CN113422011A - Carbon nanotube-in-tube @ manganese dioxide nanosheet composite material and preparation and application thereof - Google Patents
Carbon nanotube-in-tube @ manganese dioxide nanosheet composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon nanotube-in-tube @ manganese dioxide nanosheet composite material, a preparation method thereof and application of the composite material in preparation of a lithium ion battery cathode. In the composite material, the carbon nano tube-in-tube is a tube-in-tube structure of an outer tube sleeve inner tube formed by taking a carbon nano tube as an inner tube and taking an amorphous carbon nano tube as an outer tube; the manganese dioxide nano-sheets are closely coupled on the inner and outer surfaces of the inner and outer carbon nano-tubes. The preparation method comprises the steps of firstly growing ZIF-8 nano on the surfaces of CNTsRice grains form a structure similar to a sugarcoated haws string, ZIF-8@ CNTs is treated by tannic acid to obtain a tube-in-tube precursor, then a carbon nano tube-in-tube is obtained by carbonization, and finally KMnO is used4MnO is grown on the inner and outer surfaces of a tube of the carbon nano tube through chemical reaction with carbon2Nanosheet to obtain the final product. The invention can improve MnO2The conductivity and the structural stability of the composite lead to high reversible capacity and stable cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon nanotube-in-tube @ manganese dioxide (MnO)2) A nano-sheet composite material and preparation and application thereof.
Background
Although Lithium Ion Batteries (LIBs) have become a major energy storage device, it is difficult to meet the increasing energy demand of electric vehicles and portable electronic devices. The theoretical capacity of the graphite cathode is only 372mAh g-1The rate performance is poor, and the rate performance becomes a key factor for limiting the performance improvement of the lithium ion battery. Much work has been devoted to developing new high performance negative electrode materials to replace traditional graphite. Transition Metal Oxides (TMOs) have long received attention due to their environmental protection, low cost, and high specific capacity. In various TMOs, MnO2Due to its high theoretical capacity (1232mAh g)-1) And natural abundance, etc. are widely paid attention. However, MnO2There are still many problems in application. MnO2The conductivity is low, the volume change is large in the charging and discharging process, the reversible capacity is low, and the structure is unstable. The rate capability is poor, and the capacity is quickly attenuated.
To overcome the above problems, MnO was increased2Performance of lithium ion battery of general MnO2The nano-material and the compounding with various high-conductivity carbon materials have become an effective strategy. The invention patent with the publication number of CN112701275A discloses a composite material of flower-ball-shaped manganese dioxide loaded on the surface of graphene, the invention patent with the publication number of CN112467120A discloses a composite material of nitrogen-phosphorus doped porous carbon coated manganese dioxide, and the invention patent with the publication number of CN11270274A discloses a composite material of graphene and manganese dioxide nanorods. Research finds that the composite structure is opposite to MnO2The lithium storage properties of (a) have a significant impact. In the composite structure, the carbon substrate is particularly prominent, and MnO improvement by the carbon substrate is required2Conductivity of (2) and also to increase MnO2The structural stability of (a), in addition,the carbon substrate is also convenient for the penetration of electrolyte and MnO2Carbon substrate and MnO meeting the above requirements in contact with an electrolyte2The number of the/C composite materials is not large at present, so that a novel carbon substrate material is designed to construct novel MnO2the/C composite structure has yet to be studied in depth.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides a carbon nanotube-middle tube @ manganese dioxide nanosheet composite material. The invention can improve MnO2The conductivity and structural stability of the polymer, and further the reversible capacity and the cycle performance of the polymer are improved. Middle tube of carbon nano tube @ MnO2The nano-sheet composite material has important application value as a lithium ion battery cathode material.
A carbon nanotube-in-tube @ manganese dioxide nanosheet composite material is characterized in that a carbon nanotube-in-tube structure is formed by using Carbon Nanotubes (CNTs) as an inner tube and using an amorphous carbon nanotube as an outer tube and sleeving the inner tube; the manganese dioxide nano-sheets are closely coupled on the inner and outer surfaces of the inner and outer carbon nano-tubes.
Preferably, the outer diameter of the inner tube of the carbon nano tube is 10-100nm, the wall thickness is 2-30nm, the outer diameter of the outer tube is 30-300nm, and the wall thickness is 2-30 nm;
the thickness of the manganese dioxide nanosheet is 2-20nm, and the mass of manganese dioxide in the composite material accounts for 30% -80%.
The outer tube of the carbon nanotube tube is preferably formed by carbonizing tannic acid.
