CN111864156A - Preparation method of metal nitride-metal oxide heterojunction modified diaphragm for lithium-sulfur battery and lithium-sulfur battery comprising diaphragm - Google Patents
Preparation method of metal nitride-metal oxide heterojunction modified diaphragm for lithium-sulfur battery and lithium-sulfur battery comprising diaphragm Download PDFInfo
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Abstract
The invention discloses a preparation method of a metal nitride-metal oxide heterojunction modified diaphragm for a lithium-sulfur battery and the lithium-sulfur battery comprising the diaphragm, and belongs to the technical field of lithium-sulfur batteries. The metal nitrogen oxide heterojunction disclosed by the invention is composed of symbiotic strong-adsorbability phase niobium oxide-strong-conductivity phase niobium nitride, and the metal nitride-metal oxide heterojunction modified diaphragm can improve the function of the diaphragm in regenerating sulfur-containing components and realize the capture of polysulfide and electrochemical catalytic conversion. The lithium-sulfur battery disclosed by the invention comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, and the diaphragm is modified by using a metal nitride-metal oxide heterojunction, so that the lithium-sulfur battery has good dynamic performance and electrochemical performance, and particularly the cycle performance and the rate performance of the lithium-sulfur battery are greatly improved.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method of a metal nitride-metal oxide heterojunction modified diaphragm for a lithium-sulfur battery and the lithium-sulfur battery comprising the diaphragm.
Background
With the development of economic society, the trend of depletion of conventional energy sources has become a recognized fact, and the active search for the next generation of green high energy density secondary batteries has been imminent. Has high theoretical specific capacity (1675 mAh g-1) And theoretical energy density (2600 Wh Kg-1) The lithium sulfur battery is considered to be one of the most promising next-generation energy storage systems, and is a hot spot in the current electrochemical research field.
However, the reaction system of the lithium-sulfur battery is very complex, and the lithium polysulfide intermediate product is dissolved in the electrolyte during the charging and discharging process, which can cause the loss of the active material of the positive electrode, leading to the attenuation of the battery capacity, and simultaneously, the polysulfide can generate redox reaction with the metal lithium after reaching the negative electrode, forming the shuttle effect, and reducing the coulomb efficiency of the system. Furthermore, in the case of high sulfur loading, the above problem is more serious. Furthermore, as far as the type of reaction is concerned, the reaction of sulphur with lithium is a dissolution-deposition reaction, the kinetics of the transition between soluble polysulphides and insoluble lithium sulphides are slow, and sulphur and its discharge products (Li)2S2And Li2S) has poor conductivity, which affects the improvement of rate capability. Therefore, how to effectively inhibit the shuttle effect of polysulfide and improve reaction kinetics is a key problem for improving the utilization rate of positive electrode sulfur, improving the electrochemical performance of the positive electrode sulfur and realizing the commercial application of lithium-sulfur batteries.
One effective strategy is to introduce a polar substance with catalytic activity into the positive electrode material or the positive electrode side of the separator, and to fix polysulfide by chemical bonding, thereby improving reaction kinetics. By modifying the positive side of the diaphragm and introducing substances with chemical adsorption and catalytic conversion characteristics into the functional layer of the diaphragm, the transmembrane diffusion of polysulfide can be inhibited, the shuttle effect is prevented, and the coulomb efficiency of the lithium-sulfur battery is improved. The current commercial polyethylene or polypropylene membrane has relatively high porosity and large micropore diameter in order to ensure higher lithium ion conductivity, and the diameter of polysulfide ions is less than 1nm, so the traditional membrane basically has no barrier effect on the polysulfide ions and cannot block polysulfide dissolution and shuttling phenomena. Through a precisely controlled membrane pore structure, such as a polymer membrane (with a pore channel of 0.8 nm) for constructing an intrinsic microporous structure, the barrier capacity to polysulfide is improved by more than 500 times compared with that of a common Celgard diaphragm, and the selective permeation function of lithium ions can be more effectively realized (NanoLett. 2015, 15, 5724).
