CN115504473A - MXene-based composite material for improving performance of lithium-sulfur battery diaphragm and preparation method thereof - Google Patents
MXene-based composite material for improving performance of lithium-sulfur battery diaphragm and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
The invention discloses an MXene-based composite material for improving the performance of a lithium-sulfur battery diaphragm and a preparation method thereof, and belongs to the technical field of battery diaphragms. The invention combines fluoride-containing salt and acid with Ti 3 AlC 2 Etching, intercalation processing and ultrasonic delamination are carried out to obtain two-dimensional Ti 3 C 2 T x (MXene) material, the surface of which has a large number of groups with negative charges and can attract transition metal cations, a sulfur source is added to carry out vulcanization treatment by a hydrothermal method, and MoS can grow on the surface of MXene in situ 2 SnS heterogeneous nano-sheet, then throughMXene/MoS is obtained after polydopamine coating carbonization treatment 2 The material is/SnS @ C, and the reinforced modified diaphragm is obtained by uniformly coating the material on a commercial PP film. The MXene has excellent conductivity and adsorption capacity, is combined with the excellent catalytic activity of the transition metal chalcogenide, can strongly adsorb polysulfide, improves reaction kinetics, accelerates the transformation of polysulfide, limits shuttle effect, and improves the rate capability, safety and cycle stability of the battery.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to an MXene-based composite material applied to performance improvement of a lithium-sulfur battery diaphragm and a preparation method of the composite material.
Background
With the continuous progress and development of science and technology and society, the demand of people for energy is continuously increased, but the traditional fossil energy has limited reserves and can cause serious environmental pollution in the using process, so that the development of renewable clean energy is urgently needed. However, clean energy sources such as wind energy and water energy have intermittent problems and are difficult to carry, energy storage devices are required to store and convert the energy sources, and the development of rechargeable batteries is considered to be an effective strategy for solving the problems. At present, the limited energy density of commercial batteries is difficult to meet the requirements of increasingly advanced technological equipment, so that the development of a battery system with high energy density is urgently needed.
The theoretical specific capacity and the theoretical specific energy of the lithium-sulfur battery are respectively up to 1675mAh/g and 2600Wh/Kg, and the elemental sulfur has the advantages of rich resources, low price and environmental protection, so the lithium-sulfur battery has wide application prospect. However, the initial discharge product of the lithium-sulfur battery is polysulfide which has high solubility in the electrolyte and can freely pass through the separator, so that a severe shuttling effect is formed on the two sides of the positive electrode and the negative electrode, and the battery performance is damaged. In addition, side reactions of polysulfides and metallic lithium can cause corrosion of the negative electrode, disrupt the formation of solid electrolyte interfacial films, and exacerbate the growth of lithium dendrites. Therefore, lithium-sulfur batteries face problems of poor cycle stability and rate performance, which severely restricts their commercial applications.
The widely used diaphragm material of the lithium-sulfur battery is a polyolefin diaphragm, and the shuttle effect of polysulfide and the growth of lithium dendrite cannot be inhibited due to the structure of the diaphragm. Therefore, the selection of suitable modifying materials and the development of a separator with higher stability are the key to solving such problems. MXene has a unique two-dimensional structure and controllable surface functional groups, can realize high sulfur catalytic activity and high lithium affinity, but Van der Waals force between sheet layers easily causes the re-stacking of MXene, so that the reduction of the active surface area and the surface functional groups is caused, and the catalytic conversion activity to polysulfide is reduced.
The invention provides a transition metal chalcogenide and MXene composite material, which improves the conductivity and catalytic activity of the composite material, accelerates the transformation of polysulfide, inhibits the formation of lithium dendrite, and thus improves the charge-discharge performance of a lithium-sulfur battery.
Disclosure of Invention
In order to solve the problems existing in the background, the invention provides an MXene-based composite material, which aims to solve the problems of poor structural stability of the transition metal chalcogenide and MXene self-accumulation, and modify the surface of the polyolefin diaphragm to improve the performance of the lithium-sulfur battery.
The invention aims to provide a preparation method of an MXene-based composite material for improving the performance of a lithium-sulfur battery diaphragm. The method comprises the steps of stripping MAX phase materials to obtain MXene, adding a molybdenum source, a tin source and a sulfur source, growing by a hydrothermal method to form a composite structure, and then carrying out polymerization and carbonization treatment on dopamine to obtain MXene/MoS 2 The material is/SnS @ C; finally, the composite material is coated on a commercial polyolefin base film to obtain the lithium-sulfur battery diaphragm with enhanced performance.
