CN110729463A - Lithium-sulfur battery positive electrode material containing three-dimensional interpenetrating composite carbon material, preparation method of lithium-sulfur battery positive electrode material, positive electrode plate containing lithium-sulfur battery positive electrode material and lithium-sulfur battery - Google Patents
Lithium-sulfur battery positive electrode material containing three-dimensional interpenetrating composite carbon material, preparation method of lithium-sulfur battery positive electrode material, positive electrode plate containing lithium-sulfur battery positive electrode material and lithium-sulfur battery Download PDFInfo
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Abstract
The invention discloses a lithium-sulfur battery positive electrode material containing a three-dimensional interpenetrating composite carbon material, a preparation method of the lithium-sulfur battery positive electrode material, a positive electrode plate containing the lithium-sulfur battery positive electrode material and a lithium-sulfur battery. The composite carbon material has a three-dimensional interpenetrating network structure, is formed by interpenetrating the interior of a carbon nano tube and a ZIF-67 derived hierarchical pore carbon polyhedron, and is activatedThe nanotube is used as a framework, ZIF-67 grows on the surface of the nanotube, and the ZIF-67 is carbonized into a hierarchical porous carbon polyhedron through high-temperature sintering. The preparation method of the positive active material of the lithium-sulfur battery comprises the following steps: weighing the composite carbon material and elemental sulfur according to the mass ratio of 1:4, and uniformly dispersing the composite carbon material and the elemental sulfur in CS2And stirring the solution until the solvent is completely volatilized, and infiltrating the elemental sulfur in the mixture into the carbon structure by adopting a melting method. The positive pole piece is composed of the positive active material, the superconducting carbon and the binder in a mass ratio of 8:1: 1. The lithium-sulfur battery mainly comprises the positive pole piece, a diaphragm, electrolyte and a lithium metal negative pole.
Description
Technical Field
The invention belongs to the technical field of preparation of carbon materials and lithium-sulfur batteries, and relates to a lithium-sulfur battery positive electrode material containing a three-dimensional interpenetrating composite carbon material, a preparation method of the lithium-sulfur battery positive electrode material, a positive electrode plate containing the lithium-sulfur battery positive electrode material, and a lithium-sulfur battery. In particular to a ZIF-67 derived three-dimensional interpenetrating network carbon material, a lithium-sulfur battery positive electrode material, a preparation method thereof, and a positive electrode plate and a lithium-sulfur battery which are prepared by adopting the lithium-sulfur battery positive electrode active material.
Background
At present, the practical energy density of commercial lithium ion batteries is low, and the demand of social development on high-end electronic equipment, electric automobiles and the like on high energy density is difficult to meet. Therefore, development of a novel high energy density secondary battery system is imperative. The lithium-sulfur battery takes elemental sulfur as a positive active material and metal lithium as a negative electrode, the theoretical specific discharge capacity can reach 1675mAh/g, and the theoretical energy density can reach 2600Wh/kg, so that the lithium-sulfur battery is regarded as one of the secondary power sources with high energy density which are most hopeful to replace the lithium-ion battery, and has recently received wide attention of researchers at home and abroad.
However, the lithium-sulfur battery positive electrode still has many problems to be solved in the practical process:
(1) the conductivity of elemental sulfur is poor, and the complete reversible proceeding of electrochemical reaction is difficult to ensure;
(2) the dissolution and shuttle flying of the discharging intermediate product polysulfide lithium in the electrolyte cause the continuous irreversible loss of active substances;
(3) the huge volume change in the discharge process causes the collapse of the electrode structure, the actual effect of the battery and the like.
The reasonable and effective solution of the problems can greatly promote the practical process of the lithium-sulfur battery.
The reasonable design and construction of the sulfur-carrying matrix of the anode can organically solve the problems:
firstly, the excellent conductivity of the carbon material can remarkably improve the electronic conductivity of the composite carbon-sulfur anode and ensure the rapid and effective implementation of electrochemical reaction;
secondly, the carbon-based material generally has larger pore volume and specific surface area, and can buffer volume expansion in the charging and discharging process so as to ensure the stability of an electrode structure;
further, the physical adsorption between the carbonaceous material and the polysulfide lithium can restrict elution of the polysulfide lithium, thereby suppressing the shuttle of the active material.
