CN114649635A - Preparation method and application of bimetal nitride multifunctional diaphragm - Google Patents

Preparation method and application of bimetal nitride multifunctional diaphragm Download PDF

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CN114649635A
CN114649635A CN202210242620.0A CN202210242620A CN114649635A CN 114649635 A CN114649635 A CN 114649635A CN 202210242620 A CN202210242620 A CN 202210242620A CN 114649635 A CN114649635 A CN 114649635A
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diaphragm
lithium
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李国春
蒋湘丽
张姗
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Jiangsu University
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Abstract

The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method and application of a bimetal nitride multifunctional diaphragm. Firstly, preparing a bimetal oxide, then calcining in an atmosphere of introducing ammonia gas and argon gas to obtain a bimetal nitride, adding the bimetal nitride, a conductive agent and a binder into an organic solvent to obtain a slurry, and coating the slurry on one surface of a PE or PP diaphragm to obtain the multifunctional bimetal nitride diaphragm; in addition, mixing the S/C composite material and the binder in a solvent to prepare slurry, coating the slurry on the surface of the carbon-coated aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery, and taking the positive pole piece as a positive pole; a multifunctional diaphragm is used as a diaphragm, and a metal lithium sheet is used as a negative electrode; and assembling the positive electrode, the electrolyte, the functional diaphragm, the electrolyte and the negative electrode in sequence under an argon atmosphere to obtain the lithium-sulfur battery. The metal nitride enhances the adsorption effect on polysulfide, improves the reaction kinetics of catalytic conversion of polysulfide, and generates excellent electrochemical performance.

Description

Preparation method and application of bimetal nitride multifunctional diaphragm
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method and application of a bimetal nitride multifunctional diaphragm.
Background
With the continuous development of electronic products and electric vehicles, the traditional lithium ion battery can not meet the demand of the market for high specific energy storage devices. Currently, lithium sulfur batteries are high in theoretical energy density (2600Wh kg)-1) High theoretical specific capacity (1675mAh g-1) Low cost and is receiving wide attention. However, complicated internal side reactions hinder practical application of lithium sulfur batteries.
Generally, lithium sulfur batteries have low electrical conductivity of charge and discharge products (sulfur and lithium sulfide) during cycling, resulting in low redox reaction kinetics; the long-chain lithium polysulfide dissolved in the electrolyte shuttles between the positive electrode and the negative electrode of the lithium-sulfur battery, so that the utilization rate of the active material sulfur is reduced, and the capacity is rapidly attenuated; in addition, the non-uniform distribution of long chain lithium polysulfides as they are converted to lithium sulfide during discharge can cause aggregation and volume expansion of the lithium sulfide, which further affects the cycle life and capacity of the battery. Currently, researchers have designed the cathode material, intermediate layer and functional separator to controllably modulate the redox kinetics and physicochemical adsorption of lithium polysulfide to prevent its shuttling effect and to promote its conversion. Among them, the polyethylene separator or polypropylene separator used in lithium sulfur batteries has a large pore size, and polypropylene and polyethylene do not have an adsorption effect on soluble polysulfides and need to be modified, so that it is of great significance to find a multifunctional separator capable of effectively promoting polysulfide conversion.
According to the current research, the dynamic behavior of the lithium polysulfide intermediate can be improved by adjusting and doping modification of various substances such as metal atoms, metal oxides, metal carbides, metal nitrides, metal sulfides, metal phosphides, organic substances and the like. However, it is difficult for a single material to simultaneously achieve an effective synergistic interface of strong adsorption, high conductivity, and high reactive sites, and thus the nucleation and growth regulation effects of lithium sulfide are weak. Therefore, studies have been made to achieve a synergistic effect of adsorption-catalysis, which can not only increase adsorption sites for lithium polysulfide and the conversion kinetics of lithium polysulfide, but also promote uniform nucleation and rapid growth of lithium sulfide.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method and application of a bimetal nitride multifunctional diaphragm; in the invention, the coupling between the metal bonds can generate adsorption sites with lithium polysulfide, so that the redox kinetics of the lithium polysulfide can be adjusted. In addition, the high-catalytic-performance bimetallic nitride in the functional diaphragm of the lithium-sulfur battery can promote the conversion of long-chain lithium polysulfide to short-chain lithium polysulfide, promote the uniform nucleation and growth of lithium sulfide, inhibit the agglomeration of the lithium sulfide and improve the utilization rate of sulfur; therefore, the lithium-sulfur battery assembled based on the bi-metal nitride multifunctional separator exhibits high rate performance, high specific capacity and long cycle stability.
The technical scheme provided by the invention is as follows: a bimetal nitride is applied to a multifunctional diaphragm of a lithium-sulfur battery; the multifunctional diaphragm is formed by uniformly coating bimetal nitride on one surface of a polyethylene or polypropylene (PE/PP) diaphragm; the bimetal nitride is of a nanorod structure with uniformly distributed metal elements and is uniform in size.
