CN112510319B - Spherical CoS/g-C3N4Composite material modified PP diaphragm and preparation method and application thereof - Google Patents

Spherical CoS/g-C3N4Composite material modified PP diaphragm and preparation method and application thereof Download PDF

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CN112510319B
CN112510319B CN202011245991.1A CN202011245991A CN112510319B CN 112510319 B CN112510319 B CN 112510319B CN 202011245991 A CN202011245991 A CN 202011245991A CN 112510319 B CN112510319 B CN 112510319B
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邓远富
刘新叶
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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Abstract

Hair brushA spherical CoS/g-C is disclosed3N4A PP diaphragm modified by a composite material, a preparation method and application thereof. The method of the invention uses g-C3N4Using cobalt chloride hexahydrate as a cobalt source and thiourea as a sulfur source as a carrier, and preparing CoS/g-C by adopting a hydrothermal method3N4Dispersing the composite material and additive in ethanol, anchoring the modified material on a PP (polypropylene) diaphragm by simple suction filtration, and drying to obtain the composite material with the CoS/g-C content3N4The PP diaphragm is modified and decorated by the composite material. The diaphragm modified by the composite material can greatly improve the rate capability and the cycling stability of the lithium-sulfur battery. Meanwhile, the process flow of the preparation of the modified layer composite material and the modification of the diaphragm is simple, low in cost, environment-friendly and suitable for scale-up.

Description

Spherical CoS/g-C3N4Composite material modified PP diaphragm and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to spherical CoS/g-C3N4A PP diaphragm modified by a composite material, a preparation method and application thereof.
Background
Since the introduction of lithium cobaltate/carbon cathode lithium ion batteries by sonoy corporation in japan in 1991, lithium ion batteries have received much attention, have rapidly developed, and are widely used in various fields of life, such as mobile phones, computers, cameras, and the like. With the development of science and technology, the demand of people for energy density of batteries is gradually increased. However, the specific energy of the lithium ion battery is difficult to increase due to the limitation of the theoretical specific capacity of the cathode material. Therefore, the development of new electrochemical energy storage systems is imperative. Elemental sulfur has a high theoretical specific capacity and abundant resource reserves, and has received wide attention in recent years. Lithium-sulfur (Li-S) batteries utilizing sulfur as the positive electrode and lithium as the negative electrode have a capacity of up to 2600Wh kg-1Is considered to be one of the most promising lithium secondary battery systems (Advanced Materials,2019,31,27) in terms of research value and application prospect. However, practical application of Li-S batteries is hampered by several properties of their own, including: firstly, the conductivity of the sulfur of the anode is poor, and the rapid transmission of electrons in the anode is limited; secondly, the sulfur anode can undergo a solid-liquid-solid process in the electrochemical circulation process, so that the volume of the sulfur anode is greatly changed; ③ shuttling effect of polysulfides: the intermediate products generated in the electrochemical reaction process are easily dissolved in the electrolyte, so that the intermediate products can directly react with the lithium of the negative electrode through the diaphragm, and the shuttle effect brings huge attenuation to the battery capacity (Energy Storage Materials,2019,23, 707-732). The above defects restrict the development of Li-S batteries, which is also a key problem to be solved in the current research of lithium-sulfur batteries. The researchers proposeMany schemes have been proposed to improve the performance of Li-S batteries, where improving the performance of Li-S batteries through separator modification is a very effective approach. In general, it is a common method to modify the membrane with a coating of nanocarbon materials. The nano carbon coating has good conductivity, has rich pore structures and can adsorb polysulfide dissolved in electrolyte, so that the polysulfide is prevented from penetrating through the diaphragm to reach a negative electrode, and the rate capability and the cycle performance of the