CN106299262B - Preparation method of carbon nano tube filled with metal sulfide and application of carbon nano tube in lithium ion battery - Google Patents
Preparation method of carbon nano tube filled with metal sulfide and application of carbon nano tube in lithium ion battery Download PDFInfo
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Abstract
The inventionThe method for preparing the carbon nano tube filled with the metal sulfide by using a solid-phase carbon source comprises the steps of fully mixing a transition metal serving as a catalyst and activated carbon, graphene, acetylene black, artificial graphite and the like serving as the solid-phase carbon source, and introducing a small amount of water vapor and thiophene or H under the protection of inert atmosphere2S and other cocatalysts are carbonized and reacted in a high-temperature carbonization furnace to finally prepare the filled carbon nano tube. The method has the advantages of simple process flow, low requirement on reaction equipment, and large diameter, thin tube wall, linear shape, short length and high internal filling rate of the prepared carbon nano tube. The filled carbon nanotube prepared by the method can be used as an electrode material of a lithium ion secondary battery and a lithium sulfur battery.
Description
Technical Field
The invention relates to a preparation method of a filled carbon nanotube and application in a lithium-sulfur battery, wherein the carbon nanotube has the characteristics of large pipe diameter, thin pipe wall, short length, linear type, full filling and the like, has higher capacity and good cycle stability when being applied to an electrode material of a lithium ion battery, and belongs to the field of synthesis and application of nanotechnology.
Background
At present, lithium ion batteries have become the hottest topic of energy storage research, and have been widely applied to portable electronic devices due to the advantages of high energy density, long cycle life, low self-discharge rate, and the like. However, the performances of high reversible capacity, high rate performance, good cycle stability and the like are required for large-scale equipment required by power batteries and long-term energy storage, and these are all problems to be solved in the development process of lithium ion batteries. When the lithium storage material is researched, the dimension of the lithium storage material is reduced to the nanoscale, so that the diffusion path of lithium ions can be effectively reduced, and the high power density of the lithium ion battery is improved. The carbon nano tube has good application prospect in the fields of electrochemical hydrogen storage, lithium ion negative electrode materials and the like due to the excellent electrochemical performance. For example, Zhangkun et al (Hongkun Zhang, Huaihe Song, Xiaohong Chen. Enhanced lithium storage property of Sn nanoparticles: the carbon nanotubes prepared by the present invention, J. Phys. chem. C2012, 116: 22774-. Guan L.H et al [ Guan L, Shi Z, Li H, et al, Super-long connecting nanoparticles in carbon nanotubes [ J ] Chemical Communications,2004, 17(17): 1988) -1989] soot from single-walled carbon nanotubes produced by arc discharge was used as a catalyst to produce ultra-long nickel metal-filled carbon nanotubes by CVD. And the carbon nano tube filled with the Iron sulfide is prepared by catalytic pyrolysis of a high-pressure reaction kettle system by [ Bin Wu, Huaihe Song, JishengZhou, X Chen, Iron but-embedded carbon microspheroidal anode material with high-rate performance [ J ]. chem. Comm. 2011 (47)8653-8655] of the et al, which can effectively make up the defects of poor circulation stability and low utilization efficiency of a single metal sulfide electrode material. However, in the above method, the amount of the metal or compound filled in the carbon nanotube by the two-step method is limited, and as the filler flows out during the charging and discharging process of the battery, the cycling stability of the battery becomes worse, and the one-step method has high requirements on experimental reaction equipment, limited yield, and cannot fill metal sulfide at a high level, so that it is of great significance to find a method which has a simple process and can realize large-scale application.
The invention is characterized in that an activated carbon source prepared by oxidizing an easily available, cheap and renewable solid-phase carbon source with mixed acid and a cheap transition metal catalyst are mixed with each other, carbonized at high temperature, and introduced with H in the process2S, thiophene (C)4H4S) and the like, finally preparing the carbon nano tube filled with the metal sulfide with better appearance and higher yield, wherein the product is used as a lithium ion negative electrode material and has higher charge and discharge capacity and good cycle stability.