The invention firstly provides a preparation method of a bimetal nitride multifunctional diaphragm, which comprises the following steps:
(1) preparing a bimetallic oxide by a hydrothermal synthesis method and a thermal annealing method: firstly, respectively dissolving A, B two metal salts in deionized water, stirring and dissolving to obtain A, B two solutions, mixing the two solutions, and stirring for a period of time to obtain an AB mixed solution; then transferring the mixture into a high-pressure reaction kettle for heating reaction; cooling, washing and drying the suspension obtained after the reaction to obtain solid powder; then calcining the solid powder to obtain a bimetallic oxide;
(2) preparing a bimetal nitride and a lithium-sulfur battery multifunctional diaphragm:
calcining the bimetallic oxide prepared in the step (1) in an atmosphere of introducing ammonia gas and argon gas, and calcining to obtain bimetallic nitride;
then adding the bimetal nitride, the conductive agent and the binder into an organic solvent, fully stirring the mixture into uniform slurry, and coating the slurry on one surface of a polyethylene or polypropylene (PE/PP) diaphragm to obtain the bimetal nitride multifunctional diaphragm; the average content of the bimetal nitride in the bimetal nitride multifunctional diaphragm on each diaphragm is 0.8-1.2 mg/cm2。
Preferably, the A, B two metal salts in step (1) include any two of cobalt chloride hexahydrate, sodium molybdate dihydrate, ammonium metavanadate and ferric chloride hexahydrate, and the ratio of the A metal salt to deionized water is 2 mmol: 120 ml; the dosage ratio of the metal salt B to the deionized water is 2-4 mmol: 120 ml; the molar ratio of the two metal salts in the AB mixed solution is 1: 1-3.
Preferably, the stirring in the step (1) is carried out for a period of time of 30-60 min; the heating reaction is carried out at the temperature of 180-200 ℃ for 12-24 hours; the calcination operation is as follows: heating to 400-600 ℃ at a heating rate of 2-5 ℃/min in an air atmosphere, and preserving heat for 3-4 h.
Preferably, the calcining temperature in the step (2) is 600-800 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1.5-2.5 h; the flow ratio of the ammonia gas to the argon gas is 1: 2-3.
Preferably, the mass ratio of the bimetallic nitride to the conductive agent to the binder in the step (2) is 8:1: 1; the conductive agent in the slurry is any one of Super P, Keqin carbon black or acetylene black; the binder is polyvinylidene fluoride (PVDF), and the organic solvent is N-methylpyrrolidone (NMP); the thickness of the bimetal nitride multifunctional diaphragm is 10-30 mu m.
The invention also provides the application of the multifunctional diaphragm based on the bimetal nitride in assembling the lithium-sulfur battery as the diaphragm in the lithium-sulfur battery, which comprises the following steps:
(1) preparing a positive electrode material: using a fusion processHeating the electric agent and the sulfur powder to a certain temperature, and preserving the temperature for a period of time to obtain an S/C composite material; then mixing the S/C composite material and the binder in a solvent to prepare slurry; finally, coating the slurry on the surface of the carbon-coated aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery; the loading capacity of the active substance sulfur on the surface of the coated positive pole piece of the lithium-sulfur battery is 1.2-4 mg/cm2(ii) a The solvent is N-methylpyrrolidone (NMP) or water;
(2) assembling the lithium-sulfur battery:
taking the positive pole piece of the lithium-sulfur battery prepared in the step (1) as a positive pole; taking a bimetal nitride multifunctional diaphragm as a functional diaphragm and a metal lithium sheet as a negative electrode; and assembling the positive electrode, the electrolyte, the functional diaphragm, the electrolyte and the negative electrode in sequence under an argon atmosphere to obtain the lithium-sulfur battery.
Preferably, the mass ratio of the conductive agent to the sulfur powder in the step (1) is 1: 1-9; and heating to a certain temperature of 155-300 ℃, and keeping the temperature for a period of 12-24 hours.
Preferably, the conductive agent in the step (1) is any one of Super P, acetylene black, ketjen black, carbon nanotube or graphene; the binder is polyvinylidene fluoride (PVDF) or LA132, the dosage ratio of the binder to the solvent in the slurry is 25mg:1ml, and the mass ratio of the S/C composite material to the binder is 9: 1.
Preferably, the electrolyte in the step (2) is a mixed solution of 1, 2-dimethoxyethane and 1, 3-dioxacycloalkane in a volume ratio of 1:1, and the mixed solution contains a bis (trifluoromethane) sulfonimide salt with a final concentration of 1.0M and 2 wt.% lithium nitrate; the addition amount of the electrolyte is 20-40 mu L.
