CN115332519A - Preparation method and application of lithium-sulfur battery positive electrode material - Google Patents
Preparation method and application of lithium-sulfur battery positive electrode material Download PDFInfo
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Abstract
The invention belongs to the field of energy materials, and relates to a preparation method and application of a lithium-sulfur battery cathode material. The invention prepares the carbon material with catalytic action by loading nitrogen atoms and cobalt compounds on the carbon material, and the preparation method comprises the following steps: firstly, preparing a nitrogen atom doped carbon material N-C; then N-C-Co is prepared on the nitrogen atom doped carbon material N-C by a coprecipitation method 3 O 4 (ii) a Finally adding N-C-Co 3 O 4 And then the mixture is roasted with sulfur powder/selenium powder at high temperature under inert atmosphere to obtain N-C-CoS/N-C-CoSe. N-C-CoS/N-C-CoSe is used as the positive electrode of the lithium-sulfur batteryWhen the active substance sulfur-carrying material in the pole piece is applied to the lithium sulfur battery, the cobalt compound loaded by the coprecipitation method has better catalytic activity compared with the cobalt compound loaded by the traditional impregnation method, the shuttle effect of lithium polysulfide can be more effectively inhibited, and the reaction kinetics, the cycle stability and the like of the lithium sulfur battery are improved.
Description
Technical Field
The invention belongs to the field of energy materials, and relates to a preparation method and application of a lithium-sulfur battery cathode material.
Background
With the rapid development of society and the rapid increase of economic level, the demand of people on energy sources is steadily increased. The lithium ion battery is the most widely applied battery type at present, and has the advantages of high energy density, low self-discharge rate, long service life and the like, so the lithium ion battery has wide application prospect. Although the specific capacity of the lithium ion battery is close to the theoretical specific capacity of 300mAhg at present -1 However, the ever-increasing energy demand of human production and life still cannot be met, and particularly, with the popularization of portable electronic devices, mobile power sources and new energy automobiles, the relatively low energy density of lithium ion batteries increasingly cannot meet the demand of large energy storage devices. It has become one of the hot spots of recent research to find an energy storage material with higher energy density, lighter weight, smaller volume and longer cycle life. In recent years, researchers at home and abroad have attracted attention to lithium-sulfur batteries using elemental sulfur as a battery positive electrode and metal lithium as a battery negative electrode material, wherein the elemental sulfur has 1675mAhg as the lithium-sulfur battery positive electrode -1 The high theoretical specific capacity shows great potential as energy storage material.
However, the commercialization of lithium sulfur batteries is also facing many obstacles: (1) The electric conductivity of sulfur and lithium sulfide is low, and the redox reaction kinetics is slow; (2) Shuttling effects due to dissolution and diffusion of soluble lithium polysulphides (LiPSs); (3) Upon lithiation, sulfur undergoes a significant volume expansion (up to 80%). Therefore, the lithium-sulfur battery has the problems of low utilization rate of sulfur, poor cycle stability, low rate performance and the like. In order to solve these problems, it is important to improve the utilization rate of active materials in an electrode material by developing a novel positive electrode material for a lithium-sulfur battery. The commercial carbon material has large specific surface area and is porous, and is suitable for lithium-sulfur batteries, however, the pure commercial carbon material lacks the chemical adsorption effect on polysulfide, and the loading of a compound with a catalytic effect on the commercial carbon material is particularly important. Because the traditional impregnation method realizes the loading by decomposing compounds at high temperature, all the compounds cannot be ensured to be loaded on the carbon material in the high-temperature decomposition process, and the quantitative loading cannot be well realized, so that the effect of loading the compounds with the catalytic action by the traditional impregnation method is not ideal all the time.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a lithium-sulfur battery positive electrode material. On the basis of high conductivity of the carbon material, the cobalt compound is loaded by a coprecipitation method, so that the anode material has a better electrocatalysis effect compared with the traditional impregnation method, the transformation of polysulfide is better promoted, the shuttle effect is effectively inhibited, and the specific capacity, the cycle performance and the rate capability of the lithium-sulfur battery are obviously improved.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a lithium-sulfur battery positive electrode material comprises the following steps:
(1) Preparing a nitrogen atom doped carbon material N-C: mixing and grinding a carbon material and a nitrogen source uniformly, and roasting at a high temperature in an inert gas atmosphere to prepare a nitrogen atom doped carbon material N-C;
(2) Preparation of Co-Supported 3 O 4 Nitrogen atom doped carbon material N-C-Co 3 O 4 : dispersing the N-C obtained in the step (1) in ammonia water by an equivalent impregnation method to obtain a solution A; dissolving cobalt chloride in deionized water to obtain a solution B; evaporating the solution A to dryness, pouring the solution B into the evaporated solution A to be uniformly dispersed, and carrying out water bath reaction to obtain a solution C; mixing the solutionC is subjected to hydrothermal reaction to prepare N-C-Co 3 O 4 ；
(3) Preparing nitrogen atom doped carbon material N-C-CoS/N-C-CoSe of a supported cobalt compound: the N-C-Co obtained in the step (2) 3 O 4 Mixing with sulfur powder or selenium powder, grinding uniformly, and roasting at high temperature in an inert gas atmosphere to obtain N-C-CoS/N-C-CoSe.