battery are improved well. However, the physical adsorption force between the carbon material and lithium polysulfide is weak, and it is difficult to effectively anchor polar polysulfide during long-term cycling. Therefore, researchers have introduced heteroatoms (e.g., N, S, etc.) as polar centers on carbon materials to improve the interaction of carbon-based materials with polar polysulfides and have achieved good results. However, the content of the introduced heteroatom in most of the heteroatom-doped carbons reported so far is low (<10%). It is reported that carbon nitride (g-C)3N4) The carbon-based material (Journal of Energy Chemistry, 2020, 43, 71-77) with high N content (about 57%) greatly improves the polarity of the carbon-based material and provides sufficient chemisorption sites for "fixing" lithium polysulfide. In addition, the shuttle effect mainly comes from the fact that high-order polysulfide soluble in electrolyte passes through the separator to the negative electrode after being dissolved, and reacts with the lithium negative electrode directly to form insoluble Li2S2/Li2S, which in turn leads to loss of active material. Reducing the diffusion of higher order lithium polysulfides into the negative electrode and catalysing the transition between lithium polysulfides are therefore two effective means of reducing the shuttling effect. Researchers have found many metal oxides (TiO)2、MnO2Etc.), sulfides (CoS)2、CoS、 MoS2Etc.), nitrides (TiN) have excellent activity of catalyzing the conversion of higher-order polysulfides into lower-order polysulfides (Advanced Energy Materials,2019, 10, 1903008).
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a spherical CoS/g-C3N4Preparation method of composite material modified PP (polypropylene) diaphragm。
The invention employs g-C3N4As a template, loading nano CoS on the surface of the template by a hydrothermal method, and then loading the flaky CoS/g-C3N4The composite material is dispersed in ethanol, two additives are added, and CoS/g-C is subjected to in-situ suction filtration3N4Spherical particles formed by the composite material are anchored on a PP diaphragm to obtain the spherical CoS/g-C3N4The composite material particle modified functional diaphragm can improve the comprehensive performance of the Li-S battery. The method avoids the defects of complex process and use of a large amount of organic solvent in the process of modifying the diaphragm by the traditional coating method, and is expected to realize large-scale production.
Another object of the present invention is to provide a spherical CoS/g-C prepared by the above method3N4The PP diaphragm is modified by the composite material.
It is still another object of the present invention to provide a spherical CoS/g-C as described above3N4The composite material modified PP diaphragm is applied to the field of lithium-sulfur batteries.
The purpose of the invention is realized by the following technical scheme:
spherical CoS/g-C3N4The preparation method of the PP diaphragm modified by the composite material comprises the following steps:
(1) g to C3N4Dispersing in solvent, adding cobalt chloride hexahydrate and thiourea, stirring uniformly, adding ethylenediamine, carrying out hydrothermal reaction, cooling, and purifying to obtain sheet CoS/g-C3N4A composite material;
(2) subjecting the flaky CoS/g-C3N4Dispersing the composite material and Keqin black in a solvent, adding a binder LA133, stirring to form slurry, performing suction filtration on the slurry on a PP diaphragm, and drying to obtain spherical CoS/g-C3N4The PP diaphragm is modified by the composite material.
Preferably, the solvent in steps (1) and (2) is at least one of ethanol and propanol.
Preferably, after the cobalt chloride hexahydrate is added in the step (1), the mixture is stirred uniformly, and then the thiourea is added and stirred uniformly.
Preferably, the ratio of the cobalt chloride hexahydrate and the ethylenediamine in the step (1) is 0.8 mmol: 1-2 ml, and the flaky CoS/g-C3N4In the composite material, the mass content of CoS is 2-20%.
Preferably, the adding of the cobalt chloride hexahydrate and the thiourea in the step (1) means adding the cobalt chloride hexahydrate and uniformly stirring, then adding the thiourea and uniformly stirring, wherein the stirring time after the cobalt chloride hexahydrate is added is 10-60 min; and stirring the thiourea for 10-60 min.
Preferably, g to C in step (1)3N4The ratio of the water to the solvent is 7.5-10 mg/ml.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 160-180 ℃ and the time is 12-24 h.