The invention has the beneficial effects that:
(1) the invention develops a synthesis strategy of a large-scale controllable prepared bimetal nitride coating multifunctional diaphragm, and the transition metal used in the invention has affinity and catalytic capability, which means that the nitrided bimetal can be uniformly distributed on the surface of a nanorod, thereby avoiding agglomeration;
(2) the invention constructs the strong coupling heterogeneous interface of the bimetal nitride, the strong coupling interaction between the bimetal nitride can enhance the chemical affinity with the lithium polysulfide, and provides more active sites for the good adsorption of the lithium polysulfide, so as to improve the defect that the PP or PE diaphragm can not adsorb the lithium polysulfide, thereby effectively inhibiting the shuttle effect of the polysulfide. The material has simple preparation method and low cost, and can improve the adsorption active sites through the strong coupling effect even if the material is not doped with the high-conductivity functionalized carbon material, thereby obviously improving the utilization rate of sulfur;
(3) according to the invention, after the bimetallic oxide is nitrided, the problem of poor conductivity is solved, and meanwhile, the interaction of M (Co, V, Fe, Mo) -N bonds can improve the transmission rate of electrons and ions, and has a strong catalytic action on the conversion-adsorption of lithium polysulfide, so that the rapid conversion of the lithium polysulfide and the uniform nucleation of lithium sulfide are realized, the reaction kinetics of polysulfide catalytic conversion is improved, and excellent electrochemical performance is obtained.
Drawings
FIG. 1 is a scanning electron microscope photograph of cobalt nitride-molybdenum nitride prepared in step (2) of example 1.
Fig. 2 is a transmission electron microscope photograph of the cobalt nitride-molybdenum nitride prepared in step (2) of example 1.
FIG. 3 is an X-ray diffraction pattern of cobalt nitride-molybdenum nitride prepared in step (2) of example 1.
FIG. 4 is a graph of long cycle performance at 0.2C based on different separator applications in a lithium sulfur battery; wherein CoN-Mo2N/PP is a long cycle performance curve of the cobalt nitride-molybdenum nitride multifunctional diaphragm prepared in the step one (2) in the example 1 at 0.2 ℃ when the diaphragm is applied to a lithium-sulfur battery; wherein CoMoO4the/PP is a long-cycle performance curve of the cobalt molybdate multifunctional diaphragm prepared in the step one (2) in the comparative example 1 at 0.2 ℃ in a lithium-sulfur battery; where PP is the long cycle performance curve at 0.2C for the polypropylene separator of comparative example 2 applied in a lithium sulfur battery.
FIG. 5 is a graph of rate performance at different current densities for different separator applications in a lithium sulfur battery; wherein CoN-Mo2N/PP is the application of the cobalt nitride-molybdenum nitride multifunctional diaphragm prepared in the step (2) in the embodiment 1 toRate performance curves at different current densities in lithium sulfur batteries; wherein CoMoO4the/PP is a rate performance curve of the cobalt molybdate multifunctional diaphragm prepared in the step one (2) in the comparative example 1 under different current densities when applied to the lithium-sulfur battery; wherein PP is the rate performance curve of the polypropylene separator in comparative example 2 applied to a lithium sulfur battery at different current densities.
The specific implementation mode is as follows:
the present invention is described in detail below with reference to specific examples.
Example 1:
a preparation method of a cobalt nitride-molybdenum nitride multifunctional diaphragm comprises the following steps:
(1) preparing cobalt molybdate by a hydrothermal synthesis method and a thermal annealing method: : firstly, respectively dissolving 2mmol of cobalt chloride hexahydrate, 2mmol of cobalt dioxide and 2mmol of sodium molybdate in 120ml of deionized water, fully stirring to obtain A, B solution, then mixing the two solutions, fully stirring for 30min to obtain AB solution, and then transferring the AB solution to a high-pressure reaction kettle to heat and react for 12h at 180 ℃; and cooling, washing and drying the reacted suspension to obtain powder, heating the powder to 400 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and preserving the temperature for 3h to react to obtain the bimetallic oxide, namely cobalt molybdate.
(2) Preparing the cobalt nitride-molybdenum nitride and the multifunctional diaphragm of the lithium-sulfur battery: and (2) heating the cobalt molybdate bimetallic oxide prepared in the step (1) to 700 ℃ at a heating rate of 10 ℃/min in an ammonia/argon (flow ratio of 1:3) atmosphere, and carrying out heat preservation for 2h for nitridation to obtain bimetallic nitride, namely cobalt nitride-molybdenum nitride.
