CN116764660A - High-activity positive electrode material catalyst for lithium-sulfur battery and preparation method thereof - Google Patents

High-activity positive electrode material catalyst for lithium-sulfur battery and preparation method thereof Download PDF

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Publication number
CN116764660A
CN116764660A CN202310577015.3A CN202310577015A CN116764660A CN 116764660 A CN116764660 A CN 116764660A CN 202310577015 A CN202310577015 A CN 202310577015A CN 116764660 A CN116764660 A CN 116764660A
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lithium
positive electrode
heat treatment
electrode material
molybdenum
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李祥村
朱鼎
于淼
姜晓滨
贺高红
肖武
郑文姬
代岩
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Dalian University of Technology
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Dalian University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • B01J37/086Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a high-activity positive electrode material catalyst for a lithium sulfur battery and a preparation method thereof, wherein the catalyst comprises a flaky nitrogen-doped carbon-based carrier and molybdenum metal nanoclusters uniformly embedded on the surface of the carrier, wherein the molybdenum metal nanoclusters are 1-10nm, the mass ratio of the molybdenum metal nanoclusters on the carrier is 10-20wt%, and the catalyst is used as the positive electrode material of the lithium sulfur battery after being melted into sulfur. The catalyst is prepared by taking a cyanamide compound and an organometallic molybdenum salt as raw materials or continuously adding a carbon material with defects, and directly carbonizing in a tube furnace in an inert atmosphere through full physical mixing. The high-specific-surface-area flaky nitrogen doped carbon conductive material with the uniformly distributed molybdenum metal nanoclusters performs physical adsorption and chemical catalysis on polysulfide formed in the charge-discharge process of the positive electrode side of the lithium-sulfur battery, captures the polysulfide, solves the shuttle effect in the charge-discharge process, and finally improves the electrochemical performance of the electrode material. The specific capacity of the first discharge can reach 1314.2mAh/g, the specific capacity decay is only 20% after 100 times of circulation, and the lithium-sulfur battery catalytic material has wide application prospect.

Description

High-activity positive electrode material catalyst for lithium-sulfur battery and preparation method thereof
Technical Field
The invention belongs to the technical field of positive electrode materials of lithium-sulfur batteries, and relates to a high-activity positive electrode material catalyst for a lithium-sulfur battery and a preparation method thereof.
Background
With the rapid development of industrial production and science and technology, the demand of human beings on energy is increased, the energy and the environment are two most important problems in the 21 st century, 80% of energy supply in the current stage is from fossil fuel, greenhouse gases are discharged in the using process of traditional energy, the environment is greatly damaged by pollutants generated by the derivative of the greenhouse gases, and the environment is reduced by using renewable energy. Therefore, new energy development which can replace the traditional energy is becoming a trend. Among them, new energy sources such as wind energy, tidal energy, solar energy, etc. are difficult to meet the production demands of people due to their instability, and in order to meet the increasing demands for renewable energy storage systems, development of batteries having high energy density, long life and high safety has become a necessary trend.
The invention and steadily improving rechargeable Lithium Ion Batteries (LiBs) have brought promise to achieve a fossil fuel free society. However, due to the lithium intercalation electrochemical structure, the formation of lithium dendrites presents a serious safety hazard,the commercial development of the LiBs is basically stagnated, and with the increasing demand for large energy storage systems, the development of LiBs with high specific capacities seems to have reached a bottleneck. Wherein, the lithium sulfur battery taking sulfur as a positive electrode and a metal lithium sheet as a negative electrode has extremely high theoretical energy density (2600 Wh kg -1 ) Specific to theory (1672 mA h g) -1 ) Attention is paid to the lithium-sulfur battery, and the lithium-sulfur battery has the advantages of abundant natural reserve of elemental sulfur, low price, easy acquisition and environmental friendliness, and is expected to be a new generation secondary battery with the highest potential and large-scale application value. However, the current positive electrode side of the lithium sulfur battery still has the problems of low sulfur carrying capacity, low elemental sulfur conductivity, shuttle effect and the like, particularly, the shuttle effect causes a great deal of loss of active substances of the battery, so that the capacity is rapidly attenuated, the cycle life is not ideal, and the practical application of the lithium sulfur battery is restricted. Therefore, how to design and optimize the structure of the electrode, and effectively inhibit the shuttle effect while simplifying the operation, has important significance for the commercial application of the lithium-sulfur battery.