Further, the carbon material in the step (1) is any one or more of ketjen black, multi-wall carbon nanotubes or conductive carbon black; the nitrogen source is one or two of thiourea and urea.
Further, the specific surface area of the carbon material in the step (1) is more than 500m 2 /g。
Further, the inert gas in the step (1) is argon or nitrogen.
Further, the mass ratio of the nitrogen source to the carbon material in the step (1) is 1 (5 to 20); the high-temperature roasting temperature is 800 to 1100 ℃, and the high-temperature roasting time is 1 to 4 hours.
Further, the heating rate of the high-temperature roasting in the step (1) is 2-10 ℃/min.
Further, the concentration of ammonia water in the step (2) is 5% -25%; the mass ratio of the cobalt chloride to the N-C is 1 (5-20).
Further, the solution C in the step (2) contains a complex formed by ammonia water and cobalt ions, the temperature of the water bath reaction is 50 ℃, and the time of the water bath reaction is 6 to 8h.
Further, the temperature of the hydrothermal reaction in the step (2) is 150 to 180 ℃, and the time of the hydrothermal reaction is 3 to 5 hours.
Further, the complex generated by the ammonia water and the cobalt ions in the step (2) has dissociation tendency at 150-180 ℃, and is dissociated into Co 3 O 4 Obtaining N-C-Co 3 O 4 。
Further, in the step (3), N-C-Co 3 O 4 The mass ratio of the sulfur powder to the selenium powder is 1 (5 to 20); the inert gas is argon or nitrogen; the high-temperature roasting temperature is 700-900 ℃, and the high-temperature roasting time is 2-5h.
Furthermore, nitrogen and a loaded cobalt compound in the lithium-sulfur battery cathode material N-C-CoS/N-C-CoSe prepared by the method are partially or completely dispersed on a carbon carrier, wherein the mass percent of the nitrogen is 1-5%, and the mass percent of the cobalt compound is 1-20%.
Further, the lithium-sulfur battery positive electrode material is used as an active substance sulfur-carrying material in a lithium-sulfur battery positive electrode piece in the application of the lithium-sulfur battery positive electrode material in a lithium-sulfur battery.
Further, the application steps are as follows:
(a) Uniformly mixing sublimed sulfur and N-C-CoS/N-C-CoSe, mixing sulfur powder and the N-C-CoS/N-C-CoSe in a melting sulfur filling mode under the vacuum or inert gas protection atmosphere to obtain a carbon/sulfur composite anode material, and keeping the temperature for 12 to 24h at the heating temperature of 155 ℃, wherein the mass ratio of the N-C-CoS/N-C-CoSe in the carbon/sulfur composite anode material is 20 to 30 percent;
(b) Mixing the carbon/sulfur composite positive electrode material obtained in the step (a), a conductive agent and a binder, uniformly mixing the materials by taking nitrogen methyl pyrrolidone as a solvent to prepare slurry, coating the slurry on a current collector, and drying the slurry in vacuum to prepare a positive electrode plate of the lithium-sulfur battery;
(c) And (c) assembling the positive pole piece, the lithium negative pole, the diaphragm, the electrolyte and the shell of the lithium-sulfur battery obtained in the step (b) to obtain the lithium-sulfur battery.
Further, the mass ratio of the sublimed sulfur to the uniform mixture of N-C-CoS/N-C-CoSe in the step (a) is 7.
Further, the inert gas in the step (a) is argon or nitrogen.
Further, the conductive agent in the step (b) is any one or more of conductive carbon black, conductive graphite or carbon nano tubes; the binder is polyvinylidene fluoride.
Further, the mass ratio of the carbon/sulfur composite cathode material, the conductive agent and the binder in the step (b) is (80-90): (5-10): 5-10).
Further, the step (b) of uniformly mixing to prepare the slurry comprises the following steps: adopting a ball milling method, wherein the ball milling time is 2 to 3 hours, and the loading capacity of the active material sulfur of the positive pole piece is 0.8 to 2mg/cm 2 。
Further, the membrane in the step (c) is a microporous polyolefin membrane, a ceramic membrane or a non-woven fabric membrane, and the like.
Preferably, the microporous polyolefin separator in step (c) consists of one or more layers of Polyethylene (PE) or polypropylene (PP).
Further, the electrolyte in the step (c) is composed of a lithium-containing electrolyte and a non-aqueous organic solvent, wherein the electrolyte is lithium bistrifluoromethanesulfonimide (LiTFSI), and the non-aqueous organic solvent is one or two of Dioxolane (DOL) and ethylene glycol dimethyl ether (DME).
The invention has the following beneficial effects:
1. the traditional impregnation method realizes loading by decomposing compounds at high temperature, and in the high-temperature decomposition process, all the compounds cannot be loaded on the carbon material, and quantitative loading cannot be well realized.