Mixing cobalt nitride-molybdenum nitride, Super P and polyvinylidene fluoride in N-methyl pyrrolidone according to the ratio of 8:1:1, fully stirring the mixture into uniform slurry, and coating the prepared slurry on one surface of a polypropylene (PP) diaphragm by using a coating machine to prepare the cobalt nitride-molybdenum nitride multifunctional diaphragm marked as CoN-Mo2N/PP. The average content of the cobalt nitride-molybdenum nitride in the multifunctional diaphragm on each diaphragm is 0.8-1.2 mg/cm2The thickness of the cobalt nitride-molybdenum nitride multifunctional diaphragm is 10-30 μm.
Secondly, the cobalt nitride-molybdenum nitride multifunctional diaphragm is used as the diaphragm in the lithium-sulfur battery, and the specific steps are as follows:
(1) preparing a positive electrode material: the method comprises the steps of preserving heat of superconducting carbon black Super P and sublimed sulfur powder in a mass ratio of 1:2 at 155 ℃ for 12 hours by using a melting method to obtain an S/C composite material, and then mixing the S/C composite material and polyvinylidene fluoride in a mass ratio of 9:1 in an N-methylpyrrolidone (NMP) solvent to prepare slurry, wherein the ratio of a binder to NMP is 25mg:1 ml; finally, coating the slurry on a carbon-coated aluminum foil current collector to serve as a positive electrode plate of the lithium-sulfur battery, wherein the load capacity of the active substance sulfur is 1.2-4 mg/cm2。
(2) Assembling the lithium-sulfur battery:
taking the positive pole piece of the lithium-sulfur battery in the step (1) as a positive pole; cobalt nitride-molybdenum nitride multifunctional diaphragm (CoN-Mo)2N/PP) as a functional separator; a metal lithium sheet is used as a negative electrode; a1, 2-dimethoxyethane and 1, 3-dioxetane mixture containing 1.0M bis (trifluoromethane) sulfonimide salt and 2 wt.% lithium nitrate in a volume ratio of 1:1 was used as an electrolyte. The lithium sulfur battery was assembled in the order of a positive electrode, an electrolyte, a multifunctional separator, an electrolyte, and a negative electrode in an argon atmosphere, wherein the amount of the electrolyte added was 30 μ L, and then subjected to an electrochemical performance test.
FIG. 1 is a scanning electron microscope photograph of cobalt nitride-molybdenum nitride prepared in step (2) of example 1. As shown in the figure, the material shows a nanorod structure with the size of 300-400nm, the appearance is uniform, and all elements are uniformly distributed.
Fig. 2 is a transmission electron microscope photograph of the cobalt nitride-molybdenum nitride prepared in step (2) of example 1, more clearly showing the dimensional and morphological features of the material.
FIG. 3 is an X-ray diffraction pattern of cobalt nitride-molybdenum nitride prepared in step (2) of example 1. It can be seen that the diffraction peaks of this material correspond to the phase structure of cobalt nitride (JCPDS No.16-0016) and molybdenum nitride (JCPDS No.25-1366), i.e., cobalt nitride-molybdenum nitride was successfully prepared.
FIG. 4 is a multifunctional separator in which cobalt nitride-molybdenum nitride prepared in step (2) of example 1 and cobalt molybdate material prepared in comparative example 1 are coated on a polypropylene separator, and a comparisonThe polypropylene separator prepared in example 2 was applied to a long cycle performance curve at 0.2C in a step two assembled lithium sulfur battery. It can be seen that the initial capacity of the lithium-sulfur battery having the cobalt nitride-molybdenum nitride multifunctional separator, the cobalt molybdate multifunctional separator, and the polypropylene separator at 0.2C was 1434.3mAh g-1、1225.3mAh g-1And 833.4mAh g-1After 200 cycles, the capacity fade rate of each cell was 0.198%, 0.276%, and 0.244% (after 200 cycles, the capacity was 866.9mAh g, respectively-1、549.8mAh g-1And 426mAh g-1)。
Fig. 5 is a rate performance curve of the multifunctional diaphragm and the polypropylene diaphragm coated with the cobalt nitride-molybdenum nitride prepared in example 1 and the cobalt molybdate material prepared in comparative example 1, applied to the lithium-sulfur battery assembled in step two under different current densities. It can be seen that the lithium sulfur battery having the cobalt nitride-molybdenum nitride multifunctional separator has reversible capacities of 1605.8, 895.4, 779.9, 703.7, and 613.9mAh g at current rates of 0.1 to 2.0C, respectively, as compared to the comparative example material-1It shows that the product has higher rate performance and reversibility.
Example 2:
a preparation method of an iron nitride-vanadium nitride multifunctional diaphragm comprises the following steps:
(1) preparing ferric vanadate by a hydrothermal synthesis method and a thermal annealing method: firstly, respectively dissolving 2mmol of ferric chloride hexahydrate and 4mmol of ammonium metavanadate in 120ml of deionized water, fully stirring to obtain A, B solution, then mixing the two solutions, fully stirring for 30min to obtain AB solution, and then transferring the AB solution to a high-pressure reaction kettle to heat and react for 24h at 180 ℃; and cooling, washing and drying the suspension after the reaction to obtain powder, heating the powder to 400 ℃ at a heating rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 3 hours to react to obtain the ferric vanadate.
