CN110627136B - 3D-NiO/Co3O4Preparation method of/CNT/S composite material and application of/CNT/S composite material in lithium-sulfur battery - Google Patents
3D-NiO/Co3O4Preparation method of/CNT/S composite material and application of/CNT/S composite material in lithium-sulfur battery Download PDFInfo
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Abstract
The invention relates to 3D-NiO/Co3O4A preparation method of the/CNT/S composite material. The method comprises the steps of carrying out Ni replacement on a three-dimensional ordered metal organic framework, then growing a carbon nano tube by self, and compounding the carbon nano tube with S powder to obtain the 3D-NiO/Co3O4A/CNT/S composite material. The material prepared by the method is used for the lithium-sulfur battery anode material, overcomes the problems of low effective load amount, unstable cycle performance, obvious polysulfide shuttle effect and the like of sulfur in the lithium-sulfur battery anode material prepared by the prior art, and has good cycle stability.
Description
Technical Field
The invention relates to 3D-NiO/Co3O4A preparation method of a/CNT/S composite material and an application of the composite material as a lithium-sulfur battery anode material belong to the field of material chemistry.
Background of the study
Lithium-sulfur (Li-S) batteries have become the ideal choice for next generation energy storage systems due to their high theoretical capacity of positive electrode materials, (1675mAh/g, almost five times the theoretical capacity of current commercial lithium battery positive electrode materials). The Li-S battery has wide application, can overcome the over dependence on fossil energy and reduce the emission of waste gas. However, the commercial application of Li-S batteries is hampered by several challenges: (1) poor conductivity of elemental sulfur and the final discharge product Li2S leads to slow electrochemical reaction kinetics and low utilization of active materials; (2) bodies of sulfur during lithiationThe volume expansion greatly destroys the integrity of the cathode structure, causing the active material to be electrically isolated from the conductive matrix, resulting in rapid capacity fade; (3) diffusion-induced "shuttling" of soluble polysulfide intermediates leads to irreversible loss of active species and corrosion of the lithium anode. In order to solve these problems, the development of new cathode materials is urgently needed. In this regard, carbon materials have been widely studied due to the advantages of high electrical conductivity, abundant pore structure, tunable surface properties, and light weight. Researchers have explored various sulfur/carbon composites. For example, the electrochemical performance of carbon fibers such as carbon nanotubes, graphene and the like and hybrid materials thereof is obviously improved. Given the different chemical bonding properties of carbon (non-polar) and polysulfides (polar), the relatively weak interaction between polysulfides and sp2 structural carbon planes is believed to be insufficient to immobilize migrating polysulfides. Therefore, there is increasing interest in modifying the surface properties of carbon materials by functionalization, e.g., nitrogen doping, has proven to be an effective method of enhancing polysulfide interaction with carbon substrates.
Recently, Metal Organic Frameworks (MOFs) derived carbon materials, with rich and controllable pore structure and intrinsic heteroatom doping, have used sulfur as host material because they show a dual limitation of polysulfides by physical encapsulation and chemisorption. The typical MOF, zeolitic imidazolate framework-8 (ZIF-8) cobalt, has been extensively studied in recent years. Previous reports used ZIF-8-derived microporous carbon polyhedra as sulfur substrates that exhibited high initial value capacities of 1500mAh/g as the electron substrate to capture polysulfides, resulting in good cycling stability. Despite these advantages, there are two challenges: first, the conductivity of MOF derived carbon materials is not high enough due to the relatively low degree of graphite crystallinity; secondly, MOFs derived carbon materials tend to aggregate together due to their high surface energy, and MOFs nanometer sized particles not only result in slow lithium ion migration, but also insufficient contact with dissolved polysulfides.
To address both of the above problems, constructing a composite structural matrix with MOF-derived carbons uniformly dispersed in the electrical conductivity is expected to be an effective method for improving the transport capabilities of electrons and lithium ions. Carbon nanotubes, a unique atomic hollow tubular structure, consists of sp2, and it is well known that bonded carbon atoms have high surface area, excellent electrical conductivity, excellent mechanical properties and good flexibility. Furthermore, carbon nanotubes provide a highly accessible surface with a rich population of exposed active sites, which provides an opportunity to build a variety of hybrid carbon nanotube-based structures.