2. The carbon material with larger pore volume and larger specific surface area is selected to be modified, and the carbon material is used as a carrier of the lithium-sulfur battery cathode material to play a role in physical confinement of polysulfide, so that the shuttle effect is reduced. The cobalt compound is loaded by a coprecipitation method instead of an impregnation method, so that the electron transport capacity and the number of active sites of the carbon material are increased, the conductivity of the carbon material is improved, the reaction kinetics of the lithium-sulfur battery can be well improved, the electron transport in the electrochemical reaction process is accelerated, the shuttle of polysulfide is reduced, and the polarization of the battery is reduced.
3. Experimental results show that the introduction of the cobalt compound by the coprecipitation method can enable the lithium-sulfur battery to have higher gram capacity (the first discharge gram capacity is 895mAh/g under 0.5C multiplying power), good cycle performance (the first discharge gram capacity is 895mAh/g under 0.5C multiplying power, and the discharge gram capacity is 756mAh/g after 200 weeks of cycle), rate performance (the discharge gram capacities after 5 weeks of cycle under 0.1C, 0.5C, 1C and 2C multiplying power are 1399mAh/g, 896mAh/g, 820mAh/g and 780mAh/g respectively), and the like, so that the electrochemical performance of the lithium-sulfur battery is remarkably improved, and the cobalt compound has important significance for further commercialization of the lithium-sulfur battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an XRD pattern of example 1, example 2, comparative example 1, and comparative example 2 of the present invention.
Fig. 2 is a graph showing the impedance of lithium-sulfur batteries according to comparative examples 1, 2, 3, 1 and 2 of the present invention after one cycle.
Fig. 3 is a graph showing different rate performance of lithium-sulfur batteries corresponding to comparative example 1, comparative example 3 and example 1 of the present invention.
Fig. 4 is a graph showing different rate performance of the lithium sulfur battery according to comparative example 2, comparative example 3, and example 2 of the present invention.
Fig. 5 is a graph of 0.5C rate cycle performance of lithium-sulfur batteries corresponding to comparative example 1, comparative example 3, and example 1 of the present invention.
Fig. 6 is a graph of 0.5C rate cycle performance of lithium sulfur batteries corresponding to comparative example 2, comparative example 3, and example 2 of the present invention.
Fig. 7 is a first charge and discharge curve diagram of a rate performance test of lithium sulfur batteries corresponding to comparative example 1, comparative example 3 and example 1 of the present invention.
Fig. 8 is a first charge-discharge curve diagram of the lithium-sulfur battery rate performance test according to comparative examples 2, 3 and 2 of the present invention.
The horizontal axis of the obtained XRD pattern is diffraction angle (2 theta), and the vertical axis is diffraction peak Intensity (Intensity).
The Cycle number (Cycle number) is plotted on the abscissa and the Specific capacity (Specific capacity) is plotted on the ordinate of the obtained Cycle performance chart and rate performance chart.
In the obtained charge/discharge graph, the abscissa represents a Specific capacity (Specific capacity) and the ordinate represents a Voltage (Voltage).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The embodiment is a preparation method of a lithium-sulfur battery cathode material N-KB-CoS prepared by a coprecipitation method and a performance test of the lithium-sulfur battery cathode material N-KB-CoS applied to the lithium-sulfur battery, and the method comprises the following steps:
(1) Preparation of N-KB: grinding 0.1g Keqin black and 0.02g urea in a mortar, placing into a small porcelain boat, and introducing N in a tube furnace 2 And (3) removing the air, keeping the temperature at 800 ℃ for 2h, keeping the temperature at the rate of 5 ℃/min, finishing the heat preservation, and taking out the sample when the temperature is reduced to the room temperature to obtain N-KB.
（2）N-KB-Co 3 O 4 The preparation of (1): adding 0.1g of N-KB and 0.013mL of 25% ammonia water into a defoaming machine, adding 5mL of deionized water, starting the defoaming machine to obtain a viscous solution A, dissolving 0.013g of cobalt chloride hexahydrate in 5mL of deionized water to obtain a solution B, transferring the solution A into a beaker, evaporating the liquid, pouring the solution B into the solution A, reacting for 6 hours at 50 ℃ in a water bath kettle, transferring into a polytetrafluoroethylene reaction kettle, reacting for 3 hours at 150 ℃, adding 25mL of deionized water each time, centrifuging for 3 times to obtain a lower-layer precipitate, placing the lower-layer precipitate into an oven, drying for 12 hours at 60 ℃ to obtain N-KB-Co 3 O 4 。
(3) Preparation of N-KB-CoS: 0.1g of N-KB-Co 3 O 4 Grinding and mixing with 0.012g of sulfur powder, placing into a small porcelain boat, introducing N2 into a tube furnace to remove air, and keeping at 800 deg.CAnd (3) heating for 2h at the heating rate of 5 ℃/min, finishing heat preservation, and taking out a sample after the temperature is reduced to room temperature to obtain the N-KB-CoS with the cobalt compound content of 5%.
(4) Weighing an N-KB-CoS material and sublimed sulfur according to a mass ratio of 3.