Preferably, the purification method in step (1) is: and (3) centrifugally separating the product mixed solution, washing and separating the product mixed solution for 1-5 times by using ethanol and water respectively, and then drying the product mixed solution for 5-20 hours in vacuum at the temperature of 50-80 ℃ to obtain a solid product.
Preferably, the flaky CoS/g-C of step (2)3N4The mass ratio of the composite material to the Ketjen black is 1-2: 1, sheet-like CoS/g-C3N4The mass ratio of the composite material to the total mass of the ketjen black and the binder LA133 is 8: 2-9: 1.
preferably, the binder LA133 in the step (2) is added in the form of a solution, and the concentration of the solution is 0.1-0.4 wt%.
Preferably, the flaky CoS/g-C of step (2)3N4The ratio of composite to solvent was 6 mg: 50 to 75 ml.
Preferably, the slurry effective component (CoS/g-C) of the step (2)3N4Ketjen black and a binder LA133) and the area ratio of the modified surface of the PP diaphragm is 0.07-0.28 mg/cm2I.e. spherical CoS/g-C3N4The mass surface density of the PP diaphragm modification layer modified by the composite material is 0.07-0.28 mg/cm2。
The binder LA133 refers to LA133 type water-based adhesive, and an effective group is cyano (-CN). The Ketjen black is one of carbon blacks.
The spherical CoS/g-C prepared by the method3N4The PP diaphragm is modified by the composite material.
The spherical CoS/g-C3N4The composite material modified PP diaphragm is applied to the field of lithium-sulfur batteries.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention is realized by adding CoS/g-C in a sheet form3N4Ketjen black and a binder LA133 are added into the material, so that the PP diaphragm modified by spherical particles can be obtained, and the preparation method is simple, unique and high in repeatability.
(2) The spherical PP membrane modified by the composite material is obtained by a simple suction filtration method, so that the use of a large amount of toxic solvent (NMP) in the membrane modification process by the traditional coating method is avoided.
(3) The modification layer of the invention not only has Ketjen black with high conductivity, but also has g-C with high capability of chemically adsorbing lithium polysulfide3N4And a CoS catalyst for catalyzing interconversion of lithium polysulfide, so that the modified diaphragm can improve the comprehensive performance of the Li-S battery through various synergistic effects.
Drawings
FIG. 1 is a graph of CoS/g-C obtained in example 13N4Scanning Electron Microscopy (SEM) of the composite (left panel) and its modified PP separator (right panel).
FIG. 2 is a graph of CoS/g-C obtained in example 13N4X-ray powder diffraction (XRD) patterns of the composite material and CoS prepared in comparative example 1.
Fig. 3 is a specific capacity-cycle number plot for a Li-S battery assembled with the modified separator prepared in example 1 and comparative example 1.
FIG. 4 shows the composite materials (CoS/g-C) obtained in examples 1 to 33N4) X-ray powder diffractogram (XRD).
Fig. 5 is a graph of specific capacity versus cycle number for 2C (1C 1670mA/g) modified separator assembled Li-S batteries prepared in examples 1 to 3.
Fig. 6 is a cross-sectional Scanning Electron Microscope (SEM) of the modified separators prepared in example 1, example 4, and example 5.
Fig. 7 is a graph of specific capacity versus cycle number at 1C (1670 mA/g) rate for modified separator assembled Li-S batteries prepared in example 1, example 4, and example 5.
FIG. 8 shows g-C obtained in comparative example 23N4Scanning Electron Microscopy (SEM) of the material (left panel) and its modified PP separator (right panel).
Fig. 9 is a graph of specific capacity versus cycle number at 1C (1C 1670mA/g) rate for Li-S batteries assembled with modified separators prepared in example 1 and comparative example 2 and a pure PP film.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Weighing 30.0g of urea in a crucible, covering the crucible cover, putting the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2.5 ℃/min, cooling to room temperature, taking out the crucible cover, heating to 500 ℃ at the heating rate of 5 ℃/min, naturally cooling to room temperature, and collecting the flake g-C3N4And (3) a solid.