Disclosure of Invention
The invention aims to provide a 3D-NiO/Co system aiming at the defects in the prior art3O4A preparation method of the/CNT/S composite material. The method comprises the steps of carrying out Ni replacement on an ordered metal organic framework, and then, self-growing a carbon nano tube to obtain 3D-NiO/Co3O4A/CNT/S composite material. Mixing the 3D-NiO/Co3O4the/CNT/S composite material is used as a positive electrode material of the lithium-sulfur battery. The invention overcomes the defects of low effective load capacity, unstable cycle performance, obvious shuttle effect of polysulfide, obvious volume expansion effect of the lithium-sulfur battery in the charging and discharging processes and the like of sulfur in the lithium-sulfur battery anode material prepared by the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a lithium-sulfur battery positive electrode material is provided, wherein the positive electrode material is 3D-NiO/Co3O4a/CNT/S composite comprising the steps of:
the first step is as follows: preparation of PS spheres
Adding 10-20g of styrene and 10-20g of polyvinylpyrrolidone into 50-100mL of deionized water, stirring for 2-5h, then placing in a round bottom flask, stirring in an oil bath at 70-80 ℃, stirring for 12-24h, then centrifuging for 3 times at the rotation speed of 800rad/min, and drying at 60-80 ℃ to obtain the PS balls.
The second step is that: preparation of ordered mesoporous ZIF67 material
Dispersing 5-10mmol of cobalt nitrate hexahydrate in 250ml of 125-sand-containing methanol to be marked as solution A, and dispersing 20-40mmol of 2-methylimidazole in 250ml of 125-sand-containing methanol to be marked as solution B; and adding the solution B into the solution A with the same volume, adding 1-2g of the PS balls prepared in the first step, stirring for 3-5min to be uniform, sealing, standing and aging for 24h, centrifuging and washing, sequentially washing for 3 times by using methanol and 3 times by using ethanol, and drying at 60-80 ℃ overnight to obtain the ordered mesoporous ZIF 67.
The third step: NiO/Co3O4Preparation of
And (3) placing 1-2g of the 3D ordered mesoporous ZIF67 material prepared in the second step into a beaker, adding 1-2g of nickel nitrate and 100-200mL of deionized water, and stirring for 1-2h at 80 ℃. Centrifugally washing, and drying at 60-80 ℃ overnight to obtain the Ni-3Dzif 67.
The fourth step: 3D-NiO/Co3O4Preparation of/CNT the Ni-3Dzif8 obtained in the third step was placed under a tube furnace under Ar/H2Heating to 600-700 ℃ in the atmosphere of mixed gas, keeping the temperature for 1-2h at the heating rate of 1-2 ℃/min, and then naturally cooling to obtain the 3D-NiO/Co3O4A CNT. Wherein Ar and H in the mixer2Is 95: 5.
The fifth step: preparation of 3D-NiO/Co3O4/CNT/S
The prepared 3D-NiO/Co3O4Mixing the CNT powder and the pure S powder according to the mass ratio of 1:3, grinding, then placing the mixture into a reaction kettle, and keeping the temperature at 155 ℃ for 12 hours to obtain the 3D-NiO/Co3O4/CNT/S。
The stirring is magnetic stirring, and the rotating speed is 100-300 r/min.
To obtain 3D-NiO/Co3O4Putting the mixture into a mortar according to the weight ratio of 3D-ZIF67@ ZIF8/S: C: polyvinylidene fluoride (8: 1: 1) to be mixed and uniformly ground, then dripping N-methyl pyrrolidone (NMP) to be ground into slurry, uniformly coating the slurry on an aluminum foil with the loading of 2mg, then putting the aluminum foil into a constant-temperature drying box at 60 ℃ to be dried for 12h, drying the aluminum foil to constant weight, and pressing the aluminum foil into slices by using a tablet press under the pressure of 5MPa, thereby preparing the 3D-NiO/Co serving as an active material, carbon powder serving as a conductive agent, polyvinylidene fluoride (PVDF) serving as a binder, and preparing the 3D-ZIF67@ ZIF8/S3O4a/CNT/S battery positive plate; the metal lithium is used as a counter electrode and a reference electrode, the lithium-sulfur electrolyte is used as an electrolyte, the porous polypropylene is used as a diaphragm, and the CR2025 button cell is assembled in a glove box filled with argon.
