CN108899504B - Antimony-carbon nanotube-carbon composite material, preparation method and application - Google Patents
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Abstract
The invention discloses an antimony/carbon nanotube/carbon composite material, a preparation method and application thereof in a lithium ion or sodium ion battery cathode material. The composite material is in a nano rod shape, wherein, the antimony nano particles are uniformly distributed in the carbon base layer generated by in-situ synthesis. The preparation method comprises the following steps: treating the original multi-walled carbon nanotube with a mixed solution of sulfuric acid and nitric acid to obtain an acidified carbon nanotube; dissolving acidified carbon nano tubes, polyethylene glycol and sodium dodecyl sulfate, then adding antimony trichloride, and then dropwise adding a sodium hydroxide solution into the mixed solution for heating and heat preservation; cooling, washing and drying to obtain antimony trioxide/carbon nano tube precursor; the antimony/carbon nano tube/carbon composite material is obtained by uniformly mixing the antimony/carbon nano tube/carbon composite material with an organic high molecular polymer, fully grinding and calcining in an inert atmosphere. The preparation process is simple, the synthesis condition is easy to control, and the product has high specific capacity, good charge-discharge efficiency, good cycle efficiency and high rate performance.
Description
Technical Field
The invention relates to an antimony/carbon nanotube/carbon (Sb-CNT-C) composite material for a lithium ion and sodium ion battery cathode material, a preparation method and application, and belongs to the technical field of energy storage materials.
Background
With the development of scientific technology, the energy problem becomes more severe, and the key point for solving the energy problem lies in finding green and efficient renewable resources. Secondary batteries have been rapidly developed due to their high energy utilization and long cycle life. Among many secondary battery systems, lithium ion batteries are widely used in portable electronic devices and electric vehicles because of their advantages of high operating voltage, high specific capacity, long cycle life, no memory effect, and environmental friendliness. The graphite carbon as the negative electrode material of the commercial lithium ion battery has good chargeable performance and safety performance, but the low specific capacity (372mAh/g) can not meet the development requirement of the high-energy-density lithium ion battery. The antimony-based negative electrode material has high theoretical specific capacity (660mAh/g), the lithiation potential platform of the antimony-based negative electrode material is stably maintained at about 0.85V and is higher than the lithium deposition potential (0.045V) of a graphite material, and the generation of lithium dendrites can be effectively avoided, so that the antimony-based negative electrode material can be used as a negative electrode material of a lithium ion battery and a sodium ion battery to improve the safety performance of the battery. However, antimony undergoes a severe volume expansion phenomenon during intercalation/deintercalation of lithium ions, resulting in a rapid capacity fade, which limits practical application of antimony negative electrode materials in batteries. In order to solve the problems of antimony-based materials, antimony simple substances and carbon materials can be compounded and nanocrystallized. Such as nanorods, nanospheres or antimony/carbon nanofibers. These nanostructures can shorten lithium ion and electron diffusion distances on the one hand and also buffer volume expansion problems on the other hand. To a certain extent, although the method can make up for the defects of the antimony electrode, the method also has the problems of complex preparation process, expensive raw materials, irregular appearance, fast capacity attenuation and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the antimony/carbon nanotube/carbon composite material, the preparation method and the application are provided, the preparation process is simple, and the synthesis conditions are easy to control; the prepared antimony/carbon nanotube/carbon composite material has high specific capacity, good charge-discharge efficiency, good cycle efficiency and high rate performance.
In order to solve the above problems, the present invention provides an antimony/carbon nanotube/carbon composite material, wherein the composite material is in the shape of a nanorod, and antimony nanoparticles are uniformly distributed in a carbon-based layer generated by in-situ synthesis.