Disclosure of Invention
Aiming at the problems, the invention provides a simpler preparation method of a carbon nano tube, which comprises the following specific synthesis steps:
the method comprises the following steps: reacting a transition metal compound with Mg (NO)3)2·6H2Mixing O and citric acid according to a molar ratio of 1-10: 1:1, weighing a certain amount of mixture, putting the mixture into a beaker, adding a certain amount of ethanol or deionized water solution, stirring the mixture in a water bath at the temperature of 60 ℃ for 1-10 hours, and volatilizing the ethanol or water; calcining the mixture in a muffle furnace at 200-1000 DEG CAfter 1-8 h, finally obtaining the (Ni, Fe, Co) O/MgO catalyst, wherein the transition metal compound is Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2O, etc.;
step two: weighing 1-25 g of solid-phase carbon source, putting the solid-phase carbon source into a three-neck flask, adding 120ml of concentrated sulfuric acid and 40ml of concentrated nitric acid, heating and stirring, and keeping the temperature at 70-110 ℃ for 1-96 h; then washing the carbon source to be neutral by deionized water, and finally drying the carbon source to obtain an activated solid carbon source, wherein the solid carbon source is selected from natural graphite, artificial graphite, activated carbon, acetylene black, graphene and the like;
step three: and (3) mixing the catalyst and the solid-phase carbon source powder in the process according to the mass ratio of 1: and uniformly mixing the raw materials in an aqueous solution, ethanol or acetone solution in a ratio of 1-10, and heating and drying to obtain a reaction precursor.
Step four: putting a certain amount of reaction precursor into a carbonization furnace, heating at the speed of 1-20 ℃/min under the protection of nitrogen, heating the carbonization furnace to 700-1200 ℃, preserving heat for 1-12H under the condition, and introducing a small amount of water vapor and H in the process2S or thiophene (C)4H4S) gas. And finally, after the reaction is finished, taking out a product, and then carrying out acid washing to obtain the final carbon nano tube.
The further preferable scheme of the invention is as follows: mixing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2Transition metal compound such as O and Mg (NO)3)2·6H2Mixing O and citric acid according to a molar ratio of 1-8: 1:1, and stirring in a water bath at 60 ℃ for 2-8 h.
The further preferable scheme of the invention is as follows: and calcining the dried catalyst in a muffle furnace at 200-900 ℃ for 2-8 h.
The further preferable scheme of the invention is as follows: weighing 2-20 g of solid-phase carbon source, heating to 70-110 ℃, and then preserving heat for 3-84 h.
The further preferable scheme of the invention is as follows: the catalyst and the activated solid-phase carbon source are mixed according to the mass ratio of 1:1 to 10 parts by weight.
The further preferable scheme of the invention is as follows: in the carbonization furnace, the temperature rising rate is controlled to be 1-10 ℃/min.
The further preferable scheme of the invention is as follows: heating the carbonization furnace to 700-1400 ℃, and preserving heat for 1-24 h under the condition.
The invention has the following advantages: simple process flow, good repeatability, low cost, no pollution and the like. The carbon nano tube filled with the metal sulfide, which has better appearance and higher yield, is prepared by utilizing the easily obtained, cheap and renewable solid-phase carbon source, and the product is used as the lithium ion negative electrode material and has higher charge and discharge capacity and good cycle stability. The requirements on reaction equipment and reaction conditions are low, other impurities in the reaction process are easy to remove, and the obtained product has high yield.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a carbon nanotube obtained in example 1 of the present invention.
FIG. 2 is a High Resolution Transmission Electron Microscopy (HRTEM) image of the carbon nanotubes obtained in example 1 of the present invention.