Disclosure of Invention
Aiming at the problems, the invention provides a high-activity cathode material catalyst for a lithium sulfur battery and a preparation method thereof, which take cyanamide compounds and organic metal molybdenum salts as raw materials or continuously add defective carbon materials, and the high-activity cathode material catalyst for the lithium sulfur battery can be obtained by directly carbonizing nitrogen-doped carbon conductive materials with uniformly distributed molybdenum metal clusters in a tube furnace under inert atmosphere through full physical mixing.
The technical scheme of the invention is as follows:
a high-activity positive electrode material catalyst for a lithium sulfur battery comprises a flaky nitrogen-doped carbon-based carrier and molybdenum metal nanoclusters uniformly embedded on the surface of the carrier, wherein the size of the molybdenum metal nanoclusters is 1-10nm, and the mass ratio of the molybdenum metal nanoclusters on the carrier is 10-20wt%.
The nitrogen-doped carbon-based carrier is a heat treatment product of organic molybdenum metal salt and cyanamide compound, or is a heat treatment product of organic molybdenum metal salt, cyanamide compound and a carbon-based carrier with defects, wherein the carbon-based carrier with defects is one or more of porous carbon, graphene oxide and carboxylated carbon nanotubes; the cyanamide compound is melamine, dicyandiamide (DCD), urea or thiourea.
The invention also provides a preparation method of the high-activity cathode material catalyst for the lithium-sulfur battery, which comprises the following steps:
(1) Mechanically mixing organic molybdenum metal salt and cyanamide compound uniformly, or continuously adding a carbon-based carrier with defects, and mechanically mixing uniformly; the mass ratio of the organic metal molybdenum salt to the cyanamide compound is 1:10-1:1000;
(2) And (3) heating the mixture obtained in the step (1) in an inert atmosphere for heat treatment to obtain the catalyst (the high-activity anode material catalyst for the lithium sulfur battery) with the nitrogen-doped carbon-based carrier and the uniform molybdenum metal nanoclusters inlaid on the surface of the carrier.
Further, the mechanical mixing is performed by ball milling or manual grinding.
Further, the mass ratio of the defective carbon-based carrier to the organic metal molybdenum salt is 1:5-1:50.
Further, the cyanamide compound is dicyandiamide.
Further, the organic metal molybdenum salt is molybdenum acetylacetonate.
Further, the mass ratio of the organic metal molybdenum salt to the cyanamide compound is 1:50-1:500.
Further, in the step (2), the mixture is heated in an inert atmosphere to perform a heat treatment process, wherein the heat treatment temperature in the first stage is 250-350 ℃, the heat treatment time is 1-4 hours, the heat treatment temperature in the second stage is 450-700 ℃, the heat treatment time is 1-4 hours, the heat treatment temperature in the third stage is 700-1000 ℃, and the heat treatment time is 0.5-3 hours.
Further, the mixture in the step (2) is heated in an inert atmosphere to perform a heat treatment process, wherein the heat treatment temperature in the first stage is 300-350 ℃, the heat treatment time is 2-3 hours, the heat treatment temperature in the second stage is 550-650 ℃, the heat treatment time is 3-4 hours, the heat treatment temperature in the third stage is 750-950 ℃, and the heat treatment time is 1-2 hours.
Further, the inert atmosphere is high-purity nitrogen.
Further, the size of the molybdenum metal clusters is precisely controlled according to the ratio of the organic molybdenum metal salt to dicyandiamide.
The invention also provides application of the catalyst in a high-activity positive electrode material for a lithium-sulfur battery.