(2) Preparing the iron nitride-vanadium nitride and lithium-sulfur battery multifunctional diaphragm: and (2) heating the ferric vanadate prepared in the step (1) to 750 ℃ at a heating rate of 10 ℃/min in an ammonia/argon (flow ratio of 1:3) atmosphere, and carrying out heat preservation for 2h for nitridation to obtain the iron nitride-vanadium nitride.
Mixing iron nitride-vanadium nitride withMixing a conductive agent and a binder in an organic solvent according to a ratio of 8:1:1, fully stirring the mixture into uniform slurry, and coating the prepared slurry on one side of a polypropylene (PP) diaphragm by using a coating machine to prepare the iron nitride-vanadium nitride multifunctional diaphragm. Wherein the conductive agent in the slurry is Super P, the binder is polyvinylidene fluoride (PVDF), and the solvent is N-methylpyrrolidone (NMP); the average content of iron nitride-vanadium nitride in the multifunctional diaphragm on each diaphragm is 0.8-1.2 mg/cm2The thickness of the iron nitride-vanadium nitride multifunctional diaphragm is 10-30 mu m.
The application of the iron nitride-vanadium nitride multifunctional diaphragm as a diaphragm in a lithium-sulfur battery comprises the following specific steps:
(1) preparing a positive electrode material: the Keqin carbon black CCB and the sublimed sulfur powder in a mass ratio of 1:3 are subjected to heat preservation at 155 ℃ for 12 hours by using a melting method to obtain an S/C composite material, and then the S/C composite material and a binder are mixed in an N-methyl pyrrolidone (NMP) solvent according to a mass ratio of 9:1 to prepare slurry, wherein the binder/NMP ratio is 25mg/ml, and the binder is polyvinylidene fluoride (PVDF). And finally, coating the slurry on a carbon-coated aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery, wherein the loading capacity of active substance sulfur is 1.2-4 mg/cm2。
(2) Assembling the lithium-sulfur battery:
taking the positive pole piece of the lithium-sulfur battery in the step (1) as a positive pole; the bimetal nitride multifunctional diaphragm prepared in the embodiment is used as a diaphragm; a metal lithium sheet is used as a negative electrode; a1, 2-dimethoxyethane and 1, 3-dioxacycloalkane mixture containing 1.0M bis (trifluoromethane) sulfonimide salt and 2 wt.% lithium nitrate in a volume ratio of 1:1 was used as an electrolyte. The lithium sulfur battery was assembled in the order of a positive electrode, an electrolyte, a multifunctional separator, an electrolyte, and a negative electrode under an argon atmosphere, wherein the amount of the electrolyte added was 30 μ L, and then subjected to an electrochemical performance test.
Example 3:
a preparation method of a cobalt nitride-vanadium nitride multifunctional diaphragm comprises the following steps:
(1) preparing cobalt vanadate by a hydrothermal synthesis method and a thermal annealing method: firstly, respectively dissolving 2mmol of cobalt chloride hexahydrate and 4mmol of ammonium metavanadate in 120ml of deionized water, fully stirring to obtain A, B solution, then mixing the two solutions, fully stirring for 30min to obtain AB solution, and then transferring the AB solution to a high-pressure reaction kettle to heat and react for 24h at 180 ℃; and cooling, washing and drying the suspension after reaction to obtain powder, heating the powder to 400 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 3h to react to obtain the cobalt vanadate.
(2) Preparing a cobalt nitride-vanadium nitride and lithium-sulfur battery multifunctional diaphragm: and (2) heating the cobalt nitride-vanadium nitride bimetal oxide prepared in the step (1) to 800 ℃ at a heating rate of 10 ℃/min in an ammonia/argon (flow ratio of 1:3) atmosphere, and carrying out heat preservation for 2h to carry out nitridation to obtain the cobalt nitride-vanadium nitride. Mixing cobalt nitride-vanadium nitride, a conductive agent and a binder in an organic solvent according to a ratio of 8:1:1, fully stirring the mixture into uniform slurry, and coating the prepared slurry on one surface of a Polyethylene (PE) diaphragm by using a coating machine to obtain the cobalt nitride-vanadium nitride multifunctional diaphragm. Wherein the conductive agent in the slurry is Super P, the binder is polyvinylidene fluoride (PVDF), and the solvent is N-methylpyrrolidone (NMP); the average content of the bimetallic nitride in the multifunctional diaphragm on each diaphragm is 0.8-1.2 mg/cm2The thickness of the cobalt nitride-vanadium nitride multifunctional diaphragm is 10-30 mu m.