The technical scheme provided by the invention is as follows:
an MXene-based composite material for improving the performance of a lithium-sulfur battery diaphragm and a preparation method of a modified diaphragm comprise the following steps:
(1) Dissolving fluoride salt in acid solution, and adding Ti 3 AlC 2 The powder was continuously stirred.
(2) The solution was centrifuged, washed three times with dilute hydrochloric acid and repeatedly washed with deionized water until the pH of the supernatant was 6.
(3) Collecting the deposit, sequentially dispersing in anhydrous ethanol and deionized water, performing ice bath ultrasonic treatment in nitrogen environment, centrifuging, collecting the supernatant, and freeze drying to obtain MXene (Ti) with less layer 3 C 2 T x )。
(4) Dispersing MXene into deionized water, adding glucose, sodium molybdate dihydrate, sodium stannate tetrahydrate and thiourea under stirring, uniformly stirring, placing into a reaction kettle for hydrothermal reaction, centrifuging, repeatedly cleaning, and freeze-drying to obtain MXene/MoS 2 SnS composite material.
(5) Preparing a Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer solution, mixing the composite material obtained in the step (4) and dopamine hydrochloride according to a ratio of 1: 0-1, fully stirring, centrifuging, cleaning, and freeze-drying.
(6) The dried powder is subjected to high-temperature heat treatment for a certain time under the protection of inert gas to obtain a final product MXene/MoS 2 /SnS@C。
Preferably, in the step (1), the fluorine-containing salt includes lithium fluoride and sodium fluoride; the acid solution comprises 6-12M hydrochloric acid and 6-9M sulfuric acid; the fluorine-containing salt and Ti 3 AlC 2 The mass ratio of the powder is 1: 1.
As a preferable scheme, in the step (4), the mass ratio of MXene, glucose, sodium molybdate dihydrate, sodium stannate tetrahydrate and thiourea is 1: 1-5: 3-5: 2-8: 5-10.
Preferably, in the step (4), the hydrothermal reaction temperature is 160-190 ℃ and the reaction time is 10-20 h.
Preferably, in the step (6), the optimal temperature for the high-temperature heat treatment is 300 to 600 ℃, the heating rate is 2 to 5 ℃/min, and the heat treatment time is 2 to 4 hours.
Compared with the prior art, the technology of the invention has the advantages that:
(1) The MXene two-dimensional material has excellent conductivity, provides a large number of lithium-philic functional groups and a high specific surface area, has a good adsorption effect on polysulfide, and can provide more active sites for the material, inhibit a shuttle effect and accelerate catalytic conversion of polysulfide due to introduction of transition metal sulfide.
(2) The composite material formed by the transition metal sulfide nanosheets and MXene can inhibit stacking of few layers of MXene, a three-dimensional heterostructure is constructed, and the three-dimensional heterostructure is coated and carbonized by polydopamine, so that the circulation stability can be greatly improved.
(3) The diaphragm modified by the composite material has excellent conductivity and electrolyte wettability, enhances the charge transfer capacity, strongly adsorbs lithium polysulfide to prevent the lithium polysulfide from shuttling to a negative electrode to cause the generation of lithium dendrite, and greatly improves the stability and the safety of the battery.
Drawings
FIG. 1 shows MXene and MXene/MoS prepared in example 1 2 Scanning Electron Microscope (SEM) image of/SnS @ C material.
FIG. 2 is a comparative XRD pattern for examples 1, 2 and 3.
FIG. 3 is a graph showing the effects of adsorption experiments in examples 1, 2 and 3 and a blank control group.
FIG. 4 shows MXene/MoS prepared in example 4 2 Scanning Electron Micrograph (SEM) of/SnS @ C modified diaphragm.
FIG. 5 shows MXene/MoS prepared in example 4 2 Macroscopic picture of/SnS @ C modified diaphragm.
FIG. 6 shows MXene/MoS prepared in example 4 2 Contact angle test results of/SnS @ C modified diaphragm and commercial PP film.
Fig. 7 is a charge-discharge curve diagram of the assembled lithium-sulfur batteries of examples 7, 8 and 9 at a charge-discharge rate of 0.5C.
Fig. 8 is a charge-discharge curve diagram of the assembled lithium-sulfur batteries of examples 7, 8 and 9 at different charge-discharge rates.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying examples and drawings, in which, however, the invention is not limited.