The invention also provides a preparation method of the carbon nanotube-in-tube @ manganese dioxide nanosheet composite material, which comprises the following steps of:
(1) 60-200mg of Zn (NO)3)2·6H2Dissolving O in 10ml of methanol; 162-542mg 2-methylimidazole was dissolved in another 10ml methanol and 20mg of acidified CNTs were further dispersed in this solution; stirring the above two solutions, further stirring for 10min, pouring the mixed solution into 50mL Teflon autoclave, heating the autoclave to 90 deg.C, keeping the temperature for 6h, cooling to room temperature, centrifuging to separate the product, washing with methanol for 3 times, drying at 80 deg.C,obtaining ZIF (zeolitic imidiazolate framework) -8@ CNTs;
(2) adding 50mg of ZIF-8@ CNTs into 25ml of ethanol to obtain a ZIF-8@ CNTs solution; then adding 25ml of water solution dissolved with 20-100mg of tannic acid into ZIF-8@ CNTs solution, stirring for 5min, separating the product, repeatedly washing, drying at 80 ℃, placing the product in a tube furnace, heating to 600 ℃ under argon, keeping the temperature for 2h, and raising the temperature rate for 1-5 ℃ for min-1(ii) a Then, immersing the carbonized product into 0.2M HCl solution for 2 hours to remove residual zinc, centrifugally separating the product, washing with deionized water, and drying at 80 ℃ to obtain a carbon nano tube middle tube;
(3) ultrasonically dispersing 15mg of carbon nanotube in 30ml of deionized water for 30min, and then adding 170mg of KMnO under stirring4And 160mg of Na2SO4And controlling the temperature to be 10-40 ℃, after 5 hours of reaction, centrifugally separating a product, washing with deionized water, and drying at 80 ℃ to obtain the carbon nanotube-in-tube @ manganese dioxide nanosheet composite material.
The preparation method comprises the steps of firstly growing ZIF-8 nano particles on the surfaces of CNTs to form a structure similar to a sugarcoated haws string, namely the ZIF-8 nano particle string CNTs, then treating the ZIF-8@ CNTs by tannic acid to obtain a tube-in-tube precursor, then obtaining a carbon nano tube-in-tube by carbonization treatment, and finally performing KMnO4MnO is grown on the inner and outer surfaces of a tube of the carbon nano tube through chemical reaction with carbon2Nanosheet to obtain the final product.
In a preferred embodiment, in step (1), the CNTs have an outer diameter of 30-50nm and a wall thickness of 7-10 nm.
The invention also provides application of the carbon nanotube-in-tube @ manganese dioxide nanosheet composite material in preparation of a lithium ion battery cathode.
The material of the invention is adopted to manufacture the cathode of the lithium ion battery: respectively weighing a carbon nano tube-in-tube @ MnO with a mass ratio of 80:10:102Dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground hollow material and acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. Then homogenizing the slurryUniformly coating the copper foil on a wafer (the diameter is 12mm), drying the copper foil in a vacuum oven at 100 ℃, and finally flattening the copper foil on a tabletting machine by using the pressure of 10MPa to obtain the electrode slice.
Assembling the prepared electrode plate, a metal lithium plate and a diaphragm into a CR2025 button-type lithium ion battery, wherein the electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a new power battery test system to test the charge-discharge performance and the cycle performance of the lithium ion battery.
The invention can improve MnO2The conductivity and the structural stability of the composite lead to high reversible capacity and stable cycle performance.
Compared with the prior art, the invention has the main advantages that:
1) ultra-thin MnO2The nano-sheet obviously shortens Li+The reaction kinetics are improved. MnO2The close coupling of the nano-sheets and the middle tube of the carbon nano tube effectively improves MnO2Electrical conductivity and structural stability of the composition, improving MnO2The cycle performance of (c).
2) Based on KMnO4Can grow MnO on the inner and outer surfaces of the inner and outer carbon nanotubes by chemical reaction with carbon2Nanosheets, which significantly increase MnO2The loading capacity and the space utilization rate of the tube in the carbon nano tube. MnO grown on the inner surface of the inner tube and the inner surface of the outer tube2The outer pipe is effectively protected, and the structure stability and the cycle performance are higher. The nano-tube-in-tube structure is favorable for the permeation of electrolyte ions and facilitates the MnO of internal growth2The electrolyte is fully contacted with the electrolyte, and the requirement of electrochemical reaction is met.