Secondly, the cobalt nitride-vanadium nitride multifunctional diaphragm is used as the diaphragm in the lithium-sulfur battery, and the specific steps are as follows:
(1) preparing a positive electrode material: the preparation method comprises the steps of preserving heat of carbon nano tube CNTs and sublimed sulfur powder at a mass ratio of 1:4 for 12 hours at 155 ℃ by using a melting method to obtain an S/C composite material, and then mixing the S/C composite material and a binder in a mass ratio of 9:1 in an N-methyl pyrrolidone (NMP) solvent to prepare slurry, wherein the ratio of the binder to the N-methyl pyrrolidone is 25mg/ml, and the binder is polyvinylidene fluoride (PVDF). And finally, coating the slurry on a carbon-coated aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery, wherein the loading capacity of active substance sulfur is 1.2-4 mg/cm2。
(2) Assembling the lithium-sulfur battery:
taking the positive pole piece of the lithium-sulfur battery in the step (1) as a positive pole; the bimetal nitride multifunctional diaphragm prepared in the embodiment is used as a diaphragm; a metal lithium sheet is used as a negative electrode; a1, 2-dimethoxyethane and 1, 3-dioxacycloalkane mixture containing 1.0M bis (trifluoromethane) sulfonimide salt and 2 wt.% lithium nitrate in a volume ratio of 1:1 was used as an electrolyte. The lithium sulfur battery was assembled in the order of a positive electrode, an electrolyte, a multifunctional separator, an electrolyte, and a negative electrode in an argon atmosphere, wherein the amount of the electrolyte added was 30 μ L, and then subjected to an electrochemical performance test.
Comparative example 1:
comparative example 1 differs from example 1 in that: the preparation method and conditions were the same as in example 1 except that cobalt molybdate was not reduced to cobalt nitride-molybdenum nitride in an ammonia/argon atmosphere.
A preparation method of a bimetal oxide cobalt molybdate multifunctional diaphragm comprises the following steps:
(1) preparing bimetallic oxide cobalt molybdate by a hydrothermal synthesis method and a thermal annealing method: : firstly, respectively dissolving 2mmol of cobalt chloride hexahydrate, 2mmol of cobalt dioxide and 2mmol of sodium molybdate in 120ml of deionized water, fully stirring to obtain A, B solution, then mixing the two solutions, fully stirring for 30min to obtain AB solution, and then transferring the AB solution to a high-pressure reaction kettle to heat and react for 12h at 180 ℃; and (3) cooling, washing and drying the suspension after the reaction to obtain powder, heating the powder to 400 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and preserving the temperature for 3h to perform reaction to obtain the bimetallic oxide cobalt molybdate.
(2) Preparation of cobalt molybdate multifunctional membrane: mixing cobalt molybdate bimetal oxide with a conductive agent and a binder in an organic solvent according to a ratio of 8:1:1, fully stirring the mixture into uniform slurry, and coating the slurry on one surface of a polypropylene (PP) diaphragm by using a coating machine to obtain the cobalt molybdate multifunctional diaphragm CoMoO4and/PP. Wherein the conductive agent in the slurry is Super P, the binder is polyvinylidene fluoride (PVDF), and the solvent is N-methylpyrrolidone (NMP); the average content of the bimetallic nitride in the multifunctional diaphragm on each diaphragm is 0.8-1.2 mg/cm2The thickness of the cobalt molybdate multifunctional diaphragm is 10-30 mu m.
The application of the cobalt molybdate multifunctional diaphragm as a diaphragm in a lithium-sulfur battery comprises the following specific steps:
(1) preparing a positive electrode material: the method comprises the steps of preserving heat of superconducting carbon black Super P and sublimed sulfur powder in a mass ratio of 1:2 at 155 ℃ for 12 hours by using a melting method to obtain an S/C composite material, and then mixing the S/C composite material and a binder in a mass ratio of 9:1 in an N-methylpyrrolidone (NMP) solvent to prepare slurry, wherein the binder/NMP ratio is 25mg/ml, and the binder is polyvinylidene fluoride (PVDF). And finally, coating the slurry on a carbon-coated aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery, wherein the loading capacity of active substance sulfur is 1.2-4 mg/cm2。
(2) Assembling the lithium-sulfur battery:
taking the positive pole piece of the lithium-sulfur battery in the step (1) as a positive pole; the bimetal nitride multifunctional diaphragm prepared in the comparative example 1 is used as a diaphragm; a metal lithium sheet is used as a negative electrode; a1, 2-dimethoxyethane and 1, 3-dioxacycloalkane mixture containing 1.0M bis (trifluoromethane) sulfonimide salt and 2 wt.% lithium nitrate in a volume ratio of 1:1 was used as an electrolyte. The lithium sulfur battery was assembled in the order of a positive electrode, an electrolyte, a multifunctional separator, an electrolyte, and a negative electrode under an argon atmosphere, wherein the amount of the electrolyte added was 30 μ L, and then subjected to an electrochemical performance test.