FIG. 3 is a curve of the cyclic charge/discharge capacity at a current density of 50mA/g when the carbon nanotube obtained in example 1 of the present invention is used as a lithium ion negative electrode.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
Mixing Ni (NO)3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 5:1:1, weighing a certain amount, placing into a beaker, adding a deionized water solution, stirring in a water bath at 60 ℃ for 8 hours, and then volatilizing water; calcining the NiO/MgO catalyst in a muffle furnace at 600 ℃ for 6 hours to finally obtain the NiO/MgO catalyst; weighing 10g of artificial graphite, putting the artificial graphite into a three-neck flask, adding 120ml of concentrated sulfuric acid and 40ml of concentrated nitric acid, heating and stirring, and keeping the temperature at 100 ℃ for 48 hours; then washing the carbon source to be neutral by deionized water, and finally drying the carbon source to obtain an activated solid carbon source; the catalyst and the activated carbon source in the process are mixed according to the proportionThe mass ratio is 1: 5, uniformly mixing the mixture in the aqueous solution in proportion, and heating and drying the mixture to obtain a reaction precursor; putting a certain amount of reaction precursor into a carbonization furnace, heating at 10 ℃/min under the protection of nitrogen to raise the temperature of the carbonization furnace to 900 ℃, preserving the temperature for 3h under the condition, and introducing a small amount of water vapor and thiophene (C)4H4S) gas. And finally, after the reaction is finished, taking out a product, and then carrying out acid washing to obtain the final carbon nano tube.
As shown in a Transmission Electron Microscope (TEM) shown in figure 1, the obtained carbon nanotube has good appearance, short length, high yield and high filling amount, the length of the prepared carbon nanotube is about 2-4 um, and the filling amount is more than 80%.
As shown in the attached FIG. 2, a High Resolution Transmission Electron Microscope (HRTEM), the obtained carbon nanotube has a large diameter, a thin wall, a linear shape, and good crystallinity, and is filled with metal sulfide.
When the carbon nanotube obtained in FIG. 3 was used as a lithium ion negative electrode, 50mAg was observed-1The first discharge capacity reaches 810.8mAhg as shown in the curve of the cyclic charge-discharge capacity under the current density-1And reversible capacity up to 605.3mAhg-1Therefore, the material has higher reversible capacity and good cycle stability when being used as an electrode negative electrode material.
Example 2
Mixing Co (NO)3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 4:1:1, weighing a certain amount, placing into a beaker, adding an ethanol solution, stirring in a water bath at 60 ℃ for 8 hours, and then volatilizing the ethanol; calcining the mixture in a muffle furnace at 600 ℃ for 6 hours to finally obtain a CoO/MgO catalyst; weighing 10g of natural graphite, putting the natural graphite into a three-neck flask, adding 120ml of concentrated sulfuric acid and 40ml of concentrated nitric acid, heating and stirring, and keeping the temperature at 100 ℃ for 48 hours; then washing the carbon source to be neutral by deionized water, and finally drying the carbon source to obtain an activated solid carbon source; and (3) mixing the catalyst and the activated carbon source in the process according to the mass ratio of 1: 5, uniformly mixing the mixture in the aqueous solution in proportion, and heating and drying the mixture to obtain a reaction precursor; by catalytic and oxidative reactions in the above-mentioned processesThe natural graphite is prepared from the following components in percentage by mass of 1: 5, uniformly mixing the mixture in the aqueous solution in proportion, and heating and drying the mixture to obtain a reaction precursor; putting a certain amount of reaction precursor into a carbonization furnace, heating at 10 ℃/min under the protection of nitrogen to raise the temperature of the carbonization furnace to 900 ℃, preserving the heat for 3H under the condition, and introducing a small amount of water vapor and H in the process2And (4) S gas. And finally, after the reaction is finished, taking out a product, and then carrying out acid washing to obtain the final carbon nano tube.