Through the current relevant research reports on the anode sulfur-loaded carbon matrix of the lithium sulfur battery, the preparation process of most carbon materials is complex, the mass production is difficult to realize, and an effective three-dimensional conductive network cannot be formed.
Disclosure of Invention
The invention provides a lithium-sulfur battery positive electrode material containing a three-dimensional interpenetrating composite carbon material, a preparation method of the lithium-sulfur battery positive electrode material, a positive electrode plate containing the lithium-sulfur battery positive electrode material and a lithium-sulfur battery. The three-dimensional interpenetrating composite carbon material is used as a sulfur-carrying matrix to be applied to the positive electrode of the lithium-sulfur battery, and is used for overcoming the problems of poor conductivity, volume expansion, shuttle effect of polysulfide lithium and the like of elemental sulfur in the charging and discharging processes, so that the lithium-sulfur battery has excellent cycle performance and rate capability, higher coulombic efficiency and long-period cycle performance under higher current density.
The invention provides a preparation method of a lithium-sulfur battery anode material containing a three-dimensional interpenetrating composite carbon material, which comprises the following steps:
(1) taking a multi-arm carbon nanotube with the average diameter of 20nm as a framework, activating by nitric acid, and growing a ZIF-67 nano polyhedron on the surface of the multi-arm carbon nanotube by adopting an in-situ growth method to obtain a CNTs/ZIF-67 precursor;
uniformly dispersing the multi-arm carbon nano tubes in a mixed solution of deionized water and concentrated nitric acid with a volume ratio of 3:1, and performing ultrasonic treatment until the carbon nano tubes are uniformly dispersed; placing the obtained dispersion liquid in a condensation reflux device, stirring in a constant-temperature water bath, repeatedly cleaning the obtained product with deionized water and absolute ethyl alcohol, centrifugally collecting, and drying to obtain the activated multi-arm carbon nano tube;
placing the activated multi-arm carbon nano-tube in methanol, ultrasonically dispersing uniformly, and adding Co (NO)3)2·6H2O, adding a methanol solution containing 2-methylimidazole after magnetic stirring, continuously magnetically stirring, standing at room temperature, washing the obtained product with absolute ethyl alcohol for several times, and drying after centrifugal separation to obtain a CNTs/ZIF-67 precursor;
(2) heating a CNTs/ZIF-67 precursor to 600 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and carrying out heat preservation for 3h to carry out high-temperature carbonization treatment to obtain a CNTs/Co-NC composite carbon material;
modifying a CNTs/Co-NC composite carbon material by adopting phosphorus: the CNTs/Co-NC is sprayed by using a water solution containing phosphoric acid, the CNTs/Co-NC modified by using an auxiliary agent phosphorus is obtained after drying and roasting, and P in the CNTs/Co-NC is controlled2O5The content is in the range of 0.1-0.5 wt%, and the CNTs/Co-NC surface P is made2O5In an amount of internal P2O51.1-1.5 times of the content, pore size distribution of 120-160nm, macropore proportion of 45-60%, pore volume of 0.8-2.0ml/g, specific surface area of 250-300m2/g；
(3) According to the mass ratio of 1: and 4, weighing the modified CNTs/Co-NC composite carbon material (three-dimensional interpenetrating composite carbon material) and elemental sulfur obtained in the previous step, uniformly dispersing the modified CNTs/Co-NC composite carbon material and elemental sulfur in the solution, magnetically stirring the solution until the solvent is completely volatilized, and collecting a product, wherein the three-dimensional interpenetrating composite carbon material (CNTs/Co-NC): elemental sulfur: CS2The solution was prepared according to 0.5-1.0 g: 2.0-4.0 g: 15-30 ml;
(4) and (4) placing the product obtained in the step (3) in a tube furnace, heating to 155 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and preserving heat for 10 hours to obtain the composite sulfur positive electrode active material.