The invention has the following beneficial effects:
the ordered 3D-NiO/Co is prepared by using a simple test method and process steps3O4The hole in the material can well adsorb polysulfide, the utilization rate of sulfur is improved, the utilization of the carbon nano tube can well enhance the conductivity of the material, and simultaneously, the metal oxides NiO and Co3O4It also has strong adsorption effect on polysulfide.
Drawings
FIG. 1 shows the 3D-NiO/Co prepared in example 13O4the/CNT/S material is used as a positive electrode material of the lithium-sulfur battery, and has 1000-time cycle performance when the current density is 1C.
FIG. 2 shows 3D-NiO/Co of example 1 of the present invention3O4XRD pattern of/CNT.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
The first step is as follows: preparation of PS spheres
10g of styrene and 10g of polyvinylpyrrolidone are added into 50mL of deionized water, stirred for 2h, then placed in an oil bath in a round bottom flask and stirred, the temperature of the oil bath is 70 ℃, the stirring is carried out for 12h, then the mixture is centrifuged for 3 times at the rotating speed of 800rad/min, and the PS spheres are obtained after drying at the temperature of 60 ℃.
The second step is that: preparation of ordered mesoporous ZIF67 material
Dispersing 5mmol of cobalt nitrate hexahydrate in 125mL of methanol to obtain solution A, and dispersing 20mmol of 2-methylimidazole in 125mL of methanol to obtain solution B; and adding the solution B into the solution A, adding 1g of the PS balls prepared in the first step, stirring for 3-5min to be uniform, sealing, standing and aging for 24h, centrifuging and washing, sequentially washing for 3 times by using methanol and 3 times by using ethanol, and drying at 60 ℃ overnight to obtain the ordered mesoporous ZIF 67. The third step: NiO/Co3O4Preparation of
And (3) putting 1g of the 3D ordered mesoporous ZIF67 material prepared in the second step into a beaker, adding 1g of nickel nitrate and 100mL of deionized water, and stirring for 1h at 80 ℃. Centrifugally washing, and drying at 60 ℃ overnight to obtain the Ni-3Dzif 67.
The fourth step: 3D-NiO/Co3O4Preparation of/CNT
Putting the Ni-3Dzif8 prepared in the third step under Ar/H in a tube furnace2Heating to 600 ℃ in the atmosphere of mixed gas, keeping the temperature for 1h at the heating rate of 1 ℃/min, and then naturally cooling to obtain the 3D-NiO/Co3O4A CNT. Wherein Ar and H in the mixer2Is 95: 5.
1g of the prepared 3D-NiO/Co3O4mixing/CNT powder and 3g of pure S powder, grinding, placing in a reaction kettle, keeping the temperature at 155 ℃ for 12 hours, taking out to obtain 3D-NiO/Co3O4/CNT/S。
To obtain 3D-NiO/Co3O4Putting the mixture into a mortar according to the weight ratio of 3D-ZIF67@ ZIF8/S: C: polyvinylidene fluoride (8: 1: 1) to be mixed and uniformly ground, then dripping N-methyl pyrrolidone (NMP) to be ground into slurry, uniformly coating the slurry on an aluminum foil with the loading of 2mg, then putting the aluminum foil into a constant-temperature drying box at 60 ℃ to be dried for 12h, drying the aluminum foil to constant weight, and pressing the aluminum foil into slices by using a tablet press under the pressure of 5MPa, thereby preparing the 3D-NiO/Co serving as an active material, carbon powder serving as a conductive agent, polyvinylidene fluoride (PVDF) serving as a binder, and preparing the 3D-ZIF67@ ZIF8/S3O4a/CNT/S battery positive plate; the metal lithium is used as a counter electrode and a reference electrode, the lithium-sulfur electrolyte is used as an electrolyte, the porous polypropylene is used as a diaphragm, and the CR2025 button cell is assembled in a glove box filled with argon.
As shown in the attached figure 1, the material has good circulation stability, and after 1000 times of circulation, the specific capacity of the material is reduced from 900mAh/g to 800 mAh/g. Because of NiO and Co in the material3O4And 3-dimensional porous structure can well absorb lithium polysulfide, and meanwhile, the carbon nano tube can enhance the structural stability of the composite material and increase the conductivity.