Transition metal compounds of strong polarity and polysulfides can efficiently fix polysulfides by forming chemical bonds, even some compounds such as having the ability to catalytically convert polysulfides. The substance is modified on the diaphragm, so that the stability and rate capability of the lithium-sulfur battery can be greatly improved. For example, in the Chinese invention patent CN106848161A, the graphene-sulfide heterojunction material is coated on the diaphragm, and the physical barrier polysulfide effect of the graphene and the adsorption effect of the sulfide on the polysulfide are combined, so that the shuttle effect of the polysulfide is greatly inhibited. For another example, chinese patent CN106848319A combines a heterojunction nano material with sulfur as a positive electrode active material layer, and the heterojunction has both strong adsorption to polysulfide and capability of converting polysulfide, thereby improving electrochemical and kinetic properties of the lithium-sulfur battery.
The symbiotic heterojunction material consisting of the oxide with high adsorbability and the nitride with high conductivity can play a synergistic role, and the high-efficiency fixed diffusion and conversion of polysulfide can be realized by modifying the material on the diaphragm through a simple preparation process and a diaphragm coating process, so that the performance of the lithium-sulfur battery is improved. In view of the above, the following technical solutions of the present invention are proposed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a metal nitride-metal oxide modified diaphragm for a lithium-sulfur battery, wherein a heterojunction material is composed of symbiotic strong-adsorption phase niobium oxide-strong-conductivity phase niobium nitride, and the metal nitride-metal oxide modified diaphragm can improve the function of the diaphragm in regenerating sulfur-containing components and realize the capture of polysulfide and electrochemical catalytic conversion.
The invention solves another technical problem by providing a lithium-sulfur battery comprising the diaphragm, which comprises a positive electrode, a negative electrode, electrolyte and the diaphragm, wherein the lithium-sulfur battery has good dynamic performance and electrochemical performance, particularly the cycle performance and the rate capability of the lithium-sulfur battery are greatly improved due to the fact that the diaphragm is modified by using a metal oxynitride heterojunction.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the metal nitride-metal oxide modified diaphragm for the lithium-sulfur battery is characterized by comprising the following specific steps:
step S1: dispersing citric acid, niobium pentachloride and urea in ethanol, heating at 60 ℃ and fully stirring until sol is formed, then placing the sol in a blast drying oven to dry at 100 ℃ for 12-24h, then taking out the sol in a corundum boat, placing the corundum boat in an atmosphere furnace, heating to 800 ℃ and 1000 ℃ under inert atmosphere, preserving heat for 1-4h, and naturally cooling to obtain a heterojunction material, wherein the heterojunction material consists of symbiotic strong-adsorbability phase niobium oxide-strong-conductivity phase niobium nitride;
step S2: and (3) preparing the metal nitrogen oxide heterojunction modified diaphragm, namely dispersing the heterojunction modified diaphragm obtained in the step (S1), the conductive material and the binder in an organic solvent according to the mass ratio of 8:1:1, stirring for 2 hours, then performing vacuum filtration on the diaphragm, and keeping the surface loading of inorganic particles on the diaphragm to be 0.1-0.3mg/cm2And then vacuum drying for 12h at 60 ℃ to obtain the heterojunction modified diaphragm.
The preparation method of the metal nitrogen oxide modified diaphragm of the lithium-sulfur battery adopts a suction filtration method, and the diaphragm modification function layer introduces a niobium compound with chemical adsorption and catalytic conversion characteristics into the diaphragm function layer, so that the function of the diaphragm for regenerating sulfur-containing components can be improved, and capture of polysulfide and electrochemical catalytic conversion are realized. Verification experiments also prove that the heterojunction material can effectively catalyze soluble polysulfide to solid-phase Li 2Electrochemical conversion of S, effective suppressionMigration of polysulfide in electrolyte is made, so that the function of effectively fixing sulfur is achieved, and the cycle stability of the lithium-sulfur battery is improved.
Preferably, in step S1, the feeding molar ratio of the citric acid to the niobium pentachloride is 0.5:1-3:1, and the feeding molar ratio of the niobium pentachloride to the urea is 1:6-1: 12.
Preferably, the temperature-rising sintering temperature of the atmosphere furnace in the step S1 is 900 ℃, and the temperature-rising rate is 1-5 ℃/min.
Preferably, the separator in step S2 is a glass fiber, a polyethylene film, a polypropylene film, or a polyethylene/polypropylene composite film.
Preferably, the organic solvent in step S2 is any one of ethanol, ethylene glycol, NMP, DMF, or acetone.
Preferably, the conductive material in step S2 is carbon nanotubes; the binder is any one of polyvinylidene fluoride, sodium alginate or carboxymethyl cellulose.