The stirring in the constant-temperature water bath in the step (1) of the invention means that the mixture is placed in a constant-temperature water bath kettle at the temperature of 80 ℃ and stirred for 6 hours.
Putting the multi-arm carbon nano tube subjected to activation treatment in methanol, ultrasonically dispersing uniformly, and adding Co (NO)3)2·6H2O, adding methanol solution containing 2-methylimidazole after magnetic stirring, continuing to magnetically stir and standing at room temperature, namely placing 0.3g of activated multi-arm carbon nano tube in 100ml of methanol, performing ultrasonic treatment for 2min to uniformly disperse, and adding 0.5mol of Co (NO)3)2·6H2O, magnetically stirring for 30min, adding 100ml of methanol solution containing 2mol of 2-methylimidazole, continuously magnetically stirring for 2h, and standing at room temperature for 24 h.
The drying in the step (1) is carried out for 12 hours in a vacuum drying oven at the temperature of 60 ℃.
The invention also relates to a composite carbon material containing the three-dimensional interpenetrating network, which is prepared by the preparation method, wherein the three-dimensional interpenetrating composite carbon material is formed by interpenetrating a multi-arm carbon nanotube framework with the average diameter of 20nm and a nano carbon polyhedron with the average diameter of 150nm, the nano carbon polyhedron is formed by high-temperature carbonization of ZIF-67, and nano Co metal particles are uniformly embedded in the nano carbon polyhedron.
The invention also relates to a lithium-sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material, which is prepared by the preparation method.
The invention also provides a lithium-sulfur battery positive pole piece, which is obtained by adopting the following preparation method:
weighing the obtained lithium-sulfur positive electrode active material, superconducting carbon and binder LA133 according to the mass ratio of 80:10:10, placing the materials into an agate ball-milling tank, preparing LA133 and deionized water according to the mass ratio of 1:30, weighing the deionized water, adding the deionized water into the ball-milling tank, carrying out high-energy ball milling for 30min at the rotating speed of 400rpm, then uniformly coating the obtained slurry on an aluminum foil, and controlling the surface density to be 1.85mg/cm on average2Putting the obtained pole piece into a vacuum drying oven, vacuum drying at 55 ℃ for 24h, and standing naturallyAnd cutting the positive plate into small wafers with the diameter of 15mm by using a cutting machine after cooling to obtain the positive plate of the lithium-sulfur battery.
The invention also provides a lithium-sulfur battery which is composed of the lithium-sulfur positive pole piece obtained by the preparation method, a diaphragm, electrolyte and a metal lithium negative pole piece and is prepared according to the prior art.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes phosphorus to modify CNTs/Co-NC and leads the surface P of the CNTs/Co-NC to be P2O5In an amount of internal P2O5The content is 1.1-1.5 times that of the composite carbon material, the obtained composite carbon material is of a three-dimensional interpenetrating network structure, the structure takes a multi-arm carbon nano tube as a three-dimensional framework, and the multi-arm carbon nano tube and a hierarchical pore nano carbon polyhedron are interpenetrating to form a three-class space rock candy gourd-like structure, compared with the currently reported single-dimensional nano carbon material, the three-dimensional interpenetrating network structure is more beneficial to the conduction of electrons and ions in the charging and discharging processes of a battery, and therefore the utilization rate of higher active substances is ensured.