(5) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of the edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven for baking for 6h at 60 ℃, and preparing the lithium-sulfur battery positive pole piece after baking, wherein the sulfur-carrying capacity of the coating surface density is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to be used as a working electrode (positive electrode), a metal lithium sheet is used as a counter electrode (negative electrode), a polyethylene/polypropylene composite diaphragm (celgard 2400), 1mol/L lithium bistrifluoromethylsulfonyl imide (LTFSI) salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1. And (3) performing cycle performance test on the battery, wherein the charging and discharging current of the first three circles is 0.1C, and then testing according to 0.5C, wherein 1C=1675mAh/g, and the test voltage range is 1.8 to 2.8V.
Example 2
This example is a preparation method of a lithium sulfur battery cathode material N-KB-CoSe prepared by a coprecipitation method and a performance test applied to the lithium sulfur battery, and includes the following steps:
(1) Preparation of N-KB: grinding 0.1g Keqin black and 0.02g urea in mortar, placing into small porcelain boat, introducing N in tube furnace 2 And (3) removing the air, keeping the temperature at 800 ℃ for 2h, keeping the temperature at the rate of 5 ℃/min, finishing the heat preservation, and taking out the sample when the temperature is reduced to the room temperature to obtain N-KB.
（2）N-KB-Co 3 O 4 The preparation of (1): adding 0.1g of N-KB and 0.013mL of 25% ammonia water into a defoaming machine, adding 5mL of deionized water, starting the defoaming machine to obtain a viscous contained solution A, dissolving 0.013g of cobalt chloride hexahydrate in 5mL of deionized water to obtain a solution B, transferring the solution A into a beaker, evaporating the liquid, pouring the solution B into the solution A, reacting for 6 hours at 50 ℃ in a water bath kettle, transferring into a polytetrafluoroethylene reaction kettle, reacting for 3 hours at 150 ℃, adding 25mL of deionized water each time, centrifuging for 3 times to obtain a lower-layer precipitate, placing the lower-layer precipitate into an oven, drying for 12 hours at 60 ℃ to obtain N-KB-Co 3 O 4 。
(3) Preparation of N-KB-CoSe: 0.1g of N-KB-Co 3 O 4 Grinding and mixing with 0.02g selenium powder, placing into a small porcelain boat, and introducing N into a tube furnace 2 And (3) removing the air, keeping the temperature at 800 ℃ for 2h at the heating rate of 5 ℃/min, finishing the heat preservation, cooling to room temperature, taking out the sample, and obtaining N-KB-CoSe with the cobalt compound content of 5%.
(4) Weighing an N-KB-CoSe material and sublimed sulfur according to a mass ratio of 3.
(5) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of a blade edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven to bake for 6h at 60 ℃, and drying to prepare the lithium-sulfur battery anode pole piece, wherein the density sulfur-carrying amount of a coating surface is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to serve as a working electrode (positive pole), a metal lithium sheet serves as a counter electrode (negative pole), a polyethylene/polypropylene composite diaphragm (celgard 2400), and an electrolyte containing 1mol/L lithium bistrifluoromethanesulfonylimide (LTFSI) lithium salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1. And (3) performing cycle performance test on the battery, wherein the charging and discharging current of the first three circles is 0.1C, and then testing according to 0.5C, wherein 1C=1675mAh/g, and the test voltage range is 1.8 to 2.8V.
Example 3
The embodiment is a preparation method of a lithium sulfur battery cathode material N-C-CoS prepared by a coprecipitation method and a performance test of the lithium sulfur battery cathode material N-C-CoS, and the steps are as follows:
(1) Preparation of N-C: grinding 0.2g of multi-wall carbon nano-tube and 0.02g of thiourea in a mortar uniformly, putting the ground mixture into a small porcelain boat, and introducing Ar in a tube furnace 2 And (3) removing the air, keeping the temperature at 800 ℃ for 4h, keeping the temperature at the rate of 3 ℃/min, finishing the heat preservation, and taking out the sample when the temperature is reduced to the room temperature to obtain the N-CNTs.
（2）N-C-Co 3 O 4 The preparation of (1): adding 0.1g of N-C and 0.013mL of 25% ammonia water into a defoaming machine, adding 5mL of deionized water, starting the defoaming machine to obtain a viscous contained solution A, dissolving 0.02g of cobalt chloride hexahydrate in 5mL of deionized water to obtain a solution B, transferring the solution A into a beaker, evaporating the liquid, pouring the solution B into the solution A, reacting for 7.5h at 50 ℃ in a water bath kettle, transferring into a polytetrafluoroethylene reaction kettle, reacting for 5h at 150 ℃, adding 25mL of deionized water each time, centrifuging for 3 times to obtain a lower-layer precipitate, drying for 12h at 60 ℃ in an oven to obtain N-CNTs-Co, and obtaining N-CNTs-Co 3 O 4 。
(3) Preparation of N-C-CoS: 0.1g of N-C-Co 3 O 4 Grinding and mixing with 0.008g of sulfur powder, putting into a small porcelain boat, and introducing N into a tube furnace 2 And (3) removing the air, keeping the temperature at 700 ℃ for 5h at the heating rate of 5 ℃/min, finishing the heat preservation, cooling to room temperature, taking out the sample, and obtaining the N-C-CoS with the cobalt compound content of 4%.