The lithium-sulfur battery comprising the diaphragm comprises a positive electrode, a negative electrode, electrolyte and the diaphragm, wherein the diaphragm is modified by adopting the heterojunction prepared by the method.
Preferably, the negative electrode is metal lithium, the electrolyte is a solution of lithium bis (trifluoromethanesulfonyl) imide LiTFSI with the concentration of 1mol/L, the solvent is a mixed solvent prepared by dioxolan DOL and glyme DME according to the volume ratio of 1:2, and the diaphragm is a heterojunction modified polyethylene/polypropylene composite membrane or a heterojunction modified polyethylene porous membrane.
The heterojunction modified diaphragm prepared by the invention is used for the lithium-sulfur battery, under the same condition, the lithium-sulfur battery prepared by the heterojunction modified diaphragm prepared by the invention has better cycling stability than the lithium-sulfur battery prepared by the traditional unmodified diaphragm, and the method has the advantages of simple and convenient operation and lower cost, is suitable for large-scale production, and has important significance for the large-scale production of the lithium-sulfur battery.
Drawings
FIG. 1 is an XRD pattern of a heterojunction material obtained in example 1 and example 2;
FIG. 2 is an optical photograph of the heterojunction modified membrane of example 1;
FIG. 3 is a sectional view and an elemental distribution diagram of the heterojunction modified membrane of example 1;
fig. 4 is a CV graph of an assembled lithium sulfur battery in example 1;
FIG. 5 is a 0.2C cycle plot of assembled lithium sulfur batteries of example 1, example 2, and comparative example;
FIG. 6 is a graph of the cycle at 2C for assembled lithium sulfur batteries of example 1, example 2, and comparative example;
FIG. 7 is a graph of rate performance of assembled lithium sulfur batteries of example 1, example 2, and comparative example;
fig. 8 is a graph of the charge and discharge of the assembled lithium sulfur battery of example 1 at different rates.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
The preparation method of the heterojunction material of the embodiment comprises the following steps: weighing citric acid, niobium pentachloride and urea according to a molar ratio of 0.5:1:10, dispersing the citric acid, niobium pentachloride and urea in 30mL of ethanol, heating at 60 ℃, fully stirring until sol is formed, then putting the mixture into a forced air drying oven, drying for 18h at 100 ℃, then putting a certain amount of dried material into a corundum boat, putting the corundum boat into an atmosphere furnace, heating to 900 ℃ at a heating rate of 3 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and naturally cooling to obtain the heterojunction material. The XRD pattern is shown in figure 1, and has characteristic peaks of niobium oxide and niobium nitride.
The preparation method of the heterojunction modified membrane comprises the following steps: dispersing the obtained heterojunction material, the carbon nano tube and the PVDF in ethanol according to the mass ratio of 8:1:1, stirring for 2 hours, coating the mixture on a polyethylene/polypropylene composite film by using a scraper, and keeping the surface loading of inorganic particles on the polyethylene/polypropylene composite film to be 0.15mg/cm2And vacuum drying at 60 ℃ for 12h to obtain the heterojunction modified diaphragm. FIG. 2 shows light of a heterojunction-modified membraneAnd (5) learning photos. Fig. 3 is a scanning electron micrograph (left) and an elemental distribution (right) of a cross section of the heterojunction-modified membrane.
The lithium-sulfur battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, wherein the negative electrode is metal lithium, the electrolyte is a solution of bis (trifluoromethanesulfonyl) imide lithium LiTFSI with the concentration of 1mol/L, the solvent is a mixed solvent prepared from dioxolane DOL and ethylene glycol dimethyl ether DME according to the volume ratio of 1:2, and the diaphragm is a heterojunction modified polyethylene/polypropylene composite membrane.
The preparation method of the positive electrode of the lithium-sulfur battery of the embodiment comprises the following steps: mixing and grinding sublimed sulfur and mesoporous carbon according to the mass ratio of 3:1 for 1h, preserving heat at 155 ℃ for 10h under the nitrogen atmosphere, and cooling to obtain the mesoporous carbon/sulfur composite material (the sulfur mass fraction is 70 wt%). The composite material, SP and PVDF are added into N-methyl-2-pyrrolidone (NMP) according to the mass ratio of 7:2:1 and ground for 1h to obtain dispersion slurry.