2. The composite carbon-sulfur positive electrode material is prepared by taking the composite carbon material as a sulfur-carrying matrix, and the CNTs/Co-NC surface is modified in a spraying mode, so that partial micropores of the CNTs/Co-NC surface can be effectively peptized, the micropore proportion of the CNTs/Co-NC surface is reduced, the mesopore-macropore proportion of the CNTs/Co-NC surface is improved, the CNTs/Co-NC surface is promoted to generate more active site load centers, and active sulfur in the composite carbon-sulfur positive electrode is mainly distributed inside a hierarchical pore nano carbon polyhedron structure, and a small part of active sulfur is in a multi-arm carbon nano tube framework. In the charging and discharging processes of the battery, the multi-arm carbon nano tube in the composite carbon-sulfur positive electrode material mainly plays a role in conducting electrons and ions, and the effective reversible proceeding of an electrochemical reaction is ensured; the hierarchical porous nanocarbon polyhedron mainly plays a role in binding remarkable active sulfur, is rich in a hierarchical porous structure, can effectively store a large amount of active sulfur, and meanwhile can limit loss of the active sulfur through van der Waals adsorption, so that the shuttle flying effect is effectively inhibited, and long-period stable circulation of the lithium-sulfur battery is guaranteed. In addition, the lithium-sulfur battery positive electrode active material is more beneficial to the infiltration of electrolyte, and can effectively reduce the transmission distance of lithium ions, thereby improving the rate capability of the battery.
3. The lithium-sulfur battery provided by the invention adopts the composite carbon material and the positive electrode active material. Compared with the lithium-sulfur battery modified by other methods, the lithium-sulfur battery provided by the invention has excellent cycle performance and rate capability, and excellent large-current long-period cycle performance.
Drawings
FIG. 1a is an SEM image of CNTs/ZIF-67 precursor in example 1.
FIG. 1b is a TEM image of CNTs/ZIF-67 precursor in example 1.
FIG. 1c is a TEM image of the lithium sulfur positive electrode active material S @ CNTs/Co-NC described in example 1.
FIG. 1d is an elemental profile of the lithium sulfur positive electrode active material S @ CNTs/Co-NC described in example 1.
Fig. 2a is a TEM image of the lithium sulfur positive electrode active material S @ CNTs described in comparative example 1.
Fig. 2b is an elemental profile of the lithium sulfur positive electrode active material S @ CNTs described in comparative example 1.
FIG. 3a is the XRD pattern of the CNTs/ZIF-67 precursor of example 1.
FIG. 3b is an XRD pattern of the positive electrode active material S @ CNTs/Co-NC described in example 1.
Fig. 4a is a graph of cycle performance curves for the lithium sulfur batteries described in example 2 and comparative example 2.
Fig. 4b is a graph of rate performance curves for the lithium sulfur batteries described in example 2 and comparative example 2.
Fig. 4c is a graph of long cycle cycling performance curves for the lithium sulfur battery described in example 2.
Detailed Description
The hydrogenation method of a petroleum resin of the present invention will be described in further detail below with reference to examples. These examples should not be construed as limiting the invention.
Example 1
A preparation method of a positive active material of a lithium-sulfur battery comprises the following steps:
(1) taking a multi-arm carbon nanotube (subjected to activation treatment) with the average diameter of 20nm as a three-dimensional framework, and producing ZIF-67 on the surface of the multi-arm carbon nanotube in situ to obtain a CNTs/ZIF-67 precursor;
uniformly dispersing 0.3g of multi-arm carbon nano tube in 100ml of a mixed solution of deionized water and concentrated nitric acid in a volume ratio of 3:1, performing ultrasonic treatment until the carbon nano tube is uniformly dispersed, then placing the mixture in a constant-temperature water bath, performing magnetic stirring treatment at 80 ℃ for 6 hours, then repeatedly washing the mixture by using deionized water and absolute ethyl alcohol and performing centrifugal separation, and drying the mixture in a vacuum drying oven at 60 ℃ for more than 12 hours to obtain an activated multi-arm carbon nano tube;
placing the activated carbon nanotube in 100ml methanol solution, ultrasonically dispersing for 2min, and adding 0.5mol Co (NO)3)2·6H2O, magnetically stirring for 30min, adding 100ml of methanol solution containing 2mol of 2-methylimidazole, continuously magnetically stirring for 2h, standing at room temperature for 24h, washing the obtained product with absolute ethyl alcohol for several times, centrifugally separating, and drying in a vacuum box at 60 ℃ for 12h to obtain a CNTs/ZIF-67 precursor;
