CN112585783A - Transition metal sulfide-based material for lithium sulfur battery - Google Patents
Transition metal sulfide-based material for lithium sulfur battery Download PDFInfo
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- -1 Transition metal sulfide Chemical class 0.000 title claims abstract description 115
- 239000000463 material Substances 0.000 title claims abstract description 109
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 65
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- 238000000034 method Methods 0.000 claims abstract description 55
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- 239000002904 solvent Substances 0.000 claims abstract description 26
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- 238000011068 loading method Methods 0.000 claims abstract description 13
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- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims description 84
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 83
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- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical group [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 6
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
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- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
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- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- XCUPBHGRVHYPQC-UHFFFAOYSA-N sulfanylidenetungsten Chemical compound [W]=S XCUPBHGRVHYPQC-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a method for synthesizing a transition metal sulfide-based carbon material for use as an electrode in a lithium sulfur battery. The method includes providing a solution comprising a group VI transition metal sulfide precursor and a solvent, immersing the carbon fiber material in the solution to form a mixture, and applying a temperature of 200 ℃ to 300 ℃ to the mixture to enable loading of the transition metal sulfide onto the carbon fiber material; and drying the supported carbon fiber material to obtain a supported carbon material based on a transition metal sulfide. The invention also relates to a transition metal sulphide based carbon material and a transition metal sulphide based carbon electrode material for a lithium sulphur battery.
Description
Cross Reference to Related Applications
This application claims priority to singapore patent application No.10201807048V filed on 20/8/2018, the entire contents of which are incorporated herein by reference.
Technical Field
The present invention relates to a transition metal sulfide-based material, a method of synthesizing a transition metal sulfide-based material, and a method of preparing a transition metal sulfide-based electrode material. In particular, the present invention relates to a transition metal sulphide based carbon fibre material, a method of synthesizing a transition metal sulphide based carbon fibre material and a method of preparing a transition metal sulphide based carbon electrode material.
Background
Global demand for energy is expected to increase in the coming decades. Although many advances have been made in alternative sources for energy production over the past century, it can be said that advances in energy storage have not kept pace. This is particularly critical since most renewable energy sources (e.g., solar, wind, hydroelectric) are periodic and intermittent. Thus, there is a need for advanced storage systems that are capable of delivering energy from batteries in small portable devices to high-energy grid-level storage systems when needed. Among the various rechargeable battery systems that are likely to exceed the existing Lithium Ion Batteries (LIBs), lithium-sulfur batteries have since the pioneering work on carbon-sulfur cathodes described by xiuli Ji et al in the publication Nature Materials 8,500-(LSB) has attracted the most attention. High theoretical specific capacity of sulfur cathode (1673mAh g)-1) Is an order of magnitude larger than a typical LIB cathode and provides up to 2500Wh kg-1Which is several times that of the existing LIB. In addition, sulfur is both inexpensive and abundant. The LSB is combined with a suitable cathode body which can be mass produced, so that it is possible to manufacture the LSB at a much lower cost.
However, the LSB itself presents some challenges. These challenges include the electrical insulating properties of the charge and discharge products that prevent full utilization of sulfur, and the potential for volumetric expansion during discharge cycles that can lead to cathode structural damage (z.w.seh et al, chem.soc.rev.,2016,45, 5605-. However, the most important challenge involves the loss of active sulfur by the dissolution of polysulfides through the polysulfide shuttling effect (z.w.seh et al, chem.soc.rev.,2016,45, 5605-. Thus, suitable host materials must inhibit lithium polysulfide (LiPS) dissolution by providing physical or chemical trapping, but not at the expense of conductivity.
It is therefore desirable to provide a transition metal sulphide based material and a method for synthesizing the material, in an attempt to address at least one of the problems described above, or at least to provide an alternative.
Disclosure of Invention
According to a first aspect of the present invention, there is provided a method of synthesizing a transition metal sulfide-based carbon material for use as an electrode in a lithium sulfur battery. The method includes providing a solution comprising a group VI transition metal sulfide precursor and a solvent; immersing a carbon fiber material in the solution to form a mixture; applying a temperature of 200 ℃ to 300 ℃ to the mixture to enable the transition metal sulphide to be loaded onto the carbon fibre material; and drying the supported carbon fiber material to obtain a supported carbon material based on a transition metal sulfide.
In one embodiment, the transition metal sulfide precursor is selected from the group consisting of ammonium tetrathiomolybdate and ammonium tetrathiotungstate.
In one embodiment, the transition metal sulfide is selected from the group consisting of molybdenum disulfide and tungsten disulfide.
In one embodiment, the method further comprises annealing the transition metal sulfide based supported carbon material to form a transition metal sulfide based supported semiconducting carbon material.
In one embodiment, the method further comprises preparing an electrode for a lithium sulfur battery using the transition metal sulfide-based supported carbon fiber material, wherein the preparing comprises: mixing and heating sulfur and carbon black to obtain a sulfur-carbon black mixture; mixing a sulfur-carbon black mixture with a binder and a solvent to obtain a sulfur-containing slurry; depositing a sulfur-containing slurry onto a transition metal sulfide-based supported carbon material; and drying the transition metal sulfide-based supported carbon material to obtain a transition metal sulfide-based sulfur-supported carbon electrode.