(2) Weighing 300.0mg of flaky g-C3N4Ultrasonically dispersing the mixture in 40mL of ethanol, adding 0.1903g of cobalt chloride hexahydrate and 0.1218g of thiourea, stirring to dissolve, adding 1.5mL of ethylenediamine, pouring the solution into a reaction kettle, keeping the temperature at 180 ℃ for 12h, cooling the reaction kettle to room temperature, centrifuging, washing with deionized water and ethanol for 3 times respectively, and drying in vacuum at 60 ℃ to obtain a label of CoS/g-C3N4-1.
(3) Weighing CoS/g-C3N4-1(12.0mg) and 6.0mg Ketjen black (additive 1), mixing, adding 150mL ethanol, sonicating for 1h, and adding 1mL 0.2wt to the mixed solution% LA133 ethanol solution (additive 2), stirring well to obtain slurry, and finally taking 8mL of the slurry as a substrate and pumping-filtering the slurry with the area of 12.56cm2And drying to obtain the PP diaphragm (marked as FPP-1) containing the functional coating modification.
As can be seen from FIG. 1, the synthesized original CoS/g-C3N4The composite material has a lamellar structure, however, after the additive 1 and the additive 2 are added into the ethanol solution of the composite material, the PP diaphragm modified by spherical particles can be finally obtained by a suction filtration method.
Comparative example 1
(1) Synthesis of flake-like g-C according to the procedure (1) in example 13N4And (3) a solid.
(2) Ultrasonically dispersing 0.1903g of cobalt chloride hexahydrate in 40mL of ethanol, adding 0.1218g of thiourea, stirring to dissolve, adding 1.5mL of ethylenediamine, pouring the solution into a reaction kettle, preserving the temperature at 180 ℃ for 12h, cooling the reaction kettle to room temperature, centrifuging, washing with deionized water and ethanol for 3 times respectively, and drying in vacuum at 60 ℃ to obtain the flaky CoS material.
(3) Weighing CoS (1.2mg), g-C3N4(10.8mg) and 6.0mg Ketjen black (additive 1), mixing, adding 150mL of ethanol, performing ultrasonic treatment for 1h, adding 1mL of 0.2 wt% LA133 (additive 2) into the mixed solution, uniformly stirring to obtain a slurry, taking a PP membrane as a substrate, taking 8mL of the slurry, performing suction filtration on the PP membrane, and drying to obtain the PP membrane (marked as FPP-2) containing the functional coating modification.
As can be seen from FIG. 2, CoS was successfully synthesized, and the XRD pattern of the material did not appear to be clearly assigned to g-C3N4Peak of (2).
FIG. 3 is the CoS/g-C obtained in example 13N4Composite and CoS and g-C obtained in comparative example 13N4The specific capacity-cycle number chart of the Li-S battery assembled by the mixed modified diaphragm is as follows: after the batteries are activated for 3 circles at the current density of 0.2C, the cycle performance test is carried out at the current density of 1C. From fig. 3, it can be seen that: compared with direct proportional mixing of CoS andg-C3N4the resulting material, composite CoS/g-C3N4The membrane modification for the lithium-sulfur battery shows better rate performance, and proves that CoS/g-C3N4The electrochemical performance of the lithium-sulfur battery is improved through synergistic effect.
Example 2
(1) Synthesis of flake-like g-C according to the procedure (1) in example 13N4。
(2) The amounts of cobalt chloride hexahydrate (0.0952g) and thiourea (0.0609g) added were varied according to step (2) in example 1 to give the symbols CoS/g-C3N4-2.
(3) Following step (3) in example 1, CoS/g-C3N4-1 to CoS/g-C3N4And (2) keeping other conditions unchanged, and obtaining the PP diaphragm (marked as FPP-3) containing the functional coating modification.