When the carbon nanotube is used as a lithium ion negative electrode, 50mA · g-1The first discharge capacity reaches 850.8mAh g-1And the reversible capacity is up to 651 mAh.g-1，
Example 3
The procedure is as in example 1, except that Fe (NO)3)3·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 4:1:1, and calcining in a muffle furnace at 500 ℃ for 6 hours; weighing 15g of natural graphite, placing the natural graphite in a three-neck flask, heating and stirring, and keeping the temperature at 80 ℃ for 84 hours; the catalyst and the oxidized natural graphite are mixed according to the mass ratio of 1: 3 proportion is evenly mixed in ethanol, the temperature is raised at 15 ℃/min to raise the temperature of the carbonization furnace to 800 ℃, the temperature is kept for 5 hours under the condition, and a small amount of water vapor and H are introduced in the process2And S gas, and finally taking out the product after the reaction is finished, and then obtaining the final carbon nano tube by acid washing.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 810.8mAhg as shown in the curve of the cyclic charge-discharge capacity under the current density-1And reversible capacity up to 620.4mAhg-1。
Example 4
The procedure was as in example 1, except that Ni (NO) was used3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 3:1:1, stirring in a water bath at 60 ℃ for 6h, placing in a muffle furnace, and calcining at 700 ℃ for 6 h; weighing 10g of acetylene black, placing the acetylene black into a three-neck flask, heating and stirring, and keeping the temperature at 90 ℃ for 76 h; catalysisThe agent and the acetylene oxide black powder are mixed according to the mass ratio of 1: 4, uniformly mixing in the aqueous solution; heating at 15 deg.C/min to 700 deg.C, maintaining the temperature for 10 hr, and introducing small amount of water vapor and H2And S gas, and finally taking out the product after the reaction is finished, and then obtaining the final carbon nano tube by acid washing.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 910.8mAhg as shown in the curve of the cyclic charge-discharge capacity under the current density-1And reversible capacity up to 725.4mAhg-1。
Example 5
The procedure was as in example 1, except that Ni (NO) was used3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 6:1:1, stirring in a water bath at 60 ℃ for 4 hours, and calcining in a muffle furnace at 800 ℃ for 6 hours; weighing 20g of activated carbon, placing the activated carbon in a three-neck flask, heating and stirring, and keeping the temperature at 105 ℃ for 48 hours; the catalyst and the graphene oxide powder are mixed according to a mass ratio of 1: 8, uniformly mixing in an ethanol solution; heating at 15 deg.c/min to 1000 deg.c, maintaining for 3 hr, and acid washing to obtain the final carbon nanotube.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 720.4mAhg as shown by the cyclic charge-discharge capacity curve under the current density-1And reversible capacity up to 510.6mAhg-1。
Example 6
The procedure was as in example 1, except that Ni (NO) was used3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 3:1:1, stirring in a water bath at 60 ℃ for 10 hours, and calcining in a muffle furnace at 500 ℃ for 6 hours; weighing 5g of graphene, placing the graphene in a three-neck flask, and preserving heat for 36 hours at 80 ℃; the catalyst and graphene oxide powder are mixed according to a mass ratio of 1: 4, uniformly mixing in acetone solution; heating up at 15 deg.C/min to 900 deg.C,and preserving the heat for 3 hours under the condition, taking out the product after the final reaction is finished, and then obtaining the final carbon nano tube by acid washing.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 780.2mAhg as shown in the curve of the cyclic charge-discharge capacity under the current density-1And reversible capacity up to 590.3mAhg-1。
Example 7
The procedure was as in example 2, except that Co (NO) was used3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 4:1:1, stirring in a water bath at 60 ℃ for 3 hours, and calcining in a muffle furnace at 800 ℃ for 5 hours; weighing 20g of activated carbon, placing the activated carbon in a three-neck flask, heating and stirring, and keeping the temperature at 105 ℃ for 48 hours; the catalyst and the graphene oxide powder are mixed according to a mass ratio of 1: 8, uniformly mixing in an ethanol solution; heating at 5 deg.C/min to 800 deg.C, maintaining the temperature for 5 hr, and introducing small amount of water vapor and thiophene (C)4H4S) after the final reaction of the gas, taking out the product, and then obtaining the final carbon nano tube by acid washing.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 910.3mAhg as shown by the cyclic charge-discharge capacity curve under the current density-1And reversible capacity up to 546.7mAhg-1。