3) The tube walls of the inner tube and the outer tube of the carbon nano tube are very thin, the lithium ion diffusion path is short, the tube-in-tube structure has extremely high specific surface area, and the inner surface and the outer surface of the inner tube and the outer tube can be contacted with electrolyte, so that a large number of electrochemical active sites are provided, the favorable structural factors endow the carbon nano tube with high electrochemical activity and high charge and discharge capacity, and important supplement is provided for lithium ion storage of the composite material. Meanwhile, the inner CNTs have higher mechanical strength, and the good integral structural strength and structural stability of the composite material are ensured.
Drawings
FIG. 1 is an SEM of ZIF-8@ CNTs prepared in example 1;
FIG. 2 is a TEM photograph of ZIF-8@ CNTs prepared in example 1;
FIG. 3 is an SEM photograph of a tube of the carbon nanotube prepared in example 1;
FIG. 4 is a TEM photograph of a tube of the carbon nanotube prepared in example 1;
FIG. 5 shows the carbon nanotube-in-tube @ MnO prepared in example 12SEM photograph of nanosheets;
FIG. 6 shows the carbon nanotube-in-tube @ MnO prepared in example 12TEM photograph of the nanosheets;
FIG. 7 shows the carbon nanotube-in-tube @ MnO prepared in example 12Nanosheet composite material having a current density of 1Ag-1Cycle performance map of (c).
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) 120mg of Zn (NO)3)2·6H2O was dissolved in 10ml of methanol. 325mg of 2-methylimidazole are dissolved in a further 10ml of methanol, and 20mg of acidified CNTs (outer diameter 30-50nm, wall thickness 7-10nm) are further dispersed in this solution. And (2) stirring and mixing the two solutions, further stirring for 10min, pouring the mixed solution into a 50mL Teflon high-pressure kettle, heating the high-pressure kettle to 90 ℃, preserving the heat for 6h, cooling to room temperature, centrifugally separating a product, washing with methanol for 3 times, and drying at 80 ℃ to obtain ZIF-8@ CNTs.
(2) 50mg ZIF-8@ CNTs was added to 25ml ethanol. Then adding 25ml of water solution dissolved with 50mg of tannic acid into ZIF-8@ CNTs solution, stirring for 5min, separating the product, repeatedly washing, drying at 80 ℃, placing the product in a tube furnace, heating to 600 ℃ under argon gas and keeping the temperatureHeating for 2h at a heating rate of 2 deg.C for min-1. And then, immersing the carbonized product into 0.2M HCl solution for 2 hours to remove residual zinc, centrifugally separating the product, washing with deionized water, and drying at 80 ℃ to obtain the middle tube of the carbon nano tube.
(3) Ultrasonically dispersing 15mg of carbon nanotube in 30ml of deionized water for 30min, and then adding 170mg of KMnO under vigorous stirring4And 160mg of Na2SO4Controlling the temperature at 25 ℃, after 5 hours of reaction, centrifugally separating the product, washing with deionized water, and drying at 80 ℃ to obtain the carbon nano tube-in-tube @ MnO2Nanosheets.
FIG. 1 is an SEM photograph of ZIF-8@ CNTs prepared in this example. A plurality of nano particles are grown on the surfaces of the CNTs tightly and uniformly to form a typical sugarcoated haw stick string structure. FIG. 2 is a TEM photograph thereof, and it can be seen that the ZIF-8 particles substantially covered the surface of the CNT, making the surface thereof very rough. After reacting ZIF-8@ CNTs with tannic acid and carbonizing, the product was as shown in FIG. 3, and the surface of the CNTs became smooth and the end openings appeared hollow. The TEM photograph (fig. 4) shows the internal structure with a small CNT fully encapsulated inside a large nanotube, representing a typical nanotube-in-nanotube structure. The outer diameter of the outer tube is about 70-100nm and the wall thickness of the outer tube is about 7-10 nm. FIG. 5 shows the middle tube of carbon nanotube @ MnO prepared in this example2SEM photograph of the nanoplatelets, the surface of the tube in the carbon nanotubes became hairy. FIG. 6 is a TEM photograph thereof, and it is possible to see a large amount of very thin MnO2The nano-sheets are grown on the surface of the tube of the carbon nano-tube, and the thickness of the nano-sheets is about 5-10 nm. Thermogravimetric analysis under air revealed MnO267.5 wt%, the remainder being carbon.
The material of the invention is adopted to manufacture the cathode of the lithium ion battery: respectively weighing a carbon nano tube-in-tube @ MnO with a mass ratio of 80:10:102Dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground hollow material and acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. Then evenly coating the slurry on a wafer copper foil (diameter is 12mm), and drying in a vacuum oven at 100 DEG CAnd finally, flattening the mixture on a tabletting machine by using the pressure of 10MPa to obtain the electrode slice.
