sn (SO) 4 ) 2 ·2H 2 Dissolving O (100 mg) in deionized water (30 mL), and stirring for 5 minutes under the condition of magnetic stirring at 300 revolutions per minute to obtain a solution A;
(2) Adding 150mg of high-purity multi-wall carbon nano tubes (purchased from Kenner carbon new material Co., ltd., purity of more than 97%, tube diameter of 3-15 μm and tube length of 15-30 μm) into the solution A obtained in the step (1), and continuously stirring for 2h to obtain a suspension B;
(3) Transferring the black suspension B obtained in the step (2) into a gas-liquid discharge plasma cylindrical reactor main body, controlling the distance between the liquid level of the suspension and the lower end of the needle-shaped hollow electrode to be 4 mm, controlling high-purity argon (15 ml/min, purity 99.999%) to directly blow the liquid level through the needle-shaped hollow electrode, switching on a plasma power supply, and continuously and stably reacting for 25 minutes under the conditions of input voltage of 30V, output high voltage of 4 kV and discharge frequency of 34.5 kHz to obtain black suspension C;
(4) And (4) carrying out suction filtration on the black suspension C in the step (3) to wash impurities and carry out solid-liquid separation, and then carrying out vacuum drying on the solid black product D which is washed and separated at 60 ℃ for 12h under 6000Pa of vacuum degree to obtain the quantum dot tin oxide metal loaded multi-walled carbon nanotube composite material which is marked as 4-QDSnO 2 /MWCNTs。
The 4-QDSnO prepared in this example 2 The MWCNTs material is used as the lithium ion battery cathode, the cycling stability of the tin oxide composite cathode can be effectively improved, the capacity of the original multi-walled carbon nanotube can be greatly improved and a more stable SEI film can be formed due to the existence of tin oxide, and the test result is similar to that of the example 1.
Example 5
(1) 98% analytically pure Sn (SO) 4 )·2H 2 Dissolving O (200 mg) in deionized water (30 mL), and stirring for 5 minutes under the magnetic stirring condition of 400 revolutions per minute to obtain a solution A;
(2) Adding 150mg of high-purity multi-wall carbon nano tubes (purchased from Kenner carbon new material Co., ltd., purity of more than 97%, tube diameter of 3-15 μm and tube length of 15-30 μm) into the solution A obtained in the step (1), and continuously stirring for 2h to obtain a suspension B;
(3) Transferring the black suspension B obtained in the step (2) into a gas-liquid discharge plasma cylindrical reactor main body, controlling the distance between the liquid level of the suspension and the lower end of the needle-shaped hollow electrode to be 5 mm, controlling high-purity argon (15 ml/min, purity 99.999%) to directly blow the liquid level through the needle-shaped hollow electrode, switching on a plasma power supply, and continuously and stably reacting for 30 minutes under the conditions of input voltage of 60V, output high voltage of 8 kV and discharge frequency of 60 kHz to obtain black suspension C;
(4) Introducing the black suspension C obtained in the step (3)Filtering to remove impurities, separating solid and liquid, and vacuum drying at 60 deg.C under 8000Pa for 12 hr to obtain quantum dot tin oxide metal loaded multi-walled carbon nanotube composite material (5-QDSnO) 2 /MWCNTs。
5-QDSnO prepared in this example 2 The MWCNTs material is used as the lithium ion battery cathode, the cycling stability of the tin oxide composite cathode can be effectively improved, the capacity of the original multi-walled carbon nanotube can be greatly improved and a more stable SEI film can be formed due to the existence of tin oxide, and the test result is similar to that of the example 1.
Claims (8)
1. A preparation method of a quantum dot tin oxide loaded multi-walled carbon nanotube composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving tin salt in water to obtain a tin salt solution;
(2) Uniformly mixing the multi-walled carbon nanotube with a tin salt solution to obtain a suspension A;
(3) Placing the suspension A obtained in the step (2) in a gas-liquid discharge plasma reaction device, and carrying out discharge reaction in an argon plasma atmosphere to obtain a suspension B; performing subsequent treatment to obtain the quantum dot tin oxide loaded multi-walled carbon nanotube composite material;
the dosage of the multi-wall carbon nano tube meets the following requirements: the mass ratio of the tin ions to the multi-walled carbon nanotubes is (0.04-0.8): 1;
the discharge reaction conditions are as follows: the input voltage is controlled to be 20-80V, the output high voltage is 1-10 kV, the discharge frequency is 10-100 kHz, and the treatment time is 5-30 minutes.
2. The preparation method of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material according to claim 1, characterized in that: the tin salt in the step (1) comprises more than one of tin chloride, stannous chloride, tin sulfate and stannous sulfate containing or not containing crystal water;
in the step (3), the distance between the liquid level of the suspension A and the lower end of the needle-shaped hollow electrode in the gas-liquid discharge plasma reaction device is 2-5 mm; argon enters the discharge plasma reaction device through the needle-shaped hollow electrode;
the flow rate of argon gas in the needle-shaped hollow electrode is 5-20 mL/min, and the purity is 99.999%;
the plasma discharge of the present invention is a pulsed dc discharge.
3. The preparation method of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material according to claim 1, characterized in that:
the mass ratio of the tin salt to the water is (10-200 mg): 30ml;
the step (2) of uniformly mixing refers to uniformly stirring; the stirring speed is 100-400 r/min, and the stirring time is 1-6 h.
4. The preparation method of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material according to claim 1, characterized in that: the gas-liquid discharge plasma reaction device comprises a needle-shaped hollow electrode, a reactor main body and a disc electrode; the reactor main body is a cavity with openings at two ends, the bottom of the reactor main body is sealed by a disc electrode, and the needle-shaped hollow electrode is arranged in the cavity of the reactor main body through the opening at the upper end of the reactor main body; the needle-shaped hollow electrode is provided with an air inlet. One end of the needle-shaped hollow electrode, which is provided with the air inlet, is connected with the negative electrode output end of the rectifier, and one end of the air outlet is arranged in the reactor main body; the disc electrode is connected with the positive electrode output end of the rectifier; the air outlet of the needle-shaped hollow electrode is connected with the air storage device; the rectifier is connected with a power supply.
5. The preparation method of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material according to claim 4, characterized in that: the reactor main body is a cylindrical reactor and is made of polytetrafluoroethylene; the needle-shaped hollow electrode is made of stainless steel, and the disc electrode is a graphite electrode; the depth of the reactor main body is 50 mm, and the diameter of the inner wall is 60 mm; after the suspension A is added, the depth of the suspension A is 25-35 mm.
6. The preparation method of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material according to claim 1, characterized in that: the subsequent treatment refers to filtration and drying; the drying is vacuum drying, the vacuum degree is 5000-10000 Pa, the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
7. A quantum dot tin oxide supported multi-walled carbon nanotube composite material obtained by the preparation method of any one of claims 1 to 6, characterized in that:
the quantum dot tin oxide-loaded multi-walled carbon nanotube material is characterized in that nano-sized tin oxide particles in the quantum dot tin oxide-loaded multi-walled carbon nanotube material are uniformly loaded on the multi-walled carbon nanotube, the loading amount of the tin oxide is 15-30%, and the size of the tin oxide particles is 4-6 nm.
8. The application of the quantum dot tin oxide loaded multi-walled carbon nanotube composite material as claimed in claim 7, wherein: the quantum dot tin oxide supported multi-walled carbon nanotube material is used for a lithium ion battery as a cathode.
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