Example 3
(1) Synthesis of flake-like g-C according to the procedure (1) in example 13N4。
(2) The amounts of cobalt chloride hexahydrate (0.3806g) and thiourea (0.2436g) added were varied according to step (2) in example 1 to give the values labeled CoS/g-C3N4-3.
(3) Following step (3) of example 1, CoS/g-C3N4-1 to CoS/g-C3N4-3, otherwise unchanged, obtaining a PP separator (labeled FPP-4) containing a functional coating modification.
As can be seen from FIG. 4, a series of CoS/g-C3N4The composite material was successfully synthesized, and as the amount of cobalt chloride hexahydrate added was increased, the diffraction peak of CoS was gradually increased in XRD results, while g-C3N4The diffraction peak (2 θ ═ 27.4) gradually decreased.
FIG. 5 shows CoS/g-C prepared in examples 1 to 33N4The specific capacity-cycle number graph of the Li-S battery assembled by the composite material modified diaphragm comprises the following battery test conditions: the batteries are activated for 3 circles under the current density of 0.2C and then are activated under the current of 2CCycle performance testing was performed at density. From fig. 5 it can be derived that: CoS/g-C3N4The content of CoS in the composite material has great influence on the performance of the battery, and the specific capacity of the battery shows the trend of increasing and then decreasing along with the increase of the content of CoS in the composite material, so that the performance of the Li-S battery can be greatly improved by the CoS with proper content in the functional coating.
Example 4
Taking 20mL of the slurry in example 1 and pumping-filtering the slurry in an area of 12.56cm by taking a PP film as a substrate2And drying to obtain the PP membrane (marked as FPP-5) containing the functional coating modification.
Example 5
Taking a PP film as a substrate, taking 30mL of the slurry in the example 1, and filtering the slurry in a suction way to form a slurry with the area of 12.56cm2And drying to obtain the PP membrane (marked as FPP-6) containing the functional coating modification.
As can be seen from fig. 6, by adjusting the volume of the slurry, PP separators modified with modification layers of different thicknesses can be successfully obtained. The modified layers obtained in examples 1, 4 and 5 had mass areal densities of 0.07, 0.18 and 0.28 mg-cm, respectively-2。
FIG. 7 shows CoS/g-C obtained in examples 1, 4 and 53N4The specific capacity-cycle number graph of the Li-S battery assembled by the composite material modified diaphragm comprises the following battery test conditions: after the batteries are activated for 3 circles at the current density of 0.2C, the cycle performance test is carried out at the current density of 1C. From fig. 6, it can be derived that: the thickness of the separator modification layer greatly affects the long cycle performance of the battery, and example 1 shows the best cycle stability, whereas the cycle stability of the battery decreases as the thickness of the modification layer increases.
Comparative example 2
(1) Weighing 30.0g of urea in a crucible, covering the crucible cover, putting the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2.5 ℃/min, cooling to room temperature, taking out the crucible cover, heating to 500 ℃ at the heating rate of 5 ℃/min, naturally cooling to room temperature, and collecting the flake g-C3N4And (3) a solid.
(2) Weighing g-C3N4(12.0mg) and 6.0mg Ketjen black (additive 1), mixing, adding 150mL ethanol, performing ultrasonic treatment for 1h, adding 1mL 0.2 wt% LA133 ethanol solution (additive 2) into the mixed solution, stirring to obtain slurry, and vacuum filtering 8mL of the slurry with PP membrane as substrate to obtain a filtrate with area of 12.56cm2And drying to obtain the PP membrane (marked as FPP-7) containing the functional coating modification.
As can be seen in FIG. 8, the synthesized g-C3N4The composite material has a lamellar structure, however, in the g-C direction3N4After the additive 1 and the additive 2 are added into the ethanol solution, the PP diaphragm modified by spherical particles can be finally obtained by a suction filtration method.