(4) Weighing an N-C-CoS material and sublimed sulfur according to a mass ratio of 3.
(5) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of a blade edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven to bake for 6h at 60 ℃, and drying to prepare the lithium-sulfur battery anode pole piece, wherein the density sulfur-carrying amount of a coating surface is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to be used as a working electrode (positive electrode), a metal lithium sheet is used as a counter electrode (negative electrode), a polyethylene/polypropylene composite diaphragm (celgard 2400), 1mol/L lithium bistrifluoromethylsulfonyl imide (LTFSI) salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1.
Example 4
The embodiment is a preparation method of a lithium-sulfur battery cathode material N-C-CoS prepared by a coprecipitation method and a performance test of the lithium-sulfur battery cathode material N-C-CoS applied to the lithium-sulfur battery, and the method comprises the following steps:
(1) Preparation of N-C: grinding 0.3g of multi-wall carbon nano-tube and 0.02g of thiourea in a mortar uniformly, putting the ground mixture into a small porcelain boat, and introducing N into a tube furnace 2 And (3) removing the air, keeping the temperature at 900 ℃ for 3h, keeping the temperature at the rate of 2 ℃/min, finishing the temperature keeping, cooling to room temperature, taking out the sample, and obtaining the N-C.
（2）N-C-Co 3 O 4 The preparation of (1): 0.13g of the above N-C and 0.04mL of aqueous ammonia (8% concentration) were added to a defoaming machine, followed by additionAdding 5mL of deionized water, starting a defoaming machine to obtain a viscous solution A, dissolving 0.013g of cobalt chloride hexahydrate in 5mL of deionized water to obtain a solution B, transferring the solution A to a beaker, evaporating the liquid to dryness, then pouring the solution B into the solution A, reacting for 7 hours at 50 ℃ in a water bath kettle, transferring to a polytetrafluoroethylene reaction kettle, reacting for 4 hours at 170 ℃, adding 25mL of deionized water each time, centrifuging for 3 times to obtain a lower-layer precipitate, putting into an oven, drying for 12 hours at 60 ℃ to obtain N-C-Co 3 O 4 。
(3) Preparation of N-C-CoS: 0.15g of N-C-Co 3 O 4 And 0.01g of sulfur powder are ground and mixed evenly, the mixture is placed into a small porcelain boat, N2 is introduced into a tube furnace to drive away air, the temperature is kept for 4 hours at 800 ℃, the heating rate is 5 ℃/min, the temperature is kept to be room temperature after the temperature is reduced, a sample is taken out, and N-C-CoS with the cobalt compound content of 3% is obtained.
(4) Weighing an N-C-CoS material and sublimed sulfur according to a mass ratio of 2.
(5) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of a blade edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven to bake for 6h at 60 ℃, and drying to prepare the lithium-sulfur battery anode pole piece, wherein the density sulfur-carrying amount of a coating surface is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to serve as a working electrode (positive pole), a metal lithium sheet serves as a counter electrode (negative pole), a polyethylene/polypropylene composite diaphragm (celgard 2400), and an electrolyte containing 1mol/L lithium bistrifluoromethanesulfonylimide (LTFSI) lithium salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1.
Example 5
This example is a method for preparing N-C-CoSe, a positive electrode material for a lithium-sulfur battery, prepared by a co-precipitation method, and a performance test applied to the lithium-sulfur battery, and includes the following steps:
(1) Preparation of N-C: grinding 0.2g of conductive carbon black and 0.01g of thiourea in a mortar uniformly, putting the ground conductive carbon black and thiourea in a small porcelain boat, and introducing N into a tube furnace 2 And (3) removing the air, keeping the temperature at 1100 ℃ for 1h, keeping the temperature at the heating rate of 4 ℃/min, finishing the temperature keeping, cooling to room temperature, taking out the sample, and obtaining the N-C.
（2）N-C-Co 3 O 4 The preparation of (1): adding 0.26g of N-C and 0.003mL of ammonia water (10% concentration) into a defoaming machine, adding 5mL of deionized water, starting the defoaming machine to obtain a viscous solution A, dissolving 0.013g of cobalt chloride hexahydrate in 5mL of deionized water to obtain a solution B, transferring the solution A into a beaker, evaporating the liquid, pouring the solution B into the solution A, reacting at 50 ℃ for 8 hours in a water bath kettle, transferring into a polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 5 hours, adding 25mL of deionized water each time, centrifuging for 3 times to obtain a lower-layer precipitate, drying in an oven at 60 ℃ for 12 hours to obtain N-C-Co-I 3 O 4 。
(3) Preparation of N-C-CoSe: 0.24g of N-KB-Co 3 O 4 Grinding and mixing with 0.012g selenium powder, placing into small porcelain boat, introducing N into tube furnace 2 And (3) removing the air, keeping the temperature at 900 ℃ for 2h, keeping the temperature at the rate of 5 ℃/min, finishing the heat preservation, cooling to room temperature, taking out the sample, and obtaining the N-C-CoSe with the cobalt compound content of 5%.