From fig. 4-5, it can be seen that the untreated cobalt molybdate material has relatively poor rate performance and long cycle stability when applied to the multifunctional diaphragm of the lithium sulfur battery compared to nitrided cobalt nitride-molybdenum nitride, which indicates that the strong catalytic action of the nitrided bimetallic nitride and the strong coupling action between metal and nitrogen can promote the adsorption and conversion of polysulfide during the charging and discharging processes of the lithium sulfur battery, and from the electrochemical results, the reversible capacities of the lithium sulfur battery of the cobalt molybdate multifunctional diaphragm are 1332.2, 830.8, 703.7, 604.1 and 526.3mAh g at the current rate of 0.1 to 2.0C, respectively-1(ii) a Initial capacity at 0.2C long cycle was 1225.3mAh g-1After 200 cycles, the capacity fade rate of the battery was 0.276% (capacity after 200 cycles was 549.8mAh g)-1). The method shows that the nitrided bimetallic oxide can obtain higher rate performance and reversibility, thereby obviously improving the electrochemical performance.
Comparative example 2:
comparative example 2 differs from example 1 in that: the multifunctional coating diaphragm is not prepared, the polypropylene diaphragm is directly used as the lithium-sulfur battery diaphragm, and the rest preparation method and conditions are the same as those of the example 1;
the application of the polypropylene diaphragm as the diaphragm in the lithium-sulfur battery specifically comprises the following operations:
(1) the preparation method of the cathode material comprises the following steps: the method comprises the steps of preserving heat of superconducting carbon black Super P and sublimed sulfur powder in a mass ratio of 1:2 at 155 ℃ for 12 hours by using a melting method to obtain an S/C composite material, and then mixing the S/C composite material and a binder in a mass ratio of 9:1 in an N-methylpyrrolidone (NMP) solvent to prepare slurry, wherein the binder/NMP ratio is 25mg/ml, and the binder is polyvinylidene fluoride (PVDF). Finally, coating the slurry on a carbon-coated aluminum foil current collector to serve as a positive electrode plate of the lithium-sulfur battery, wherein the load capacity of the active substance sulfur is 1.2-4 mg/cm2。
(2) Assembling the lithium-sulfur battery:
taking the positive pole piece of the lithium-sulfur battery in the step (1) as a positive pole; taking a polypropylene diaphragm as a diaphragm; a metal lithium sheet is used as a negative electrode; a1, 2-dimethoxyethane and 1, 3-dioxacycloalkane mixture containing 1.0M bis (trifluoromethane) sulfonimide salt and 2 wt.% lithium nitrate in a volume ratio of 1:1 was used as an electrolyte. The lithium sulfur battery was assembled in the order of a positive electrode, an electrolyte, a multifunctional separator, an electrolyte, and a negative electrode in an argon atmosphere, wherein the amount of the electrolyte added was 30 μ L, and then subjected to an electrochemical performance test.
As can be seen from fig. 4-5, the lithium sulfur battery using the polypropylene separator had poorer performance than the lithium sulfur battery to which the multifunctional coated separator was added, and as can be seen from the electrochemical results, the lithium sulfur battery having the polypropylene separator had reversible capacities of 866.5, 634.8, 209.6, 166 and 117.4mAh g at current rates of 0.1 to 2.0C, respectively-1(ii) a Initial capacity at 0.2C long cycle was 833.4mAh g-1After 200 cycles, the capacity fade rate of the battery was 0.244% (capacity after 200 cycles was 426mAh g-1). The multifunctional coating membrane is proved to effectively block the shuttle of polysulfide to a negative electrode, promote the catalytic conversion of the polysulfide and improve the utilization rate of sulfur.
In conclusion, the bimetal nitride prepared by the invention is applied to the multifunctional diaphragm of the lithium-sulfur battery, can effectively solve the problems of polysulfide shuttle effect, slow redox reaction kinetics in conversion and the like, promotes the conversion of long-chain lithium polysulfide into short-chain lithium polysulfide and the uniform nucleation and growth of lithium sulfide, and thus remarkably improves the electrochemical performance of the lithium-sulfur battery.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the various embodiments thereof, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.