The invention also provides a preparation method of the antimony/carbon nanotube/carbon composite material, which is characterized by comprising the following steps of:
step 1): treating the original multi-walled carbon nanotube for 0.5-2 hours by using a mixed solution of sulfuric acid and nitric acid at the temperature of 50-100 ℃, and then diluting, filtering, washing and drying to obtain an acidified carbon nanotube;
step 2): dissolving acidified carbon nanotubes, polyethylene glycol and sodium dodecyl sulfate in absolute ethyl alcohol according to a ratio, performing ultrasonic treatment to uniformly disperse the carbon nanotubes, adding antimony trichloride, stirring to dissolve the antimony trichloride, dropwise adding a sodium hydroxide solution into the mixed solution, stirring, transferring the mixed solution into a high-pressure kettle with a polytetrafluoroethylene lining, heating to 120-180 ℃, and keeping the temperature for 12-48 hours; after cooling to room temperature, washing, centrifuging and drying to obtain antimony trioxide/carbon nano tube precursor;
step 3): and uniformly mixing the antimony trioxide/carbon nanotube precursor with the organic high molecular polymer, fully grinding, and calcining in an inert atmosphere to obtain the antimony/carbon nanotube/carbon composite material, wherein the calcining temperature is 300-600 ℃, and the calcining time is 1-10 hours.
Preferably, the volume ratio of the sulfuric acid to the nitric acid in the step 1) is 1: 1.
Preferably, the ratio of the carbon nano tube, the polyethylene glycol, the sodium dodecyl sulfate and the absolute ethyl alcohol after acidification in the step 2) is 0.01-0.1 g:1g:1g:40 mL; the mass ratio of the acidified carbon nano tube to the antimony trichloride is 0.01-0.1: 1.
Preferably, the concentration of the sodium hydroxide solution in the step 2) is 1 mol/L.
Preferably, PEG 200 is used as the polyethylene glycol in the step 2).
Preferably, the amount of the organic high molecular polymer added in the step 3) is 5-500 g/mol of antimony trioxide/carbon nanotube precursor.
Preferably, the temperature rise rate of the calcination in the step 3) is 5-20 ℃/min; argon is used as inert atmosphere.
Preferably, the organic high molecular polymer in the step 3) is any one or more of polyethylene glycol, p-phenylenediamine and polyvinyl alcohol.
The invention also provides an application of the antimony/carbon nanotube/carbon composite material in a lithium ion or sodium ion battery cathode material.
The invention prepares the nanometer rod-shaped antimony trioxide/carbon nano tube precursor by a solvothermal method, and the composite material is prepared by uniformly mixing the antimony trioxide/carbon nano tube precursor and an organic high molecular polymer and then calcining the mixture in an inert atmosphere. The so-called solvothermal method is developed on the basis of a hydrothermal method, and refers to a synthetic method in which an original mixture is reacted in a closed system such as an autoclave by using an organic or non-aqueous solvent as a solvent at a certain temperature and under the autogenous pressure of the solution. It differs from hydrothermal reactions in that the solvent used is organic rather than water. The process is relatively simple and easy to control, and can effectively prevent the volatilization of toxic substances and prepare the precursor sensitive to air in a closed system.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of uniformly mixing a reaction precursor and an organic high molecular polymer, and then calcining in an inert atmosphere to obtain a target product; most of the used main raw materials have rich sources and low price; is an economic, clean and efficient green synthesis method;
(2) the method has the advantages of simple process, easy control of process parameters, good repeatability and good application prospect;
(3) polyethylene glycol, one of the raw materials, is a carbon source, the carbon obtained by in-situ decomposition of the polyethylene glycol improves the conductivity of the material, and the polyethylene glycol is used as a reducing agent to reduce antimony trioxide in situ, and hydrogen, carbon monoxide and carbon generated by in-situ decomposition of the polyethylene glycol provide a strong reduction atmosphere for the generation of antimony products;
(4) the antimony/carbon nanotube/carbon composite material prepared by the invention has excellent electrochemical performance as a cathode material of a lithium ion battery and a sodium ion battery, antimony nanoparticles in the antimony/carbon nanotube/carbon composite material obtained by reduction are uniformly distributed in synchronously generated carbon groups, and the coated carbon groups are beneficial to transmission of ions and electrons in an electrochemical process and can be used as a protective layer to buffer volume change of an electrode material in a charging and discharging process. Antimony nanostructures can shorten the diffusion distance of ions and electrons. Meanwhile, the carbon nano tube also increases the conductivity and the cycling stability of the electrode material.