Fig. 9 is a specific capacity-cycle number graph of a Li-S battery assembled with the separator prepared in example 1 and the pure PP separator prepared in comparative example 2, and the battery test conditions were as follows: after the batteries are activated for 3 circles at the current density of 0.2C, the cycle performance test is carried out at the current density of 1C. From fig. 9 it can be derived that: the functional diaphragm coated by the composite material effectively improves the electrochemical performance of the lithium-sulfur battery, and the capacity fading rate of 500 cycles per cycle of the lithium-sulfur battery adopting the modified diaphragm in the embodiment 1 is only 0.037% at 1C.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. Spherical CoS/g-C3N4The preparation method of the PP membrane modified by the composite material is characterized by comprising the following steps:
(1) g to C3N4Dispersing in solvent, adding cobalt chloride hexahydrate and thiourea, stirring uniformly, adding ethylenediamine, carrying out hydrothermal reaction, cooling, and purifying to obtain sheet CoS/g-C3N4A composite material;
(2) subjecting the flaky CoS/g-C3N4Dispersing the composite material and Keqin black in a solvent, adding a binder LA133, stirring to form slurry, performing suction filtration on the slurry on a PP diaphragm, and drying to obtain spherical CoS/g-C3N4Modifying a PP diaphragm by using a composite material;
the flaky CoS/g-C of step (1)3N4In the composite material, the mass content of CoS is 2-20%;
spherical CoS/g-C obtained in step (2)3N4The mass surface density of the PP diaphragm modification layer modified by the composite material is 0.07-0.28 mg/cm2；
The flaky CoS/g-C of step (2)3N4The mass ratio of the composite material to the ketjen black is 1-2: 1, sheet-like CoS/g-C3N4The mass ratio of the composite material to the total mass of the ketjen black and the binder LA133 is 8: 2-9: 1.
2. spherical CoS/g-C according to claim 13N4The preparation method of the PP diaphragm modified by the composite material is characterized in that the proportion of cobalt chloride hexahydrate and ethylenediamine in the step (1) is 0.8 mmol: 1-2 ml.
3. Spherical CoS/g-C according to claim 13N4The preparation method of the PP diaphragm modified by the composite material is characterized in that the temperature of the hydrothermal reaction in the step (1) is 160-180 ℃, and the time is 12-24 hours.
4. Spherical CoS/g-C according to claim 13N4The preparation method of the PP diaphragm modified by the composite material is characterized in that the flaky CoS/g-C in the step (2)3N4The ratio of composite to solvent was 6 mg: 50-75 ml.
5. Spherical CoS/g-C according to claim 13N4The preparation method of the PP diaphragm modified by the composite material is characterized in that the g-C in the step (1)3N4The ratio of the solvent to the solvent is 7.5-10mg/ml; and (3) adding the binder LA133 in the step (2) in the form of a solution, wherein the concentration of the solution is 0.1-0.4 wt%.
6. Spherical CoS/g-C according to claim 13N4The preparation method of the composite material modified PP diaphragm is characterized in that the solvents in the steps (1) and (2) are both ethanol;
adding cobalt chloride hexahydrate and thiourea in the step (1) means adding cobalt chloride hexahydrate and uniformly stirring, adding thiourea and uniformly stirring, wherein the stirring time after adding cobalt chloride hexahydrate is 10-60 min; the time for stirring the thiourea is 10-60 min;
the purification method in the step (1) comprises the following steps: and (3) centrifugally separating the product mixed solution, washing and separating the product mixed solution for 1-5 times by using ethanol and water respectively, and then drying the product mixed solution for 5-20 hours in vacuum at the temperature of 50-80 ℃ to obtain a solid product.
7. A spherical CoS/g-C produced by the method of any of claims 1 to 63N4The PP diaphragm is modified by the composite material.
8. A spherical CoS/g-C as defined in claim 73N4The application of the composite material modified PP diaphragm in the field of lithium-sulfur batteries.
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