Example 8
The procedure was as in example 2, except that Co (NO) was used3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 6:1:1, stirring in a water bath at 60 ℃ for 8 hours, and calcining in a muffle furnace at 400 ℃ for 4 hours; weighing 15g of activated carbon, placing the activated carbon in a three-neck flask, heating and stirring, and keeping the temperature at 90 ℃ for 56 hours; the catalyst and the oxidized activated carbon powder are mixed according to the mass ratio of 1: 8, uniformly mixing in an acetone solution; heating at 10 deg.C/min to 700 deg.C, maintaining the temperature for 10 hr, and introducing small amount of water vapor and thiophene (C)4H4S) after the final reaction of the gas, taking out the product, and then obtaining the final carbon nano tube by acid washing.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 789.4mAhg as shown in the curve of the cyclic charge-discharge capacity under the current density-1And reversible capacity up to 542.3mAhg-1。
Example 9
The procedure was as in example 2, except that Co (NO) was used3)2·6H2O、Mg(NO3)2·6H2Mixing O and citric acid according to a molar ratio of 7:1:1, stirring in a water bath at 60 ℃ for 5 hours, and calcining in a muffle furnace at 500 ℃ for 6 hours; weighing 15g of artificial graphite, placing the artificial graphite in a three-neck flask, heating and stirring, and keeping the temperature at 105 ℃ for 56 hours; the catalyst and the oxidized natural graphite powder are mixed according to the mass ratio of 1: 4, uniformly mixing in the aqueous solution; heating at 15 deg.c/min to 1000 deg.c, maintaining for 2 hr, taking out the product, and acid washing to obtain the final carbon nanotube.
When the carbon nanotube is used as a lithium ion negative electrode, 50mAg-1The first discharge capacity reaches 730.8mAhg as shown in the curve of the cyclic charge-discharge capacity under the current density-1And reversible capacity up to 570.1mAhg-1。
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A method for preparing a carbon nano tube filled with metal sulfide is characterized by comprising the following steps:
the method comprises the following steps: mixing transition metal nitrate with Mg (NO)3)2·6H2Mixing O and citric acid according to the mol ratio of 1-10: 1:1, weighing a certain amount, placing the mixture into a beaker, adding a certain amount of solution for dissolving, and dissolving in a water bath at 60 DEG CStirring for 1-10 h, and then volatilizing the solution; calcining the catalyst in a muffle furnace at the temperature of between 200 and 1000 ℃ for 1 to 8 hours to finally obtain the catalyst;
step two: weighing 1-25 g of solid-phase carbon source, putting the solid-phase carbon source into a three-neck flask, adding 120ml of concentrated sulfuric acid and 40ml of concentrated nitric acid, heating and stirring, and keeping the temperature at 70-110 ℃ for 1-96 hours; then washing the carbon source with deionized water to be neutral, and finally drying the carbon source to obtain an oxidized solid carbon source;
step three: and (3) mixing the catalyst and the oxidized solid carbon source powder in the process according to the mass ratio of 1: 1-10, uniformly mixing in the solution, and heating and drying to obtain a reaction precursor;
step four: putting a certain amount of reaction precursor into a carbonization furnace, heating at the speed of 1-20 ℃/min under the protection of nitrogen, heating the carbonization furnace to 700-1400 ℃, preserving heat for 1-24H under the condition, and introducing a small amount of water vapor and H in the process2S or thiophene (C)4H4S) gas; and finally, after the reaction is finished, taking out a product, and then carrying out acid washing to obtain the final carbon nano tube.
2. The method for producing carbon nanotubes according to claim 1, wherein: the transition metal nitrate is selected from Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2And O is any one of the above.
3. The method for producing carbon nanotubes according to claim 1, wherein: the dissolved transition metal nitrate and Mg (NO)3)2·6H2The solvent of O and citric acid is selected from water and ethanol.
4. The method for producing carbon nanotubes according to claim 1, wherein: the solid-phase carbon source is any one of natural graphite, artificial graphite, activated carbon, acetylene black, graphene and the like.
5. The method for producing carbon nanotubes according to claim 1, wherein: the carbonization temperature is 700-1200 ℃.
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