Assembling the prepared electrode plate, a metal lithium plate and a diaphragm into a CR2025 button-type lithium ion battery, wherein the electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a new power battery test system to test the charge-discharge performance and the cycle performance of the lithium ion battery.
FIG. 7 is a diagram of the prepared carbon nanotube-in-tube @ MnO2Nanosheet composite material having a current density of 1Ag-1The cycle performance of (c). The charge-discharge voltage range is 0.01-3.0V. The specific discharge capacity of the 2 nd cycle is 785mAh g-1Then the discharge capacity slowly dropped, and at the 500 th cycle, the discharge capacity still reached 585.6mAh g-1Compared with the second cycle, the capacity fading rate is only 0.05% per cycle, and stable cycle performance is shown. The coulombic efficiency basically exceeds 98 percent except for the first circulation, and the good reversibility is shown. Middle tube of carbon nano tube @ MnO2The specific capacity and the cycle performance of the nano-sheets exceed the cycle performance of the CN111952557A hollow carbon sphere loaded manganese dioxide material at the current density of 0.3C (60 cycle specific capacities are stabilized at about 330mAh g-1) And work of C.H.Jiang et al (C.H.Jiang, Z.L.Tang, Z.T.Zhang, furniture synthesis of a structural mangnese oxide hydrate for super-inorganic-base anode, Ionics 2019,25,3577-3586) -Current Density 1Ag-1After 300 times of circulation, the discharge capacity is reduced to 508.9mAh g-1。
Example 2
(1) 120mg of Zn (NO)3)2·6H2O was dissolved in 10ml of methanol. 325mg of 2-methylimidazole are dissolved in a further 10ml of methanol, and 20mg of acidified CNTs (outer diameter 30-50nm, wall thickness 7-10nm) are further dispersed in this solution. And stirring and mixing the two solutions, further stirring for 10min, pouring the mixed solution into a 50mL Teflon high-pressure kettle, heating the high-pressure kettle to 90 ℃, preserving the heat for 6h, cooling to room temperature, centrifugally separating a product, washing with methanol for 3 times, and drying at 80 ℃ to obtain ZIF-8@ CNTs.
(2) 50mg ZIF-8@ CNTs was added to 25ml ethanol. Then will contain 70mg of the monoAdding 25ml of aqueous solution of tannic acid into ZIF-8@ CNTs solution, stirring for 5min, separating the product, repeatedly washing, drying at 80 ℃, placing the product in a tube furnace, heating to 600 ℃ under argon, keeping the temperature for 2h, and increasing the temperature for 2 min-1. And then, immersing the carbonized product into 0.2M HCl solution for 2 hours to remove residual zinc, centrifugally separating the product, washing with deionized water, and drying at 80 ℃ to obtain the middle tube of the carbon nano tube.
The subsequent steps were the same as in example 1.
Product of carbon nano tube-in-tube @ MnO2The structure of the nano-sheet composite material is similar to that of the nano-sheet composite material in the embodiment 1, and the main difference is that the thickness of the outer tube wall of the tube in the carbon nano tube is increased to 10-13nm, MnO2The content of (B) was reduced to 54.4 wt%.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 1A g-1And carrying out cyclic charge and discharge test in the voltage range of 0.01-3.0V. The specific discharge capacity of the 2 nd cycle is 721mAh g-1Then the discharge capacity slowly drops, and the discharge capacity still reaches 512mAh g by the 500 th cycle-1Compared with the second cycle, the capacity fading rate is only 0.06% per cycle, and stable cycle performance is shown. The coulombic efficiency basically exceeds 98 percent except for the first circulation, and the good reversibility is shown.
Example 3
(1) 168mg of Zn (NO)3)2·6H2O was dissolved in 10ml of methanol. 455mg of 2-methylimidazole was dissolved in a further 10ml of methanol, and 20mg of acidified CNTs (outer diameter 30-50nm, wall thickness 7-10nm) were further dispersed in this solution. And stirring and mixing the two solutions, further stirring for 10min, pouring the mixed solution into a 50mL Teflon high-pressure kettle, heating the high-pressure kettle to 90 ℃, preserving the heat for 6h, cooling to room temperature, centrifugally separating a product, washing with methanol for 3 times, and drying at 80 ℃ to obtain ZIF-8@ CNTs.
The subsequent steps were the same as in example 1.