(4) Weighing an N-C-CoSe material and sublimed sulfur according to a mass ratio of 2.
(5) The obtained sulfur-carbon composite anodeThe material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) are mixed according to the mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of the edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven for baking for 6h at 60 ℃, and preparing the lithium-sulfur battery positive pole piece after baking, wherein the sulfur-carrying capacity of the coating surface density is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to be used as a working electrode (positive electrode), a metal lithium sheet is used as a counter electrode (negative electrode), a polyethylene/polypropylene composite diaphragm (celgard 2400), 1mol/L lithium bistrifluoromethylsulfonyl imide (LTFSI) salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1.
Comparative example 1
This comparative example is a test of the preparation of N-KB-CoS material obtained by the conventional impregnation method and its performance for use in lithium sulfur batteries, and the procedure was as follows:
(1) Preparation of N-KB: grinding 0.1g Keqin black and 0.02g urea in mortar, placing into small porcelain boat, introducing N in tube furnace 2 And (3) removing the air, keeping the temperature at 700 ℃ for 2h, keeping the temperature at the rate of 5 ℃/min, finishing the heat preservation, and taking out the sample when the temperature is reduced to the room temperature to obtain N-KB.
（2）N-KB-Co 3 O 4 The preparation of (1): dissolving the 0.1g of N-KB and 0.013g of cobalt nitrate in 5mL of deionized water, evaporating the liquid to dryness, drying in an oven at 60 ℃ for 12h, putting the obtained sample into a small porcelain boat, and introducing N in a tube furnace 2 Removing air, keeping the temperature at 650 deg.C for 2 hr at a temperature rise rate of 5 deg.C/min, and decomposing cobalt nitrate into cobaltosic oxide (Co) at high temperature 3 O 4 ) Obtaining N-KB-Co 3 O 4 。
(3) Preparation of N-KB-CoS: 0.1g of N-KB-Co 3 O 4 Grinding and mixing with 0.012g of sulfur powder, putting into a small porcelain boat, and introducing N into a tube furnace 2 And (3) removing the air, keeping the temperature at 650 ℃ for 2h at the heating rate of 5 ℃/min, finishing the heat preservation, cooling to room temperature, taking out the sample, and obtaining the N-KB-CoSe.
(4) Weighing an N-KB-CoSe material and sublimed sulfur according to a mass ratio of 3.
(5) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of a blade edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven to bake for 6h at 60 ℃, and drying to prepare the lithium-sulfur battery anode pole piece, wherein the density sulfur-carrying amount of a coating surface is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to be used as a working electrode (positive electrode), a metal lithium sheet is used as a counter electrode (negative electrode), a polyethylene/polypropylene composite diaphragm (celgard 2400), 1mol/L lithium bistrifluoromethylsulfonyl imide (LTFSI) salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1. And (3) performing cycle performance test on the battery, wherein the charging and discharging current of the first three circles is 0.1C, and then testing according to 0.5C, wherein 1C=1675mAh/g, and the test voltage range is 1.8 to 2.8V.
Comparative example 2
This comparative example is a test of the preparation of a N-KB-CoSe material obtained by a conventional impregnation method and its performance for use in a lithium sulfur battery, and the procedure was as follows:
(1) Preparation of N-KB: grinding 0.1g Keqin black and 0.02g urea in a mortar, placing into a small porcelain boat, and introducing N in a tube furnace 2 Drive the airAnd keeping the temperature at 700 ℃ for 2h at the heating rate of 5 ℃/min, finishing the heat preservation, and taking out the sample when the temperature is reduced to room temperature to obtain the N-KB.
（2）N-KB-Co 3 O 4 The preparation of (1): dissolving the 0.1g of N-KB and 0.013g of cobalt nitrate in 5mL of deionized water, evaporating the liquid to dryness, putting the dried liquid in an oven for drying at 60 ℃ for 12h, putting the obtained sample in a small porcelain boat, and introducing N into a tube furnace 2 Removing air, keeping the temperature at 650 deg.C for 2 hr at a temperature rise rate of 5 deg.C/min, and decomposing cobalt nitrate into cobaltosic oxide (Co) at high temperature 3 O 4 ) Obtaining N-KB-Co 3 O 4 。
(3) Preparation of N-KB-CoSe: 0.1g of N-KB-Co 3 O 4 Grinding and mixing with 0.02g selenium powder, placing into a small porcelain boat, and introducing N into a tube furnace 2 And (3) removing the air, keeping the temperature at 650 ℃ for 2h at the heating rate of 5 ℃/min, finishing the heat preservation, cooling to room temperature, taking out the sample, and obtaining the N-KB-CoSe.
(4) Weighing an N-KB-CoSe material and sublimed sulfur according to a mass ratio of 3.