(2) heating a CNTs/ZIF-67 precursor to 600 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and carrying out heat preservation for 3h to carry out high-temperature carbonization treatment to obtain a CNTs/Co-NC composite carbon material;
modifying a CNTs/Co-NC composite carbon material by adopting phosphorus: the CNTs/Co-NC is sprayed by using a water solution containing phosphoric acid, the CNTs/Co-NC modified by using an auxiliary agent phosphorus is obtained after drying and roasting, and P in the CNTs/Co-NC is controlled2O5The content is in the range of 0.1-0.5 wt%, and the CNTs/Co-NC surface P is made2O5In an amount of internal P2O51.1-1.5 times of the content, pore size distribution of 120-160nm, macropore proportion of 45-60%, pore volume of 0.8-2.0ml/g, specific surface area of 250-300m2/g；
(3) Weighing the modified CNTs/Co-NC and elemental sulfur according to the mass ratio of 1:4, uniformly dispersing in 20ml of CS2 solution, and magnetically stirring until the solvent is completely volatilized, wherein the CNTs/Co-NC: elemental sulfur: CS2The solution was measured as 0.5 g: 2.0 g: a proportion of 30 ml; then the mixture is put into a tube furnace and heated to 155 ℃ at a heating rate of 5 ℃/min under the argon atmosphereAnd keeping the temperature at the temperature for 10 hours to obtain the composite lithium-sulfur positive electrode active material.
Comparative example 1
In the present comparative example, the carbon material was a single activated multi-arm carbon nanotube material; the single multi-arm carbon nanotube is used as a sulfur-carrying matrix of the lithium-sulfur battery positive active material.
Referring to fig. 2, the present comparative example provides a method for preparing a positive active material of a lithium-sulfur battery, including the steps of:
(1) uniformly dispersing 0.3g of multi-arm carbon nano tube in 100ml of a mixed solution of deionized water and concentrated nitric acid in a volume ratio of 3:1, performing ultrasonic treatment until the carbon nano tube is uniformly dispersed, then placing the mixture in a constant-temperature water bath, performing magnetic stirring treatment at 80 ℃ for 6 hours, then repeatedly washing the mixture by using deionized water and absolute ethyl alcohol and performing centrifugal separation, and drying the mixture in a vacuum drying oven at 60 ℃ for more than 12 hours to obtain an activated multi-arm carbon nano tube;
(2) weighing the activated multi-arm carbon nano tube and elemental sulfur according to the mass ratio of 1:4, and uniformly dispersing the activated multi-arm carbon nano tube and the elemental sulfur in 20ml of CS2And magnetically stirring the solution until the solvent is completely volatilized, then placing the obtained mixture in a tube furnace, heating the mixture to 155 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and preserving the heat for 10 hours to obtain the composite lithium-sulfur positive electrode active material.
Example 2
A lithium-sulfur battery using the positive electrode active material for a lithium-sulfur battery described in example 1.
Referring to fig. 3 to 4, the present embodiment provides a method for manufacturing a lithium-sulfur battery, including the following steps:
(1) and preparing the positive pole piece. Weighing the lithium-sulfur positive electrode active material, the superconducting carbon and the binder LA133 in the embodiment 1 according to the mass ratio of 80:10:10, placing the materials into an agate ball milling tank, weighing deionized water according to the mass ratio of 1:30 of LA133 and the deionized water, adding the materials into the ball milling tank, carrying out high-energy ball milling at the rotating speed of 400rpm for 30min, then uniformly coating the obtained slurry on an aluminum foil, and controlling the surface density to be 1.85mg/cm on average2Placing the obtained pole piece in a vacuum drying oven, vacuum drying at 55 deg.C for 24 hr, naturally cooling, and cutting into pieces by a cutting machineA small disc with a diameter of 15 mm;
(2) a lithium sulfur battery is assembled. The assembling process of all the batteries is completed in a high-purity argon glove box, the water content in the glove box is lower than 1ppm, the oxygen content in the glove box is lower than 1ppm, and all the batteries are 2032 type button batteries. Using the small wafer in the step (1) as a positive electrode piece, using Celgard 2400 with the diameter of 19mm as a diaphragm, using a metal lithium piece with the diameter of 15.4mm as a negative electrode piece, and using 0.5M LiTFSI/DOL + DME (volume ratio of 1:1) as electrolyte (containing 0.2M LiNO)3Additive) button cells were assembled at a press pressure of 1000 psi.