The beneficial effects of the invention include:
the invention takes cyanamide compound and organic metal molybdenum salt as raw materials, or continuously adds carbon materials with defects, and the nitrogen doped conductive carbon materials with uniformly distributed molybdenum metal clusters can be obtained by fully and physically mixing and directly carbonizing in a tube furnace under inert atmosphere. The conductive carbon material prepared by the invention has a macroscopically abundant pore structure, a three-dimensional conductive network and a microscopic morphology similar to a graphene structure, has a higher specific surface area, is thinner in carbon layer, has a physical adsorption effect on polysulfide, and has a chemical adsorption and catalytic conversion effect on polysulfide by molybdenum metal nano particles (nanoclusters) inlaid on the surface of the carbon layer. The method is favorable for lithium ion and electron transfer, has physical adsorption and chemical catalysis effects on polysulfide formed in the charge-discharge process in the anode side of the lithium-sulfur battery, effectively captures polysulfide, inhibits the shuttle effect of polysulfide, improves the electrochemical stability, the multiplying power performance and the coulomb efficiency of the battery, and finally improves the electrochemical performance of the electrode material.
The material is applied to a lithium sulfur battery, effectively solves the problems of serious shuttle effect and the like in the lithium sulfur battery, improves the cycle stability and the rate capability of the battery, and shows excellent electrochemical performance. The material is used as the positive electrode of the lithium-sulfur battery, and after the material is circulated for 100 circles under the current density of 0.2C, the specific capacity is 1038.4mA h g -1 The capacity loss rate of each circle is 0.2%, and the coulomb efficiency is close to 100%; after the aluminum foil circulates for 100 circles under the current density of 0.2C, the specific capacity is only 399.2mA h g -1 . In the rate performance test, the specific capacity of the electrode loaded with the molybdenum metal nanocluster nitrogen-doped carbon material is maintained at 690.2mA h g under the current density of 2.0C -1 When the current density recoversWhen the temperature is returned to 0.2 ℃, the specific capacity can be kept at 1086.6mA h g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific capacity of the aluminum foil electrode is kept at 427.3mA h g under the current density of 2.0C -1 When the current density is recovered to 0.2C, the specific capacity can be kept at 605.7mA h g -1 The specific capacity drops faster.
Drawings
FIG. 1 is a scanning electron microscope image at a magnification of 4000 of the Mo/NC material prepared in example 1.
FIG. 2 is a scanning electron microscope image of the Mo/NC material prepared in example 1 at a magnification of 15000.
FIG. 3 is a transmission electron microscope image of the Mo/NC material prepared in example 1 at a magnification of 1.0M.
FIG. 4 is a transmission electron microscope image at a magnification of 1.2M of the Mo/NC material prepared in example 1.
Fig. 5 is a graph of the cycling performance of the example 1 assembled Mo/NC electrode lithium sulfur cell and the comparative cell at a current density of 0.2C.
Fig. 6 is a graph showing the rate performance of the lithium sulfur battery and the comparative battery in which the Mo/NC electrode is assembled in example 1.
FIG. 7 is a scanning electron microscope image of the Mo/NC material prepared in example 2.
Detailed Description
Specific experimental protocols of the present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples. Unless specified, the method is a conventional method, and all raw materials and instruments used can be purchased in the market.
Example 1
Respectively weighing 20g dicyandiamide and 0.2g molybdenum acetylacetonate in a reagent bottle according to the mass ratio (100:1), adding 200ml ethanol, mechanically stirring and dispersing, placing a centrifugal machine at 5000r/min for drying at 60 ℃ in a blast drying oven after particles are uniformly dispersed, ball milling for about 12 hours by using a ball mill, uniformly mixing the two precursors, placing the mixture in a tubular furnace, taking high-purity argon as inert shielding gas, heating to 300 ℃ from the initial temperature of 30 ℃ in the whole process at the heating rate of 2 ℃/min, carrying out heat treatment for 2 hours, then continuously heating to 600 ℃, continuously heating to 900 ℃ again, carrying out heat treatment for 3 hours, and cooling to room temperature in an inert atmosphere to obtain a nitrogen-doped conductive carbon material (a high-activity anode material catalyst for lithium sulfur batteries) with uniformly distributed molybdenum metal clusters, wherein the overall appearance of the carbon-loaded molybdenum metal nano-cluster catalyst can be seen by using a scanning electron microscope at the multiple of 4000 as shown in figures 1-4; FIG. 2 is a scanning electron microscope image of the Mo/NC material prepared in example 1 at a multiple of 15000, and can show that the material has a macroscopically abundant pore structure, a three-dimensional conductive network, a microstructure with a graphene-like structure and a higher specific surface area; fig. 3 and fig. 4 are transmission electron microscope diagrams of the Mo/NC material prepared in example 1 under ultra high power, and it can be clearly seen that the thin carbon layer surface having a graphene-like structure is inlaid with uniform molybdenum metal clusters, and the size of the metal clusters is about 1-3nm.