Claims (8)

1. The preparation method of the bimetal nitride multifunctional diaphragm is characterized by comprising the following steps:
(1) firstly, respectively dissolving A, B two metal salts in deionized water, stirring and dissolving to obtain A, B two solutions, mixing the two solutions, and stirring for a period of time to obtain an AB mixed solution; then transferring the mixture into a high-pressure reaction kettle for heating reaction; cooling, washing and drying the suspension obtained after the reaction to obtain solid powder; then calcining the solid powder to obtain a bimetallic oxide;
(2) calcining the bimetallic oxide prepared in the step (1) in an atmosphere of introducing ammonia gas and argon gas, and calcining to obtain bimetallic nitride;
then adding the bimetal nitride, the conductive agent and the binder into an organic solvent, fully stirring the mixture into uniform slurry, and coating the slurry on one surface of a polyethylene or polypropylene diaphragm to obtain the bimetal nitride multifunctional diaphragm; the average content of the bimetal nitride in the bimetal nitride multifunctional diaphragm on each diaphragm is 0.8-1.2 mg/cm2。
2. The method for preparing the bimetal nitride multifunctional diaphragm according to claim 1, wherein the A, B two metal salts in step (1) comprise any two of cobalt chloride hexahydrate, sodium molybdate dihydrate, ammonium metavanadate and ferric chloride hexahydrate, and the ratio of the metal salt A to the deionized water is 2 mmol: 120 ml; the dosage ratio of the metal salt B to the deionized water is 2-4 mmol: 120 ml; the molar ratio of the two metal salts in the AB mixed solution is 1: 1-3.
3. The method for preparing the bimetal nitride multifunctional membrane according to claim 1, wherein the stirring in the step (1) is carried out for a period of time of 30 to 60 min; the heating reaction is carried out at the temperature of 180-200 ℃ for 12-24 hours; the calcination operation is as follows: heating to 400-600 ℃ at a heating rate of 2-5 ℃/min in an air atmosphere, and preserving heat for 3-4 h.
4. The preparation method of the bimetal nitride multifunctional membrane according to claim 1, wherein in the step (2), the calcining temperature in the step (2) is 600-800 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1.5-2.5 h; the flow ratio of the ammonia gas to the argon gas is 1: 2-3.
5. The method for preparing the bimetal nitride multifunctional membrane according to claim 1, wherein the mass ratio of the bimetal nitride, the conductive agent and the binder in the step (2) is 8:1: 1; the conductive agent in the slurry is any one of Super P, Keqin carbon black or acetylene black; the binder is polyvinylidene fluoride, and the organic solvent is N-methyl pyrrolidone; the thickness of the bimetal nitride multifunctional diaphragm is 10-30 mu m.
6. Use of the bi-metal nitride multifunctional separator prepared according to any one of claims 1 to 5 as a separator in a lithium sulfur battery for assembling the lithium sulfur battery, characterized by the steps of:
(1) heating conductive agent and sulfur powder by melting methodKeeping the temperature for a period of time to obtain an S/C composite material; then mixing the S/C composite material and the binder in a solvent to prepare slurry; finally, coating the slurry on the surface of the carbon-coated aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery; the loading capacity of the active substance sulfur on the surface of the coated positive pole piece of the lithium-sulfur battery is 1.2-4 mg/cm2(ii) a The solvent is N-methyl pyrrolidone or water;
(2) taking the positive pole piece of the lithium-sulfur battery prepared in the step (1) as a positive pole; taking a bimetal nitride multifunctional diaphragm as a functional diaphragm and a metal lithium sheet as a negative electrode; and assembling the positive electrode, the electrolyte, the functional diaphragm, the electrolyte and the negative electrode in sequence under an argon atmosphere to obtain the lithium-sulfur battery.
7. The use according to claim 6, wherein the conductive agent in step (1) is any one of Super P, acetylene black, ketjen black, carbon nanotube or graphene; the binder is polyvinylidene fluoride or LA132, the dosage ratio of the binder to the solvent in the slurry is 25mg:1ml, and the mass ratio of the S/C composite material to the binder is 9: 1.
8. The use according to claim 6, wherein the electrolyte in the step (2) is a mixed solution of 1, 2-dimethoxyethane and 1, 3-dioxacycloalkane in a volume ratio of 1:1, and the mixed solution contains a bis (trifluoromethane) sulfonimide salt in a final concentration of 1.0M and 2 wt.% of lithium nitrate; the addition amount of the electrolyte is 20-40 mu L.
CN202210242620.0A 2022-03-11 2022-03-11 Preparation method and application of bimetal nitride multifunctional diaphragm Pending CN114649635A (en)

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CN111416091A (en) * 2020-03-13 2020-07-14 上海电力大学 Bimetal nitride modified diaphragm and preparation method and application thereof
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CN111864156A (en) * 2019-04-26 2020-10-30 河南师范大学 Preparation method of metal nitride-metal oxide heterojunction modified diaphragm for lithium-sulfur battery and lithium-sulfur battery comprising diaphragm
CN111416091A (en) * 2020-03-13 2020-07-14 上海电力大学 Bimetal nitride modified diaphragm and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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CN115498357A (en) * 2022-07-07 2022-12-20 陕西科技大学 Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof

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