Comparative example 2
A positive electrode active material for a lithium-sulfur battery was used as the positive electrode active material for the lithium-sulfur battery described in comparative example 1.
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
(1) and preparing the positive pole piece. Weighing the lithium-sulfur positive electrode active material, the superconducting carbon and the binder LA133 in the comparative example 1 according to the mass ratio of 80:10:10, placing the materials into an agate ball milling tank, weighing the LA133 and deionized water according to the mass ratio of 1:30, adding the weighed materials into the ball milling tank, carrying out high-energy ball milling at the rotating speed of 400rpm for 30min, then uniformly coating the obtained slurry on an aluminum foil, and controlling the surface density to be 1.88mg/cm on average2And (3) placing the obtained pole piece in a vacuum drying oven, carrying out vacuum drying at 55 ℃ for 24h, and cutting the pole piece into a small wafer with the diameter of 15mm by using a cutting machine after natural cooling.
(2) And (6) assembling the battery. Same as in step (2) of example 2.
The composite carbon material and the composite lithium sulfur positive electrode active material described in example 1 and comparative example 1 were characterized as follows:
(1) x-ray diffraction (XRD).
The diffraction phenomenon of X-rays in a material is utilized to analyze the crystalline state, the crystalline structure, the crystalline size, the crystalline components and the like of the material. The present inventors have conducted qualitative analysis on the positive active materials of the lithium sulfur batteries described in example 2 and comparative example 2 accordingly.
Testing an instrument: RIGAKU TTR-3X-ray diffractometer; and (3) testing conditions are as follows: the radiation source is a Cu target
Scanning range: 2 θ is 10-80 °; scanning speed: 6 °/min.
(2) X-ray photoelectron spectroscopy (XPS). The present invention qualitatively analyzes the surface composition and the valence state of the element of the composite carbon material described in example 1. Testing an instrument: PHI-1600 model electron spectrometer.
(3) Scanning Electron Microscope (SEM).
The invention observes the surface topography of the composite carbon material described in example 1 and comparative example 1 with this instrument. Testing an instrument: hitachi S-4800 type field emission scanning electron microscope.
(4) Transmission Electron Microscope (TEM), High Resolution Transmission Electron Microscope (HRTEM). The present invention observes the internal structural feature information of the composite carbon material described in example 1 and comparative example 1 with this instrument. Testing an instrument: transmission electron microscope model Tecnai F30.
The lithium sulfur cell described in example 2, comparative example 2 was characterized as follows:
(1) cyclic voltammetry test (CV). Testing an instrument: princeton Versa STAT electrochemical workstation; scanning rate: 0.05 mV/s; voltage window: 1.7-2.8V.
(2) Constant current charge/discharge test. Testing an instrument: a model ladlct 2001A multichannel charge-discharge test system; test voltage range: 1.7-2.8V.
(3) And (6) testing alternating current impedance. Testing an instrument: princeton Versa STAT electrochemical workstation; frequency range: 0.1-1M Hz.
The test characterization method is a standard test characterization method in the technical field of lithium-sulfur battery preparation, and is selected according to the conventional operation requirements in the field when unpublished parameters are involved.