Mixing and grinding sublimed sulfur and Mo/NC conductive material according to the mass ratio of 3:1, placing the mixture into a reaction kettle, vacuumizing, transferring the reaction kettle into a muffle furnace, and carrying out heat preservation for 12h at the melting temperature of 155 ℃ and the heating rate of 5 ℃/min to obtain the Mo/NC@S composite material.
Mixing the prepared Mo/NC@S composite material with Super-P and polyvinylidene fluoride (PVDF) according to a mass ratio of 7:2:1, mixing, preparing slurry by taking N-methyl pyrrolidone (NMP) as a solvent, scraping and coating on aluminum foil, putting the scraped aluminum electrode slice into a vacuum drying oven for drying for 10 hours, and punching into a pole slice by using a punching machine. Assembling in a glove box filled with argon, wherein an electrode plate of the scraped slurry is used as a positive electrode, a lithium plate is used as a negative electrode, a Celgard2325 polypropylene film is used as a battery diaphragm, and 1M LiTFSI/DOL is DMC (1:1) +1%LiNO 3 The electrolyte is assembled into a button cell. The comparative cell was prepared by grinding sublimed sulfur with Super-P to a Super-P@S composite by mixing Super-P@S composite with polyvinylidene fluoride (PVDF) in a mass ratio of 9:1, preparing slurry after mixing, and assembling the same with the other processes into a button cell by using a glove box. After the battery is kept stand for 12 hours, the constant current charge-discharge cycle performance and the multiplying power performance are completed through a blue electric testing system, and the testing voltage window is 1.7-2.8V. The current densities of the rate performance tests were 0.2C,0.5C,1.0C,2.0C (1c=1675 mA h g -1 ). FIG. 5 shows a real objectExample 1 cycle performance graphs of assembled Mo/NC@S composite electrode and comparative battery at 0.2C current density after 100 cycles of Mo/NC@S composite electrode at 0.2C current density, specific capacity was 1038.4mA h g -1 The capacity loss rate of each circle is 0.20%, and the coulomb efficiency is close to 100%; after the aluminum foil electrode circulates for 100 circles under the current density of 0.2C, the specific capacity is only 399.2mA h g -1 The capacity loss per turn was 0.50% and the coulombic efficiency was very low. As shown in FIG. 6, in the rate performance test, the specific capacity of the Mo/NC@S composite material electrode is maintained at 690.2mA h g at a current density of 2.0C -1 When the current density is recovered to 0.2C, the specific capacity can be kept at 1086.6mA h g -1 The specific capacity of the aluminum foil electrode is kept at 427.3mA h g under the current density of 2.0C -1 When the current density is recovered to 0.2C, the specific capacity can be kept at 605.7mA h g -1 The specific capacity drops faster. From the above data, it can be seen that uniformly distributed molybdenum metal nanoclusters can significantly improve electrochemical stability, rate capability and coulombic efficiency of the battery.
Example 2
Weighing potassium citrate/sodium citrate (6.12 g of potassium citrate and 5.16g of sodium citrate) in a porcelain boat, putting the porcelain boat into an oven for drying for 1 hour, removing water in raw materials, putting the dried potassium citrate/sodium citrate in a tubular furnace, and pyrolyzing the dried potassium citrate/sodium citrate in an argon atmosphere at a heating rate of 5 ℃/min in the whole course at 800 ℃ for 1 hour. The inorganic impurities were removed with HCl solution (1M) and water (18.2 mΩ). After drying at 60 ℃, a porous carbon support with defects was obtained.