3D-NiO/Co3O4the/CNT material is similar to a spherical shape, the surface of the/CNT material is covered with a layer of carbon nano tubes, so that the conductivity of the material is greatly enhanced, and meanwhile, the material is shown to have a plurality of pores, so that the sulfur carrying performance of the material is increased, and meanwhile, the material also has a certain promotion effect on adsorbing polysulfide.
From FIG. 2, it is clear that the NiO/Co ratio is 3D-NiO3O4In the/CNT diffraction peak, with NiO and Co3O4The correspondence is good. This indicates that the synthesized material is of high purity and essentially free of impurities.
Example 2
20g of styrene and 20g of polyvinylpyrrolidone are added into 100mL of deionized water, stirred for 5h, then placed in a round bottom flask and stirred in an oil bath at the temperature of 80 ℃, stirred for 24h, then centrifuged for 3 times at the rotating speed of 800rad/min, and dried at the temperature of 80 ℃ to obtain the PS spheres.
The second step is that: preparation of ordered mesoporous ZIF67 material
Dispersing 10mmol of cobalt nitrate hexahydrate in 250mL of methanol to obtain solution A, and dispersing 40mmol of 2-methylimidazole in 250mL of methanol to obtain solution B; and adding the solution B into the solution A, adding 2g of the PS balls prepared in the first step, stirring for 5min to be uniform, sealing, standing and aging for 24h, centrifugally washing, washing for 3 times by using methanol and 3 times by using ethanol in sequence, and drying at 80 ℃ overnight to obtain the ordered mesoporous ZIF67 (3Dzif 67).
The third step: NiO/Co3O4Preparation of
2g of the 3D ordered mesoporous ZIF67 material prepared in the second step is placed in a beaker, 2g of nickel nitrate and 200mL of deionized water are added, and the mixture is stirred for 2 hours at 80 ℃. Centrifugally washing, and drying at 80 ℃ overnight to obtain the Ni-3Dzif 67.
The fourth step: 3D-NiO/Co3O4Preparation of/CNT
Putting the Ni-3Dzif8 prepared in the third step under Ar/H in a tube furnace2Heating to 700 ℃ under the atmosphere of the mixed gas, keeping the temperature for 2h at the heating speed of 2 ℃/min, and then naturally cooling to obtain the 3D-NiO/Co3O4A CNT. Wherein Ar and H in the mixer2Is 95: 5.
1g of the prepared 3D-NiO/Co3O4mixing/CNT powder and 3g of pure S powder, grinding, placing in a reaction kettle, keeping the temperature at 155 ℃ for 12 hours, taking out to obtain 3D-NiO/Co3O4/CNT/S。
To makeThe obtained 3D-NiO/Co3O4Putting the mixture into a mortar according to the weight ratio of 3D-ZIF67@ ZIF8/S: C: polyvinylidene fluoride (8: 1: 1) to be mixed and uniformly ground, then dripping N-methyl pyrrolidone (NMP) to be ground into slurry, uniformly coating the slurry on an aluminum foil with the loading of 2mg, then putting the aluminum foil into a constant-temperature drying box at 60 ℃ to be dried for 12h, drying the aluminum foil to constant weight, and pressing the aluminum foil into slices by using a tablet press under the pressure of 5MPa, thereby preparing the 3D-NiO/Co serving as an active material, carbon powder serving as a conductive agent, polyvinylidene fluoride (PVDF) serving as a binder, and preparing the 3D-ZIF67@ ZIF8/S3O4a/CNT/S battery positive plate; the metal lithium is used as a counter electrode and a reference electrode, the lithium-sulfur electrolyte is used as an electrolyte, the porous polypropylene is used as a diaphragm, and the CR2025 button cell is assembled in a glove box filled with argon.