Product of carbon nano tube-in-tube @ MnO2The structure of the nano-sheet composite material is similar to that of the nano-sheet composite material in the embodiment 1, and the main difference is that the outer diameter of the outer pipe of the middle pipe of the carbon nano-tube is increased to 90-120nm，MnO2The size of (A) was substantially unchanged and the content was reduced to 52.8 wt%.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 1Ag-1And carrying out cyclic charge and discharge test in the voltage range of 0.01-3.0V. The specific discharge capacity of the 2 nd cycle is 708mAh g-1Then the discharge capacity slowly drops to 500 th cycle, the discharge capacity still reaches 519mAh g-1Compared with the second cycle, the capacity fading rate is only 0.05% per cycle, and stable cycle performance is shown. The coulombic efficiency basically exceeds 98 percent except for the first circulation, and the good reversibility is shown.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. The carbon nanotube-in-tube @ manganese dioxide nanosheet composite material is characterized in that the carbon nanotube-in-tube is of a tube-in-tube structure in which a carbon nanotube is used as an inner tube and an amorphous carbon nanotube is used as an outer tube, and the inner tube is sleeved with the outer tube; the manganese dioxide nano-sheets are closely coupled on the inner and outer surfaces of the inner and outer carbon nano-tubes.
2. The carbon nanotube-in-tube @ manganese dioxide nanosheet composite material as claimed in claim 1, wherein the carbon nanotube-in-tube has an inner tube outer diameter of 10-100nm, a wall thickness of 2-30nm, an outer tube outer diameter of 30-300nm, and a wall thickness of 2-30 nm;
the thickness of the manganese dioxide nanosheet is 2-20nm, and the mass of manganese dioxide in the composite material accounts for 30% -80%.
3. The carbon nanotube-in-tube @ manganese dioxide nanosheet composite of claim 1 or 2, wherein the outer tube of the carbon nanotube-in-tube is formed from tannic acid carbonization.
4. The preparation method of the carbon nanotube-in-tube @ manganese dioxide nanosheet composite material as claimed in any one of claims 1 to 3, comprising the steps of:
(1) 60-200mg of Zn (NO)3)2·6H2Dissolving O in 10ml of methanol; 162-542mg 2-methylimidazole was dissolved in another 10ml methanol and 20mg of acidified CNTs were further dispersed in this solution; stirring and mixing the two solutions, further stirring for 10min, pouring the mixed solution into a 50mL Teflon high-pressure kettle, heating the high-pressure kettle to 90 ℃, preserving the heat for 6h, cooling to room temperature, centrifugally separating a product, washing with methanol for 3 times, and drying at 80 ℃ to obtain ZIF-8@ CNTs;
(2) adding 50mg of ZIF-8@ CNTs into 25ml of ethanol to obtain a ZIF-8@ CNTs solution; then adding 25ml of water solution dissolved with 20-100mg of tannic acid into ZIF-8@ CNTs solution, stirring for 5min, separating the product, repeatedly washing, drying at 80 ℃, placing the product in a tube furnace, heating to 600 ℃ under argon, keeping the temperature for 2h, and raising the temperature rate for 1-5 ℃ for min-1(ii) a Then, immersing the carbonized product into 0.2M HCl solution for 2 hours to remove residual zinc, centrifugally separating the product, washing with deionized water, and drying at 80 ℃ to obtain a carbon nano tube middle tube;
(3) ultrasonically dispersing 15mg of carbon nanotube in 30ml of deionized water for 30min, and then adding 170mg of KMnO under stirring4And 160mg of Na2SO4And controlling the temperature to be 10-40 ℃, after 5 hours of reaction, centrifugally separating a product, washing with deionized water, and drying at 80 ℃ to obtain the carbon nanotube-in-tube @ manganese dioxide nanosheet composite material.
5. The method according to claim 4, wherein in step (1), the CNTs have an outer diameter of 30 to 50nm and a wall thickness of 7 to 10 nm.
6. The application of the carbon nanotube-in-tube @ manganese dioxide nanosheet composite material as defined in any one of claims 1 to 3 in the preparation of a negative electrode of a lithium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031125A (en) * | 2021-11-05 | 2022-02-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nanosheet @ carbon nanotube positive electrode material, product and application thereof |
| CN114084907A (en) * | 2021-10-26 | 2022-02-25 | 西安交通大学 | Mesoporous manganese dioxide synthesized by redox method, metal-doped mesoporous manganese dioxide and method |
| CN114975970A (en) * | 2022-07-01 | 2022-08-30 | 长春理工大学 | Carbon nano tube/tin dioxide nano composite material and preparation method and application thereof |
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| CN114975970A (en) * | 2022-07-01 | 2022-08-30 | 长春理工大学 | Carbon nano tube/tin dioxide nano composite material and preparation method and application thereof |
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