Drawings
FIG. 1 is an XRD pattern of the antimony trioxide/carbon nanotube precursor and the antimony/carbon nanotube/carbon composite material of example 1;
FIG. 2 is a SEM photograph (a and b are different magnifications) of an antimony trioxide/carbon nanotube precursor in example 1 and a comparison photograph of SEM photographs (c and d are different magnifications) of an antimony/carbon nanotube/carbon composite material obtained after calcination;
FIG. 3 is a comparison of TEM images of the antimony trioxide/carbon nanotube precursor in example 1 (a and b are different magnifications) and TEM images of the antimony/carbon nanotube/carbon composite material obtained after calcination (c and d are different magnifications);
FIG. 4 is a plot of cyclic voltammetry curves obtained for the antimony/carbon nanotube/carbon composite as the negative electrode material of a lithium ion battery in example 1 at a sweep rate of 0.1 mV/s;
fig. 5 is a graph of 500 cycles of cycle performance and coulombic efficiency when the antimony/carbon nanotube/carbon composite material in example 1 is used as a negative electrode material of a lithium ion battery at a current density of 100 mA/g.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of an antimony/carbon nanotube/carbon composite material comprises the following steps:
(1) mixing the components in a volume ratio of 1:1, treating the original carbon nano tube for 1h at 70 ℃, then diluting, filtering, washing, drying at 80 ℃ overnight, and collecting the product for later use;
(2) dissolving the acidified carbon nano tube, polyethylene glycol (200) and sodium dodecyl sulfate in 40mL of absolute ethyl alcohol according to the mass ratio of 0.05:1:1, performing ultrasonic treatment for 2 hours until the carbon tube is uniformly dispersed, and then adding 4mmol of antimony trichloride (SbCl)3) Is dissolved inStirring the mixed solution for 1 hour under magnetic force;
(3) measuring 27mL of 1M sodium hydroxide solution by using a constant-pressure separating funnel, dropwise adding the solution into the mixed solution, and continuously stirring for 1.5 hours by magnetic force;
(4) the mixed solution was transferred to a 100mL autoclave lined with Teflon and heated to 150 ℃ for 24 hours. After the reaction kettle is naturally cooled to room temperature, washing and centrifuging the reactant by using distilled water and absolute ethyl alcohol, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain an antimony trioxide/carbon nano tube precursor;
(5) antimony trioxide/carbon nanotube precursor and polyethylene glycol (4000) (10 g/mol Sb/mol)2O3) Uniformly mixing, fully grinding, and calcining in an inert atmosphere to obtain an antimony/carbon nanotube/carbon composite material; wherein the calcining temperature is 500 ℃, the calcining time is 6h, the heating rate is 5 ℃ per minute, and the inert atmosphere is argon.
II, test data:
the morphology and structure of the antimony/carbon nanotube/carbon composite material prepared in example 1 and the electrochemical performance of the electrode material used as a lithium ion battery were characterized using an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM), a projection electron microscope (TEM), an electrochemical workstation and a battery test system, with the following results:
(1) XRD test results show that: the diffraction peak of the nanometer rod-shaped antimony trioxide/carbon nano tube precursor can correspond to orthorhombic phase antimony trioxide (JCPDS card number is 11-0689), the crystallinity of nanometer antimony trioxide particles is good, the interlayer spacing is about 0.312nm, and the crystal face is (121). The diffraction peak of the nano rod-shaped antimony/carbon nano tube/carbon composite material can correspond to hexagonal phase antimony (JCPDS card number is 35-0732), and the strong diffraction peak shows that the nano rod-shaped antimony trioxide/carbon nano tube precursor is completely reduced into antimony after being calcined, and the crystal structure cannot be damaged. The nano antimony particles have good crystallinity, with an interlayer spacing of about 0.311nm and a crystal plane of (012) (as shown in fig. 1).