Respectively weighing 20g dicyandiamide and 0.2g molybdenum acetylacetonate in a reagent bottle in a mass ratio of 100:1, adding 200ml ethanol, mechanically stirring and dispersing, standing at 5000r/min by a centrifugal machine, drying at 60 ℃ by a blast drying oven, adding porous carbon with a mass ratio of 1:5 to the organic metal molybdenum salt, transferring to a ball milling tank together, ball milling for about 12 hours by using a ball mill to uniformly mix the two materials, placing in a tubular furnace, taking argon as inert protective gas, heating to 300 ℃ from an initial temperature of 30 ℃ for 2 hours at the whole process, continuing to heat-treat to 600 ℃ for 2 hours, then heating to 900 ℃ again, cooling to room temperature under an inert atmosphere, and obtaining the Mo/NC of the nitrogen doped conductive carbon material (the high-activity positive electrode material catalyst for the lithium sulfur battery) with uniformly distributed molybdenum metal clusters, as shown in figure 7.

Claims (8)

1. A high-activity positive electrode material catalyst for a lithium sulfur battery is characterized in that: comprises a flaky nitrogen-doped carbon-based carrier and molybdenum metal nanoclusters uniformly embedded on the surface of the carrier, wherein the size of the molybdenum metal nanoclusters is 1-10nm, and the mass ratio of the molybdenum metal nanoclusters on the carrier is 10-20wt%.
2. The high-activity positive electrode material catalyst for lithium-sulfur batteries according to claim 1, wherein: the nitrogen-doped carbon-based carrier is a heat treatment product of an organic molybdenum metal salt and a cyanamide compound, or is a heat treatment product of an organic molybdenum metal salt, a cyanamide compound and a carbon-based carrier with defects; the defective carbon-based carrier is one or more of porous carbon, graphene oxide and carboxylated carbon nanotubes; the cyanamide compound is melamine, dicyandiamide, urea or thiourea.
3. A method for preparing the high-activity cathode material catalyst for the lithium-sulfur battery as claimed in claim 1, which is characterized by comprising the following steps:
(1) Mechanically mixing organic molybdenum metal salt and cyanamide compound uniformly, or continuously adding a carbon-based carrier with defects, and mechanically mixing uniformly; the mass ratio of the organic metal molybdenum salt to the cyanamide compound is 1:10-1:1000;
(2) And (3) heating the mixture obtained in the step (1) in an inert atmosphere for heat treatment, and obtaining the high-activity positive electrode material catalyst for the lithium-sulfur battery.
4. The method for preparing a high-activity positive electrode material catalyst for lithium-sulfur batteries according to claim 3, wherein said organometallic molybdenum salt is molybdenum acetylacetonate.
5. The method for preparing the high-activity positive electrode material catalyst for lithium-sulfur batteries according to claim 3, wherein: the mass ratio of the organic metal molybdenum salt to the cyanamide compound is 1:50-1:500.
6. The method for preparing a high-activity positive electrode material catalyst for lithium-sulfur batteries according to claim 3, wherein the mass ratio of the defective carbon-based carrier to the organometallic molybdenum salt is 1:5 to 1:50.
7. The method for preparing the high-activity positive electrode material catalyst for lithium-sulfur batteries according to claim 3, wherein: in the step (2), the mixture is heated in an inert atmosphere to perform a heat treatment process, wherein the heat treatment temperature of the first stage is 250-350 ℃, the heat treatment time is 1-4 hours, the heat treatment temperature of the second stage is 450-700 ℃, the heat treatment time is 1-4 hours, the heat treatment temperature of the third stage is 700-1000 ℃, and the heat treatment time is 0.5-3 hours.
8. Use of the catalyst of claim 1 or 2 in a high activity cathode material for lithium sulfur batteries.
CN202310577015.3A 2023-05-22 2023-05-22 High-activity positive electrode material catalyst for lithium-sulfur battery and preparation method thereof Pending CN116764660A (en)

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