Electrochemical tests were performed on the button cells prepared in this example using a simulated cell, and the assembly of the cell was performed in an environment where the water and oxygen partial pressures were all below 0.1 ppm: assembling the anode, the cathode, the diaphragm, the electrolyte and the shell in a glove box according to the method in the prior art to prepare the button cell, and standing for 2 hours to obtain the battery.
The comparative analysis was carried out using a lithium-sulfur button cell assembled with an unmodified polyethylene/polypropylene composite membrane as a comparative example.
And (3) carrying out electrochemical performance test on the battery by using a land test system (Wuhanland electronics, Inc.), wherein the voltage range is 1.8-3.0V. When the charge-discharge current density is 0.2C (1C =1675 mAh), the first discharge specific capacity of the battery reaches 1197.3mAh/g, and the specific capacity can be kept at 624.1mAh/g after 250 cycles; the first discharge specific capacity of the comparative example was 230.5mAh/g, and the specific capacity after 250 cycles was 186.1mAh/g (FIG. 5). When the charge-discharge current density is 2C, the specific capacity is 499.6mAh/g after 450 cycles (figure 6). As can be seen from fig. 7, the rate performance of example 1 is much higher than that of the comparative example.
Example 2
The preparation method of the heterojunction material of the embodiment comprises the following steps: weighing citric acid, niobium pentachloride and urea according to a molar ratio of 2:1:12, dispersing the citric acid, niobium pentachloride and urea in 30mL of ethanol, heating at 60 ℃, fully stirring until a sol is formed, then putting the sol in a forced air drying oven, drying at 100 ℃ for 18h, then putting a certain amount of dried material in a corundum boat, putting the corundum boat in an atmosphere furnace, heating to 900 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, and naturally cooling to obtain the heterojunction material. The XRD pattern is shown in figure 1, and has characteristic peaks of niobium oxide and niobium nitride. It can be seen from the figure that the heterojunction materials prepared in example 2 and example 1 have different peak intensity ratios of niobium oxide/niobium nitride, that is, the heterojunction with different ratios of oxide and nitride can be obtained by changing the ratio of citric acid, niobium pentachloride and urea.
The preparation method of the heterojunction modified membrane comprises the following steps: dispersing the obtained heterojunction material, the carbon nano tube and sodium alginate in ethanol according to the mass ratio of 8:1:1, stirring for 2h, vacuum filtering on the polyethylene porous membrane, and keeping the surface loading of inorganic particles on the polyethylene porous membrane at 0.25mg/cm 2And then drying the membrane in a 60 ℃ blast drying oven for 2h, and transferring the membrane to a 60 ℃ vacuum drying oven overnight to obtain the heterojunction modified membrane.
The lithium-sulfur battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, wherein the negative electrode is metal lithium, the electrolyte is a solution of bis (trifluoromethanesulfonyl) imide lithium LiTFSI with the concentration of 1mol/L, the solvent is a mixed solvent prepared from dioxolan DOL and ethylene glycol dimethyl ether DME according to the volume ratio of 1:2, and the diaphragm is a heterojunction modified polyethylene porous membrane.
The preparation method of the positive electrode of the lithium-sulfur battery of the embodiment comprises the following steps: mixing and grinding sublimed sulfur and mesoporous carbon according to the mass ratio of 3:1 for 1h, preserving heat at 155 ℃ for 10h under the nitrogen atmosphere, cooling to obtain a mesoporous carbon/sulfur composite material (the mass fraction of sulfur is 70 wt%), adding the composite material, SP and PVDF into N-methyl-2-pyrrolidone (NMP) according to the mass ratio of 7:2:1, and grinding for 1h to obtain dispersion slurry.
Fig. 4 is a CV curve of the lithium-sulfur battery having the composition of example 1. The electrochemical performance of the battery is tested by using a land test system (Wuhanland electronics, Inc.), and the voltage range is 1.8-3.0V. When the charge and discharge current density is 0.2C (1C =1675 mAh), the first discharge specific capacity of the battery reaches 1220.1mAh/g, the specific capacity can be kept at 782.9mAh/g after 250 cycles, the first discharge specific capacity of the comparative example is 230.5mAh/g, and the specific capacity of the comparative example is 186.1mAh/g after 250 cycles (figure 5). When the charge-discharge current density is 2C, the specific capacity is 579.2mAh/g after 450 cycles (figure 6). As can be seen from fig. 7, the rate performance of the example is much higher than that of the comparative example. Fig. 8 is a charge-discharge curve diagram of the lithium-sulfur battery under different multiplying powers, which shows that the lithium-sulfur battery has higher specific discharge capacity under different current densities.