Claims (9)
1. A preparation method of a lithium-sulfur battery positive electrode material is provided, wherein the positive electrode material is 3D-NiO/Co3O4The preparation method of the/CNT/S composite material comprises the following steps:
the first step is as follows: preparation of PS spheres
Adding styrene and polyvinylpyrrolidone into deionized water according to the mass ratio of 1:1 for stirring, then placing the mixture into a round bottom flask for oil bath stirring at the rotating speed of 100-300 r/min, centrifuging the product after oil bath stirring for 3 times at the rotating speed of 800rad/min, and drying at the temperature of 60-80 ℃ to obtain a PS ball;
the second step is that: preparation of ordered mesoporous ZIF67 material
Dispersing cobalt nitrate hexahydrate in methanol to obtain solution A, and dispersing 2-methylimidazole in methanol to obtain solution B; adding the solution B into the equal volume of the solution A, adding the PS balls prepared in the first step, stirring for 3-5min at the rotating speed of 100-300 r/min until the mixture is uniform, sealing, standing for aging, centrifugally washing, washing for 3 times by sequentially adopting methanol and 3 times by adopting ethanol, and drying overnight to obtain the ordered mesoporous ZIF67 material;
the third step: NiO/Co3O4Preparation of
Putting the ordered mesoporous ZIF67 material prepared in the second step into a beaker, adding nickel nitrate and deionized water, stirring, centrifuging, washing, and drying overnight to obtain NiO/Co3O4；
The fourth step: 3D-NiO/Co3O4Preparation of/CNT
NiO/Co prepared in the third step3O4Placed under a tube furnace at Ar/H2High-temperature calcination under the atmosphere of mixed gas, namely firstly heating to 200-300 ℃, preserving heat for 1-2 hours, then heating to 600-700 ℃, preserving heat for 2-3 hours, and then naturally cooling to obtain the 3D-NiO/Co3O4/CNT；
The fifth step: preparation of 3D-NiO/Co3O4/CNT/S
The prepared 3D-NiO/Co3O4Mixing the CNT powder and the pure S powder according to the mass ratio of 1:3, grinding, then placing the mixture into a reaction kettle, and keeping the temperature at 155 ℃ for 12 hours to obtain the 3D-NiO/Co3O4/CNT/S。
2. The preparation method according to claim 1, wherein in the first step, the mass of styrene is 10-20g, the mass of polyvinylpyrrolidone is 10-20g, the volume of deionized water is 50-100mL, and the stirring time is 2-5 h.
3. The process according to claim 1, wherein in the first step, the stirring temperature of the oil bath is 70 to 80 ℃ and the stirring time of the oil bath is 12 to 24 hours.
4. The method as claimed in claim 1, wherein in the second step, the amount of cobalt nitrate hexahydrate for preparing solution A is 5-10mmol, and the amount of methanol is 125-250 mL; the solution B was prepared with 20-40mmol of 2-methylimidazole and 250mL of 125-methanol.
5. The method according to claim 1, wherein in the second step, the PS beads are added after the solution A and the solution B are mixed, the weight of the PS beads is 1 to 2g, the aging time is 24 hours, and the overnight drying temperature is 60 to 80 ℃.
6. The preparation method as claimed in claim 1, wherein in the third step, the mass of the ordered mesoporous ZIF67 material is 1-2g, the mass of the nickel nitrate is 1-2g, and the volume of the deionized water is 100-200 mL.
7. The preparation method according to claim 1, wherein in the third step, the stirring temperature is 80 ℃, the stirring time is 1-2h, the rotation speed is 100-300 r/min, and the drying overnight temperature is 60-80 ℃.
8. The method of claim 1, wherein in the fourth step, Ar and H2The volume ratio of (A) to (B) is 95:5, and the temperature rise speed during high-temperature calcination is 1-2 ℃/min.
9. The use of the positive electrode material for lithium-sulfur battery prepared by the preparation method of claim 1, wherein the 3D-NiO/Co prepared by the method of claim 1 is used3O4The material is prepared from/CNT/S as active material, carbon powder as conductive agent, polyvinylidene fluoride as binder, and 3D-NiO/Co3O4Putting the mixture into a mortar according to the weight ratio of the/CNT/S: C: polyvinylidene fluoride (8: 1: 1) to be mixed and ground uniformly, then dripping a nitrogen methyl pyrrolidone solvent to be ground into slurry, uniformly coating the slurry on an aluminum foil with the loading of 2mg, drying for 12h in a constant-temperature drying box at 60 ℃, drying until the weight is constant, and pressing into sheets to obtain the 3D-NiO/Co composite material3O4a/CNT/S battery positive plate; the metal lithium is used as a counter electrode and a reference electrode, the lithium-sulfur electrolyte is used as an electrolyte, the porous polypropylene is used as a diaphragm, and the CR2025 button cell is assembled in a glove box filled with argon.
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