(5) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of the edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven to bake for 6h at 60 ℃, and preparing the lithium-sulfur battery positive pole piece after baking, wherein the sulfur carrying capacity of the coating surface is about 1mg/cm 2 。
(6) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to serve as a working electrode (positive pole), a metal lithium sheet serves as a counter electrode (negative pole), a polyethylene/polypropylene composite diaphragm (celgard 2400), and an electrolyte containing 1mol/L lithium bistrifluoromethanesulfonylimide (LTFSI) lithium salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1. And (3) carrying out cycle performance test on the battery, wherein the current for charging and discharging in the first three circles is 0.1C, and then carrying out test according to 0.5C, wherein 1C =1675mAh/g, and the test voltage range is 1.8-2.8V.
Comparative example 3
This comparative example is a performance test of an unmodified commercial carbon material KB for use in a lithium sulfur battery, the procedure was as follows:
unlike the examples, this comparative example directly used commercial Ketjen Black (KB) for a lithium sulfur battery.
(1) Weighing KB materials and sublimed sulfur according to the mass ratio of 3.
(2) Mixing the obtained sulfur-carbon composite positive electrode material, a conductive agent (conductive carbon black, super P) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8. Coating the slurry on an aluminum foil current collector by using a scraper, wherein the height of the edge of the scraper is 150 mu m, placing the pole piece in a vacuum oven for baking for 6h at 60 ℃, and preparing the lithium-sulfur battery positive pole piece after baking, wherein the sulfur-carrying capacity of the coating surface density is about 1mg/cm 2 。
(3) A positive pole piece of the lithium-sulfur battery is cut into a circular sheet with the diameter of 12mm to be used as a working electrode (positive electrode), a metal lithium sheet is used as a counter electrode (negative electrode), a polyethylene/polypropylene composite diaphragm (celgard 2400), 1mol/L lithium bistrifluoromethylsulfonyl imide (LTFSI) salt, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1. And (3) performing cycle performance test on the battery, wherein the charging and discharging current of the first three circles is 0.1C, and then testing according to 0.5C, wherein 1C=1675mAh/g, and the test voltage range is 1.8 to 2.8V.
Fig. 1 is XRD patterns of example 1, example 2, comparative example 1, and comparative example 2. According to the positions of the peaks, the cobalt sulfide and the cobalt selenide are successfully loaded on Ketjen Black (KB) by the traditional impregnation method and the coprecipitation method, and compounds are successfully loaded by different loading methods, but the performance difference is large.
Fig. 2 is a graph showing the impedance of example 1, example 2, comparative example 1, comparative example 2, and comparative example 3 for the first-cycle discharge of the lithium sulfur battery. As can be seen from the graph, the resistance properties of examples 1 and 2 are superior to those of comparative examples 1, 2 and 3.
Fig. 3 is a cycle chart of example 1, comparative example 1, and comparative example 3 at different magnifications. As can be seen from the figure, the discharging gram capacities after 5 weeks of each circulation of example 1 under the magnifications of 0.1C, 0.5C, 1C and 2C are 1399mAh/g, 896mAh/g, 820mAh/g and 780mAh/g respectively, the discharging gram capacities of corresponding comparative example 1 are 1189mAh/g,801mAh/g,780mAh/g and 710mAh/g respectively, and the discharging gram capacities of comparative example 3 are 1024mAh/g, 785mAh/g, 763mAh/g and 695mAh/g respectively.
Fig. 4 is a cycle chart of example 2, comparative example 2, and comparative example 3 at different magnifications. As can be seen from the graph, the discharging gram capacities after 5 weeks of each circulation under the magnifications of 0.1C, 0.5C, 1C and 2C of the example 2 are 1295mAh/g, 815mAh/g, 770mAh/g and 756mAh/g respectively, the discharging gram capacities of the comparative example 2 are 1186mAh/g, 813mAh/g, 735mAh/g and 550mAh/g respectively, and the discharging gram capacities of the comparative example 3 are 1024mAh/g, 785mAh/g, 763mAh/g and 695mAh/g respectively.
Fig. 5 is a graph of 0.5C rate cycle performance of lithium-sulfur batteries corresponding to comparative example 1, comparative example 3, and example 1 of the present invention. As shown in FIG. 5, the first-time-discharge gram-capacity of example 1 was 895mAh/g, the first-time-discharge gram-capacity of comparative example 1 was 815mAh/g, and the first-time-discharge gram-capacity of comparative example 3 was 700mAh/g, and after 200 weeks of cycling, the first-time-discharge gram-capacity of example 1 was 756mAh/g, the first-time-discharge gram-capacity of comparative example 1 was 395mAh/g, and the first-time-discharge gram-capacity of comparative example 3 was only 312mAh/g.
Fig. 6 is a graph of 0.5C rate cycle performance of lithium sulfur batteries corresponding to comparative example 2, comparative example 3, and example 2 of the present invention. As shown in FIG. 6, the first-time-discharge gram-capacity of example 2 is 902mAh/g, the first-time-discharge gram-capacity of comparative example 2 is 803mAh/g, the first-time-discharge gram-capacity of comparative example 3 is 700mAh/g, and after 200 weeks of cycling, the first-time-discharge gram-capacity of example 2 is 635mAh/g, the first-time-discharge gram-capacity of comparative example 2 is 395mAh/g, and the first-time-discharge gram-capacity of comparative example 3 is only 312mAh/g.