As can be seen from fig. 4 to 8, the lithium-sulfur battery obtained by the technical scheme of the present invention has greatly improved specific capacity and cycle stability, which indicates that the heterojunction modified membrane of the present invention can effectively promote the adsorption and conversion of polysulfides, thereby improving the cycle stability of the lithium-sulfur battery, and having important significance for realizing the industrial production of the lithium-sulfur battery.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (8)
1. The preparation method of the metal nitride-metal oxide heterojunction modified diaphragm for the lithium-sulfur battery is characterized by comprising the following specific steps of:
step S1: dispersing citric acid, niobium pentachloride and urea in ethanol, heating at 60 ℃ and fully stirring until sol is formed, then placing the sol in a blast drying oven to dry at 100 ℃ for 12-24h, then taking out the sol in a corundum boat, placing the corundum boat in an atmosphere furnace, heating to 800 ℃ and 1000 ℃ under inert atmosphere, preserving heat for 1-4h, and naturally cooling to obtain a heterojunction material, wherein the heterojunction material consists of symbiotic strong-adsorbability phase niobium oxide-strong-conductivity phase niobium nitride;
Step S2: and (3) preparing the metal nitride-metal oxide heterojunction modified diaphragm, namely dispersing the heterojunction modified diaphragm obtained in the step (S1), the conductive material and the binder in an organic solvent according to the mass ratio of 8:1:1, stirring for 2 hours, then performing vacuum filtration on the diaphragm, and keeping the surface loading of inorganic particles on the diaphragm to be 0.1-0.3mg/cm2And then vacuum drying for 12h at 60 ℃ to obtain the heterojunction modified diaphragm.
2. The method of preparing a metal nitride-metal oxide heterojunction modified separator for a lithium-sulfur battery according to claim 1, wherein: in the step S1, the feeding molar ratio of the citric acid to the niobium pentachloride is 0.5:1-3:1, and the feeding molar ratio of the niobium pentachloride to the urea is 1:6-1: 12.
3. The method of preparing a metal nitride-metal oxide heterojunction modified separator for a lithium-sulfur battery according to claim 1, wherein: in step S1, the temperature of the atmosphere furnace is increased to 900 ℃, and the temperature increase rate is 1-5 ℃/min.
4. The method of preparing a metal nitride-metal oxide heterojunction modified separator for a lithium-sulfur battery according to claim 1, wherein: in the step S2, the diaphragm is a glass fiber, a polyethylene film, a polypropylene film or a polyethylene/polypropylene composite film.
5. The method of preparing a metal nitride-metal oxide heterojunction modified separator for a lithium-sulfur battery according to claim 1, wherein: in step S2, the organic solvent is any one of ethanol, ethylene glycol, NMP, DMF, or acetone.
6. The method of preparing a metal nitride-metal oxide heterojunction modified separator for a lithium-sulfur battery according to claim 1, wherein: in step S2, the conductive material is a carbon nanotube; the binder is any one of polyvinylidene fluoride, sodium alginate or carboxymethyl cellulose.
7. A lithium-sulfur battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, characterized in that: the diaphragm is modified by the metal nitride-metal oxide heterojunction prepared by the method of any one of claims 1 to 6.
8. The lithium sulfur battery of claim 7, wherein: the negative electrode is metal lithium, the electrolyte is a solution of bis (trifluoromethanesulfonyl) imide lithium LiTFSI with the concentration of 1mol/L, the solvent is a mixed solvent prepared from dioxolan DOL and glycol dimethyl ether DME according to the volume ratio of 1:2, and the diaphragm is a heterojunction modified polyethylene/polypropylene composite membrane or a heterojunction modified polyethylene porous membrane.
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| CN115377605A (en) * | 2022-08-22 | 2022-11-22 | 成都大学 | Hollow metal oxide-metal phosphide heterojunction material and preparation method and application thereof |
| CN115377605B (en) * | 2022-08-22 | 2023-07-21 | 成都大学 | Hollow metal oxide-metal phosphide heterojunction material and preparation method and application thereof |
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