(2) SEM and TEM test results show that: in the SEM picture, the nano antimony trioxide particles in the nano rod-like antimony trioxide/carbon nanotube precursor are uniformly distributed on the surface of the carbon nanotube, and the antimony/carbon nanotube/carbon composite material after the simultaneous calcination carbon reduction basically maintains the rod-like structure of the precursor (as shown in fig. 2). The TEM images further show that after calcination, the surface of the nanorods is tightly coated with a layer of carbon, so that the diameter is enlarged, and the carbon layer is beneficial to increasing the conductivity and structural stability of the material (as shown in fig. 3).
(3) The electrochemical test results show that: the nano rod-shaped antimony/carbon nano tube/carbon composite material is used as the negative electrode material of the lithium ion battery, a cyclic voltammogram obtained at the sweep rate of 0.1mV/s has a pair of electrochemical reduction oxidation peaks at 0.72 and 1.1V, and the electrochemical reduction oxidation peaks respectively correspond to lithium antimonide (Li) generated by lithiation3Sb) alloy and lithium antimonide (Li)3Sb) alloy delithiation (as shown in fig. 4). When the current density is 100mA/g, the charge and discharge test shows that the lithium ion battery has stable cycle performance, the reversible capacity can be stabilized at 457.8mAh/g after 500 cycles, the capacity retention rate is 66.5%, and the coulomb efficiency is kept at 100% (as shown in figure 5).
Example 2
A preparation method of an antimony/carbon nanotube/carbon composite material comprises the following steps:
(1) mixing the components in a volume ratio of 1:1, treating the original carbon nano tube for 1h at 70 ℃, then diluting, filtering, washing, drying at 80 ℃ overnight, and collecting the product for later use;
(2) dissolving the acidified carbon nano tube, polyethylene glycol (200) and sodium dodecyl sulfate in 40mL of absolute ethyl alcohol according to the mass ratio of 0.05:1:1, performing ultrasonic treatment for 2 hours until the carbon tube is uniformly dispersed, and then adding 4mmol of antimony trichloride (SbCl)3) Dissolved in the above mixed solution and stirred magnetically for 1 h. (ii) a
(3) Measuring 27mL of 1M sodium hydroxide solution by using a constant-pressure separating funnel, dropwise adding the solution into the mixed solution, and continuously stirring for 1 hour by magnetic force;
(4) the mixed solution was transferred to a 100mL autoclave lined with Teflon and heated to 150 ℃ for 24 hours. After the reaction kettle is naturally cooled to room temperature, washing and centrifuging the reactant by using distilled water and absolute ethyl alcohol, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain an antimony trioxide/carbon nano tube precursor;
(5) antimony trioxide/carbon nanotube precursor and polyethylene glycol (4000) (100 g/mol Sb/mol)2O3) Uniformly mixing, fully grinding, and calcining in an inert atmosphere to obtain an antimony/carbon nanotube/carbon composite material; wherein the calcining temperature is 500 ℃, the calcining time is 6h, the heating rate is 5 ℃ per minute, and the inert atmosphere is argon.
Example 3
A preparation method of an antimony/carbon nanotube/carbon composite material comprises the following steps:
(1) mixing the components in a volume ratio of 1:1, treating the original carbon nano tube for 1h at 70 ℃, then diluting, filtering, washing, drying at 80 ℃ overnight, and collecting the product for later use;
(2) dissolving the acidified carbon nano tube, polyethylene glycol (200) and sodium dodecyl sulfate in 40mL of absolute ethyl alcohol according to the mass ratio of 0.05:1:1, performing ultrasonic treatment for 2 hours until the carbon tube is uniformly dispersed, dissolving 4mmol of antimony trichloride (SbCl3) in the mixed solution, and stirring for 1 hour under magnetic force;
(3) measuring 27mL of 1M sodium hydroxide solution by using a constant-pressure separating funnel, dropwise adding the solution into the mixed solution, and continuously stirring for 2 hours by magnetic force;
(4) the mixed solution was transferred to a 100mL autoclave lined with Teflon and heated to 150 ℃ for 24 hours. After the reaction kettle is naturally cooled to room temperature, washing and centrifuging the reactant by using distilled water and absolute ethyl alcohol, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain an antimony trioxide/carbon nano tube precursor;
(5) antimony trioxide/carbon nanotube precursor and polyethylene glycol (4000) (added in an amount of 500g/mol Sb)2O3) Uniformly mixing, fully grinding, and calcining in an inert atmosphere to obtain an antimony/carbon nanotube/carbon composite material; wherein the calcining temperature is 500 ℃, the calcining time is 6h, the heating rate is 5 ℃ per minute, and the inert atmosphere is argon.