FIG. 1a is an SEM picture of a CNTs/ZIF-67 precursor in example 1, FIG. 1b is a TEM picture of the CNTs/ZIF-67 precursor in example 1, FIG. 1c is a TEM picture of a lithium sulfur positive electrode active material S @ CNTs/Co-NC described in example 1, and FIG. 1d is an elemental map of the lithium sulfur positive electrode active material S @ CNTs/Co-NC described in example 1. As can be seen from FIGS. 1a and 1b, the CNTs/ZIF-67 precursor has a three-dimensional interpenetrating network structure, and a multi-arm carbon nanotube with an average diameter of 20nm is used as a three-dimensional framework to connect ZIF-67 nano polyhedrons in series; as shown in FIGS. 1c and 1d, after the CNTs/ZIF-67 precursor is carbonized into CNTs/Co-NC by high-temperature sintering, the microscopic morphology of the precursor is retained, the intact three-dimensional interpenetrating network structure is still maintained, and after elemental sulfur is loaded by a melting method, the elemental sulfur is mainly stored in the hierarchical porous nanocarbon polyhedron.
Fig. 2a is a TEM image of the lithium sulfur positive electrode active material S @ CNTs described in comparative example 1, and fig. 2b is an elemental surface scan of the lithium sulfur positive electrode active material S @ CNTs described in comparative example 1. It can be seen from the figure that after the sulfur is carried by melting, the elemental sulfur is mainly stored in the carbon nanotubes.
FIG. 3a is an XRD pattern of CNTs/ZIF-67 precursor in example 1, and FIG. 3b is an XRD pattern of S @ CNTs/Co-NC, the positive electrode active material in example 1. As can be seen from the figure, the prepared CNTs/ZIF-67 precursor has high crystallinity, and the peak position has good correspondence with the peak positions of ZIF-67 and CNTs; the prepared S @ CNTs/Co-NC lithium sulfur battery positive electrode material presents standard peaks of elemental sulfur and metal Co, and the standard peaks show that the elemental sulfur is uniformly loaded in the composite carbon material after being molten and loaded with sulfur, and the composite carbon material contains metal Co particles.
Fig. 4a is a cycle performance curve of the lithium sulfur battery described in example 2 and comparative example 2, fig. 4b is a rate performance curve of the lithium sulfur battery described in example 2 and comparative example 2, and fig. 4c is a long-term cycle performance curve of the lithium sulfur battery described in example 2. As can be seen from the figure, the S @ CNTs/Co-NC positive electrode with the three-dimensional interpenetrating network structure has more excellent cycle performance and rate capability compared with the S @ CNTs positive electrode with the single carbon nanotube structure, and presents excellent large-current long-period cycle performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (8)
1. The preparation method of the lithium-sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material is characterized by comprising the following steps of:
(1) taking a multi-arm carbon nanotube with the average diameter of 20nm as a framework, activating by nitric acid, and growing a ZIF-67 nano polyhedron on the surface of the multi-arm carbon nanotube by adopting an in-situ growth method to obtain a CNTs/ZIF-67 precursor;
uniformly dispersing the multi-arm carbon nano tubes in a mixed solution of deionized water and concentrated nitric acid with a volume ratio of 3:1, and performing ultrasonic treatment until the carbon nano tubes are uniformly dispersed; placing the obtained dispersion liquid in a condensation reflux device, stirring in a constant-temperature water bath, repeatedly cleaning the obtained product with deionized water and absolute ethyl alcohol, centrifugally collecting, and drying to obtain the activated multi-arm carbon nano tube;
placing the activated multi-arm carbon nano-tube in methanol, ultrasonically dispersing uniformly, and adding Co (NO)3)2·6H2O, adding a methanol solution containing 2-methylimidazole after magnetic stirring, continuously magnetically stirring, standing at room temperature, washing the obtained product with absolute ethyl alcohol for several times, and drying after centrifugal separation to obtain a CNTs/ZIF-67 precursor;
(2) heating a CNTs/ZIF-67 precursor to 600 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and carrying out heat preservation for 3h to carry out high-temperature carbonization treatment to obtain a CNTs/Co-NC composite carbon material;
modifying a CNTs/Co-NC composite carbon material by adopting phosphorus: the CNTs/Co-NC is sprayed by using a water solution containing phosphoric acid, the CNTs/Co-NC modified by using an auxiliary agent phosphorus is obtained after drying and roasting, and P in the CNTs/Co-NC is controlled2O5The content is in the range of 0.1-0.5 wt%, and the CNTs/Co-NC surface P is made2O5In an amount of internal P2O51.1-1.5 times of the content, pore size distribution of 120-160nm, macropore proportion of 45-60%, pore volume of 0.8-2.0ml/g, specific surface area of 250-300m2/g；
(3) According to the mass ratio of 1: and 4, weighing the modified CNTs/Co-NC composite carbon material and elemental sulfur, uniformly dispersing the materials in a solution, magnetically stirring until the solvent is completely volatilized, and collecting a product, wherein the CNTs/Co-NC: elemental sulfur: CS2The solution was prepared according to 0.5-1.0 g: 2.0-4.0 g: 15-30 ml;
(4) and (4) placing the product obtained in the step (3) in a tube furnace, heating to 155 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and preserving heat for 10 hours to obtain the composite sulfur positive electrode active material.