The experimental procedures in the following examples are all conventional ones unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
MXene/MoS 2 Preparation of/SnS @ C composite material
(1) Dissolving 2.0g of lithium fluoride in 40mL of 12M hydrochloric acid aqueous solution, and adding 2.0g of Ti in the solution within 15-20 min under ice bath condition 3 AlC 2 And then stirred at 35 ℃. After etching, the solution is washed for 3 times by 1M hydrochloric acid and then washed by deionized water until the pH of the upper layer centrifugate is 6, and then the sediment is multi-layer MXene. Dispersing the mixture in an ethanol solution, carrying out ice bath ultrasonic treatment for 1h in a nitrogen environment, and cleaning the mixtureDispersing in deionized water, performing ice-bath ultrasonic treatment for 0.5h in a nitrogen environment, and freeze-drying the supernatant to obtain small-layer MXene.
(2) Dispersing 50mg of MXene into deionized water, adding 150mg of glucose, adding 100mg of sodium molybdate dihydrate, 150mg of sodium stannate tetrahydrate and 450mg of thiourea, stirring for 30min, putting into a reaction kettle, reacting for 20h at 190 ℃, centrifugally cleaning for 5 times by using deionized water after reaction, and freeze-drying to obtain MXene/MoS 2 a/SnS material.
(3) Preparing a trihydroxymethyl aminomethane hydrochloride (Tris-HCl) buffer solution, then adding 100mg dopamine hydrochloride and the materials, stirring for 12h, centrifugally cleaning for 3 times by deionized water, freeze-drying, and sintering a dried product for 2h at 550 ℃ in a tubular furnace under the atmosphere of argon to obtain MXene/MoS 2 The material is/SnS @ C.
Prepared MXene and MXene/MoS 2 The shape of the/SnS @ C material is shown in figure 1, MXene (figure 1 a) is a single-layer corrugated sheet structure, and MoS grows in situ 2 And after SnS, the MXene surface is covered by a lamellar structure, so that self-stacking of MXene materials is avoided, and a three-dimensional space structure is formed between layers (figure 1 b).
Prepared MXene and MXene/MoS 2 The XRD of the/SnS @ C material is shown in figure 2, the characteristic peak of 6 degrees in the figure confirms the successful synthesis of MXene material, and the characteristic peak of aluminum disappears, which indicates that the material does not contain unetched Ti 3 AlC 2 Impurities. By comparing standard PDF cards, MXene/MoS can be seen 2 The material/SnS @ C is successfully synthesized.
Example 2
MXene/MoS 2 Preparation of @ C composite
MXene/MoS was obtained by adding 250mg of sodium molybdate and no sodium stannate under the same conditions as in example 1 2 @ C composite.
Example 3
Preparation of MXene @ C composite material
(1) Dissolving 2.0g of lithium fluoride in 40mL 12M hydrochloric acid solution, and adding 2.0g of Ti within 15-20 min under ice bath condition 3 AlC 2 And then stirred and etched at 35 ℃ for 48h. Carving toolAfter etching, the solution is washed 3 times by 1M hydrochloric acid and then washed by deionized water until the pH of the upper centrifugate is 6, and then the precipitate is multi-layer MXene. Dispersing the MXene in an ethanol solution, carrying out ice bath ultrasonic treatment for 1h in a nitrogen environment, cleaning, dispersing in deionized water, carrying out ice bath ultrasonic treatment for 0.5h in the nitrogen environment, carrying out ultrasonic treatment, taking supernatant, and carrying out freeze drying to obtain the layered MXene.
(2) Preparing Tris-HCl buffer solution, then adding 100mg of dopamine hydrochloride and MXene, stirring for 12h, centrifugally cleaning for 3 times by deionized water, freeze-drying, and carrying out heat treatment on a dried product for 2h at 550 ℃ in a tubular furnace under the argon atmosphere to obtain the MXene @ C material.