Fig. 7 and 8 are first charge and discharge curves corresponding to fig. 5 and 6. As can be seen from the figure, the N-C-CoS/N-C-CoSe material shows a charge-discharge platform curve peculiar to a typical lithium-sulfur battery, the voltage delta E of the example 1 and the example 2 is far smaller than the overvoltage of the comparative example 1, the comparative example 2 and the comparative example 3, and the conversion rate of polysulfide ions is improved, and the examples have certain catalytic action. From experimental data, the performance of the example is obviously superior to that of the comparative example in the aspects of gram discharge capacity, cycle performance, rate performance and the like of the battery, and the electrochemical performance is better. Therefore, the application of the modified commercial carbon material in the lithium-sulfur battery is feasible and has a good performance improvement effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
(1) Preparing a nitrogen atom doped carbon material N-C: mixing and grinding a carbon material and a nitrogen source uniformly, and roasting at a high temperature in an inert gas atmosphere to prepare a nitrogen atom doped carbon material N-C;
(2) Preparation of Co-Supported 3 O 4 Nitrogen atom doped carbon material N-C-Co 3 O 4 : dispersing the N-C obtained in the step (1) in ammonia water by an equivalent impregnation method to obtain a solution A; dissolving cobalt chloride in deionized water to obtain a solution B; evaporating the solution A to dryness, then pouring the solution B to drynessAfter the solution A is uniformly dispersed, carrying out water bath reaction to obtain a solution C; carrying out hydrothermal reaction on the solution C to obtain N-C-Co 3 O 4 ；
(3) Preparing nitrogen atom doped carbon material N-C-CoS/N-C-CoSe of a supported cobalt compound: the N-C-Co obtained in the step (2) 3 O 4 Mixing with sulfur powder or selenium powder, grinding uniformly, and roasting at high temperature in an inert gas atmosphere to obtain N-C-CoS/N-C-CoSe.
2. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the carbon material in the step (1) is any one or more of Ketjen black, multi-walled carbon nanotubes or conductive carbon black; the nitrogen source is one or two of thiourea or urea; the inert gas is argon or nitrogen.
3. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 2, characterized in that: the mass ratio of the nitrogen source to the carbon material in the step (1) is 1 (5 to 20); the high-temperature baking temperature is 800 to 1100 ℃, and the high-temperature baking time is 1 to 4 hours.
4. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 3, wherein: the concentration of the ammonia water in the step (2) is 5% -25%; the mass ratio of the cobalt chloride to the N-C is 1 (5-20).
5. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 4, wherein: and (3) the solution C in the step (2) contains a complex formed by ammonia water and cobalt ions, the water bath reaction temperature is 50 ℃, and the water bath reaction time is 6-8h.
6. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 5, wherein: the temperature of the hydrothermal reaction in the step (2) is 150 to 180 ℃, and the time of the hydrothermal reaction is 3 to 5h.
7. According to claim6, the preparation method of the lithium-sulfur battery positive electrode material is characterized by comprising the following steps: N-C-Co in the step (3) 3 O 4 The mass ratio of the sulfur powder to the selenium powder is 1 (5 to 20); the inert gas is argon or nitrogen; the high-temperature roasting temperature is 700-900 ℃, and the high-temperature roasting time is 2-5h.
8. A lithium sulfur battery positive electrode material prepared by the method of any one of claims 1 to 7, characterized in that: the nitrogen doped in the N-C-CoS/N-C-CoSe and the loaded cobalt compound are partially or completely dispersed on the carbon carrier, the mass percent of the nitrogen is 1-5%, and the mass percent of the cobalt compound is 1-20%.
9. The use of the lithium sulfur battery positive electrode material of claim 8 as an active material sulfur-carrying material in a lithium sulfur battery positive electrode sheet in a lithium sulfur battery.
10. Use according to claim 9, characterized in that the steps are as follows:
(a) Uniformly mixing sublimed sulfur and N-C-CoS/N-C-CoSe, mixing sulfur powder and the N-C-CoS/N-C-CoSe in a melting sulfur filling mode under the vacuum or inert gas protection atmosphere to obtain a carbon/sulfur composite anode material, and keeping the temperature for 12 to 24h at the heating temperature of 155 ℃, wherein the mass ratio of the N-C-CoS/N-C-CoSe in the carbon/sulfur composite anode material is 20 to 30 percent;
(b) Mixing the carbon/sulfur composite positive electrode material obtained in the step (a), a conductive agent and a binder, uniformly mixing the materials by taking N-methylpyrrolidone as a solvent to prepare slurry, coating the slurry on a current collector, and drying the slurry in vacuum to prepare a positive electrode plate of the lithium-sulfur battery;
(c) And (c) assembling the positive pole piece, the lithium negative pole, the diaphragm, the electrolyte and the shell of the lithium-sulfur battery obtained in the step (b) to obtain the lithium-sulfur battery.
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