Claims (9)
1. The antimony/carbon nanotube/carbon composite material is characterized in that the composite material is in a nano rod shape, wherein antimony nano particles are uniformly distributed in a carbon base layer generated by in-situ synthesis;
the preparation method of the antimony/carbon nanotube/carbon composite material is characterized by comprising the following steps of:
step 1): treating the original multi-walled carbon nanotube for 0.5-2 hours by using a mixed solution of sulfuric acid and nitric acid at the temperature of 50-100 ℃, and then diluting, filtering, washing and drying to obtain an acidified carbon nanotube;
step 2): dissolving acidified carbon nanotubes, polyethylene glycol and sodium dodecyl sulfate in absolute ethyl alcohol according to a ratio, performing ultrasonic treatment to uniformly disperse the carbon nanotubes, adding antimony trichloride, stirring to dissolve the antimony trichloride, dropwise adding a sodium hydroxide solution into the mixed solution, stirring, transferring the mixed solution into a high-pressure kettle with a polytetrafluoroethylene lining, heating to 120-180 ℃, and keeping the temperature for 12-48 hours; after cooling to room temperature, washing, centrifuging and drying to obtain antimony trioxide/carbon nano tube precursor;
step 3): and uniformly mixing the antimony trioxide/carbon nanotube precursor with the organic high molecular polymer, fully grinding, and calcining in an inert atmosphere to obtain the antimony/carbon nanotube/carbon composite material, wherein the calcining temperature is 300-600 ℃, and the calcining time is 1-10 hours.
2. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein the volume ratio of sulfuric acid to nitric acid in the step 1) in the preparation method is 1: 1.
3. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein the ratio of the carbon nanotubes, polyethylene glycol, sodium dodecyl sulfate and absolute ethyl alcohol acidified in the step 2) in the preparation method is 0.01-0.1 g:1g:1g:40 mL; the mass ratio of the acidified carbon nano tube to the antimony trichloride is 0.01-0.1: 1.
4. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein the concentration of the sodium hydroxide solution in the step 2) in the preparation method is 1 mol/L.
5. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein the polyethylene glycol in the step 2) is PEG 200.
6. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein the amount of the organic high molecular polymer added in the step 3) is 5 to 500g/mol of antimony trioxide/carbon nanotube precursor.
7. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein in the preparation method, the temperature rise rate of the calcination in the step 3) is 5-20 ℃/min; argon is used as inert atmosphere.
8. The antimony/carbon nanotube/carbon composite material according to claim 1, wherein the organic high molecular polymer in the step 3) in the preparation method is one or more of polyethylene glycol, p-phenylenediamine and polyvinyl alcohol.
9. Use of the antimony/carbon nanotube/carbon composite material of claim 1 in a negative electrode material of a lithium ion or sodium ion battery.
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| CN111710532B (en) * | 2020-05-20 | 2022-08-23 | 上海应用技术大学 | Antimony trioxide-carbon nanotube composite material and preparation and application thereof |
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| CN114639815A (en) * | 2022-04-08 | 2022-06-17 | 东莞市沃泰通新能源有限公司 | Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery |
| CN114715936B (en) * | 2022-04-18 | 2023-10-03 | 鸡西市唯大新材料科技有限公司 | Negative electrode NaSbS of lithium or sodium ion battery 2 Preparation method of @ C composite material |
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