FIG. 3 is a graph showing the effects of adsorption experiments on the materials prepared in examples 1, 2 and 3. The method comprises the following specific steps: mixing Li 2 S and S 8 Dispersed in a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) according to a molar ratio of 1: 5. Heating the mixed liquid to 60 ℃ and keeping the temperature for 24 hours, wherein the color of the solution gradually changes to dark reddish brown to obtain Li 2 S 6 And (3) solution. Weighing different samples with equal mass to be added into Li 2 S 6 (5 mM) in the solution, the solution was sealed and left to stand, and the color of the solution was observed to change. MXene possesses a large number of lithium-philic functional groups and a large specific surface area, and has a good adsorption capacity for polysulfides, so that the solution color becomes clear (FIG. 3 b). MXene/MoS 2 @ C (FIG. 3C) showed no significant color change compared to the blank control (FIG. 3 a), indicating poor adsorption of polysulfides. MXene/MoS 2 The adsorption effect of/SnS @ C is shown in FIG. 3d, and a clear solution shows that it still retains the adsorption capacity for polysulfides no inferior to MXene after addition of a large amount of active substance.
Example 4
MXene/MoS 2 Preparation of/SnS @ C material modified lithium-sulfur battery diaphragm
MXene/MoS obtained in example 1 2 Mixing and grinding the/SnS @ C material, a conductive agent (Super P) and a binder (PVDF) according to the proportion of 5: 4: 1 for 10min, adding an N-methylpyrrolidone (NMP) solution, continuously and uniformly grinding, then coating the slurry on a commercial PP diaphragm substrate, placing the commercial PP diaphragm substrate in an oven and drying at 50 ℃ to obtain a modified PP diaphragm。
SEM images of the prepared modified separator before and after charge and discharge cycles are shown in fig. 4a and 4b, respectively. It can be seen that the material was uniformly coated on the separator and the uniformity of the material was maintained after 200 cycles of charge and discharge at a charge and discharge rate of 0.5C. Fig. 4c is an SEM image of a cross section of the separator, and it can be seen that the coating thickness of the material is 10 μm.
A macroscopic picture of the prepared modified membrane is shown in fig. 5. It can be seen that the modified diaphragm still maintains the original flexibility, and the material cannot fall off due to bending.
The contact angle data graph of the prepared modified separator and the commercial PP film is shown in fig. 6, the contact angle of the modified separator (fig. 6 a) is close to 0 °, compared with the contact angle of the commercial PP film being 32 °, which shows good wettability of the modified separator with the electrolyte.
Example 5
MXene/MoS 2 Preparation of @ C material modified lithium-sulfur battery diaphragm
MXene/MoS obtained in example 2 2 Mixing and grinding the @ C material, a conductive agent (Super P) and a binder (PVDF) according to the ratio of 5: 4: 1 for 10min, adding an NMP solution, continuously and uniformly grinding, then coating the slurry on a commercial PP diaphragm substrate, and placing the commercial PP diaphragm substrate in an oven to dry at 50 ℃ to obtain the modified diaphragm.
Example 6
Preparation of MXene @ C material modified lithium-sulfur battery diaphragm
Mixing MXene @ C material obtained in example 3, a conductive agent (Super P) and a binder (PVDF) according to a ratio of 5: 4: 1, grinding for 10min, adding an NMP solution, continuously and uniformly grinding, then coating the slurry on a commercial PP diaphragm substrate, and placing the commercial PP diaphragm substrate in an oven to dry at 50 ℃ to obtain the modified diaphragm.
Example 7
MXene/MoS 2 the/SnS @ C composite material is applied to the lithium-sulfur battery.
The modified separator obtained in example 4 was assembled with a sulfur/macroporous carbon (S/HPC) positive electrode and a lithium negative electrode into a lithium sulfur battery, and 20 μ L of the electrolyte was added to the negative electrode side and 25 μ L was added to the positive electrode side, and the assembled battery was left to stand for 10 hours and then subjected to electrochemical test.
Example 8
MXene/MoS 2 Application of @ C composite material to lithium-sulfur battery
The modified separator obtained in example 5 was assembled with a sulfur/macroporous carbon (S/HPC) positive electrode and a lithium negative electrode to form a lithium-sulfur battery, and 20 μ L of the electrolyte was added to the negative electrode side and 25 μ L was added to the positive electrode side, and the assembled battery was allowed to stand for 10 hours and then subjected to electrochemical testing.
Example 9
Application of MXene @ C composite material to lithium-sulfur battery
The modified separator obtained in example 6 was assembled with a sulfur/macroporous carbon (S/HPC) positive electrode and a lithium negative electrode into a lithium sulfur battery, and 20 μ L of the electrolyte was added to the negative electrode side and 25 μ L was added to the positive electrode side, and the assembled battery was left to stand for 10 hours and then subjected to electrochemical test.