2. The method for preparing the lithium-sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material according to claim 1, wherein: the stirring in the constant-temperature water bath in the step (1) refers to stirring for 6 hours in a constant-temperature water bath kettle at the temperature of 80 ℃.
3. The method for preparing the lithium-sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material according to claim 1, wherein: putting the multi-arm carbon nano tube subjected to activation treatment in methanol, ultrasonically dispersing uniformly, and adding Co (NO)3)2·6H2O, adding methanol solution containing 2-methylimidazole after magnetic stirring, continuing to magnetically stir, standing at room temperature, namely placing 0.3g of activated multi-arm carbon nano-tube in 100ml of methanol, performing ultrasonic treatment for 2min to uniformly disperse, and adding 0.5mol Co (NO)3)2·6H2O, magnetically stirring for 30min, adding 100ml of methanol solution containing 2mol of 2-methylimidazole, continuously magnetically stirring for 2h, and standing at room temperature for 24 h.
4. The method for preparing the lithium-sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material according to claim 1, wherein: the drying in the step (1) is carried out for 12 hours in a vacuum drying oven at the temperature of 60 ℃.
5. The three-dimensional interpenetrating composite carbon-containing material obtained by the preparation method of the three-dimensional interpenetrating composite carbon-containing material for the positive electrode material of the lithium-sulfur battery according to claims 1 to 4, wherein the three-dimensional interpenetrating composite carbon-containing material is formed by interpenetrating a multi-arm carbon nanotube framework with the average diameter of 20nm and the inside of a nano carbon polyhedron with the average diameter of 150nm, the nano carbon polyhedron is formed by high-temperature carbonization of ZIF-67, and nano Co metal particles are uniformly embedded in the nano carbon polyhedron.
6. The lithium sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material obtained by the preparation method of the lithium sulfur battery positive electrode material containing the three-dimensional interpenetrating composite carbon material according to claims 1 to 4.
7. The utility model provides a lithium sulphur battery positive pole piece which characterized in that: the preparation method comprises the following steps: weighing the lithium-sulfur positive electrode active material, the superconducting carbon and the binder LA133 obtained by the preparation method of claims 1-4 according to the mass ratio of 80:10:10, placing the materials in an agate ball milling tank, preparing the LA133 and deionized water according to the mass ratio of 1:30, weighing the deionized water, adding the deionized water into the agate ball milling tank, performing high-energy ball milling at the rotating speed of 400rpm for 30min, then uniformly coating the obtained slurry on an aluminum foil, and controlling the surface density to be 1.55mg/cm on average2And placing the obtained pole piece in a vacuum drying oven, vacuum drying at 55 ℃ for 24h, and cutting the pole piece into small wafers with the diameter of 15mm by using a cutting machine after natural cooling to obtain the lithium-sulfur battery positive pole piece.
8. A lithium-sulfur battery, which is prepared by the prior art and comprises the lithium-sulfur positive pole piece obtained by the preparation method of claim 7, a diaphragm, electrolyte and a metallic lithium negative pole piece.
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