FIG. 7 is a graph of electrochemical data of the assembled lithium-sulfur batteries of examples 7, 8 and 9 at a charge/discharge rate of 0.5C, after 200 cycles of charge/discharge, MXene/MoS 2 The specific capacity of the lithium-sulfur battery assembled by the/SnS @ C diaphragm modified material is 648mAh/g, which is higher than MXene/MoS 2 Specific capacities of @ C (552 mAh/g) and MXene @ C (455 mAh/g).
Fig. 8 is a graph of electrochemical data of the assembled lithium-sulfur batteries of examples 7, 8 and 9 at different charge and discharge rates. MXene/MoS calculated from the discharge curves 2 The lithium-sulfur battery corresponding to/SnS @ C has a specific capacity of 690mAh/g under a charge-discharge rate of 4C, which is much higher than MXene/MoS 2 The specific capacities of the materials of @ C and MXene @ C (458 mAh/g and 302mAh/g respectively) are higher than that of the MXene @ C, and particularly, the specific capacity of the target composite material is 2 times higher than that of the MXene @ C.
The above results indicate that MXene/MoS 2 the/SnS @ C composite material still has excellent charge and discharge performance under high current density corresponding to a battery, so that the composite material has huge application potential.
Claims (6)
1. A preparation method of an MXene-based composite material for improving the performance of a lithium-sulfur battery diaphragm is characterized by comprising the following steps:
(1) Dissolving fluorine-containing salt in acid solutionThen adding Ti 3 AlC 2 The powder was continuously stirred.
(2) The solution was centrifuged three times with dilute hydrochloric acid and repeatedly washed with deionized water until the pH of the supernatant was 6.
(3) Collecting the deposit, sequentially dispersing in anhydrous ethanol and deionized water, performing ice bath ultrasonic treatment in nitrogen environment, centrifuging, collecting the supernatant, and freeze drying to obtain MXene (Ti) with less layer 3 C 2 T x )。
(4) Dispersing MXene into deionized water, adding glucose, sodium molybdate dihydrate, sodium stannate tetrahydrate and thiourea under stirring, uniformly stirring, placing into a reaction kettle for hydrothermal reaction, centrifuging, repeatedly cleaning, and freeze-drying to obtain MXene/MoS 2 SnS composite material.
(5) Preparing a Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer solution, mixing the composite material obtained in the step (4) with dopamine hydrochloride according to the ratio of 1: 0-1, fully stirring, centrifuging, cleaning, and freeze-drying.
(6) The dried powder is subjected to high-temperature heat treatment for a certain time under the protection of inert gas to obtain a final product MXene/MoS 2 /SnS@C。
2. The method for preparing the MXene-based composite material for improving the performance of the lithium-sulfur battery separator according to claim 1, wherein in the step (1), the fluorine-containing salt comprises lithium fluoride and sodium fluoride; the acid solution comprises 6-12M hydrochloric acid and 6-9M sulfuric acid; containing fluoride salt and Ti 3 AlC 2 The mass ratio of the powder is 1: 1.
3. The preparation method of the MXene-based composite material for improving the performance of the lithium-sulfur battery diaphragm, according to the claim 1, is characterized in that in the step (4), the mass ratio of MXene, glucose, sodium molybdate dihydrate, sodium stannate tetrahydrate and thiourea is 1: 1-5: 3-5: 2-8: 5-10.
4. The method for preparing the MXene-based composite material for improving the performance of the lithium-sulfur battery separator according to claim 1, wherein in the step (4), the hydrothermal reaction temperature is 160-190 ℃ and the reaction time is 10-20 h.
5. The method for preparing the MXene-based composite material for improving the performance of the lithium-sulfur battery separator according to claim 1, wherein in the step (6), the optimal temperature for the high-temperature heat treatment is 300-600 ℃, the heating rate is 2-5 ℃/min, and the heat treatment time is 2-4 h.
6. An MXene-based composite material for improving the performance of a lithium-sulfur battery separator prepared by the preparation method of any one of claims 1 to 5, wherein the MXene/MoS is 2 the/SnS @ C material is attached to the surface of one side of a commercial PP diaphragm and is assembled into a lithium-sulfur battery together with a sulfur/macroporous carbon (S/HPC) positive electrode and a lithium negative electrode, and one side of the attached composite material is close to the positive electrode, so that the performance of the lithium-sulfur battery is improved.
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