According to a second aspect of the present invention, there is provided a transition metal sulphide based carbon material. The transition metal sulfide-based carbon material comprises a carbon fiber material and a group VI transition metal sulfide selected from the group consisting of molybdenum disulfide and tungsten disulfide, wherein the transition metal sulfide is supported on the carbon fiber material.
According to a third aspect of the present invention, there is provided a transition metal sulphide based carbon electrode. The transition metal sulfide-based carbon electrode comprises the transition metal sulfide-based carbon material of the present invention loaded with sulfur.
According to a fourth aspect of the present invention, a lithium sulfur battery is provided. The lithium-sulfur battery includes an anode and a cathode, wherein the cathode contains the transition metal sulfide-based carbon material of the present invention supporting sulfur.
Drawings
The above advantages and features of materials and methods according to the present invention are described in the following detailed description and are shown in the accompanying drawings:
fig. 1 is a schematic diagram of the synthesis of a transition metal sulfide-based carbon material. The scheme shows phase and morphology control. FIG. 1(a) shows unmodified interwoven carbon fibers; FIG. 1(b) shows a metallic phase edge oriented sheet; FIG. 1(c) shows a semiconductor phase edge oriented sheet; fig. 1(d) shows metal phase basal plane oriented nanoplatelets.
FIG. 2 shows (a) MoS2And (b) WS2X-ray diffraction patterns of the 1T-edge, 2H-edge and 1T-basal plane of (a), wherein the spectra were normalized to the carbon (002) peak of the unmodified carbon cloth for comparison.
FIG. 3 shows (a) bare unmodified carbon fiber cloth, (b-d) structured MoS2And (e-g) WS2SEM image of morphology of material.
FIG. 4 shows a 1T-edge polytype MoS2Sulfur cathode and WS2A set of plots of the performance and characterization of the sulfur cathode. (a) Galvanostatic charge/discharge curves and (b) cyclic voltammogram after initial stabilization (v ═ 0.05mV · s-1) Shown as a control with unmodified sulfur-loaded carbon cloth; the key is as follows: MoS2Sulfur (dotted line), WS2Sulfur (dotted line), unmodified sulfur-loaded carbon cloth (solid line). (c) Lithium polysulphides were adsorbed, one cathode each being placed in 1mM Li2S4In DOL/DME solution. (d) In a solution containing 2% by weight of LiNO3Additive dissolved in 1:1(v/v) DOL/DME solution in 1M LiTFSI electrolyte at 0.1mA cm-2The first five activation cycles were performed and then at 0.2mA cm-2Circulate to the 1T-edge MoS2Sulfur (solid diamonds), WS2Sulfur (open circles) and sulfur-loaded carbon cloth controls (open squares) were subjected to cycling studies.
FIG. 5 shows a structured MoS based on different phases and morphologies2Sulfur and WS2Comparison of the cathodic performances of sulfur. Graphs (a, c) are rate stability at increasing area current; 1T-edge (solid squares), 2H-edge (solid diamonds), 1T-basal (open circles), unmodified (open squares). The graphs (b, d) are cyclic voltammograms of a TMD-sulfur cathode, shown with unmodified sulfur-loaded carbon cloth as a control (v ═ 0.05mV · s-1) (ii) a 1T-edge (solid line), 2H-edge (short dashed line), 1T-basal plane (long dashed line), unmodified (dotted line). Structured (e) MoS2-sulfur and(f)WS2cycling performance of sulfur cathodes.
Fig. 6 shows (a) a constant current charge/discharge curve; and (b) at 4.1mg(S)·cm-2At high sulfur loading, 1T-edge MoS2Cycling performance of sulfur cathodes. Conditions are as follows: at 0.5mA cm-2The first five activation cycles were performed, followed by 1.0mA cm-2Circulating; the electrolyte solution contains 2 wt% of LiNO31M LiTFSI electrolyte of additives dissolved in 1:1(v/v) DOL/DME solution.
FIG. 7 shows a control MoS without sulfur loading2Cyclic voltammogram of the cathode. No reaction corresponding to the lithium-sulfur system was observed, nor was MoS observed2Intercalation/conversion reaction.
FIG. 8 shows a sulfur loaded structured (a) MoS2Cathode and (b) WS2Electrochemical impedance spectrum (nyquist plot) of cathode after charge/discharge cycles (forty cycles) at about 2.3V (vs. Li/Li)+) Obtained with an amplitude of 10mV at a typical open circuit potential.
Fig. 9 shows the relationship between (a) specific capacity and (b) area capacity obtained on an unmodified carbon cloth and the current C rate employed. (c) The sulfur content in the surface of the product is 4.6mg(S)·cm-2The rate stability of the unmodified carbon cloth of (1).
Detailed Description
In one aspect of the invention, a method of synthesizing a transition metal sulfide-based carbon fiber material for use as an electrode in a lithium sulfur battery or cell is provided. The method includes providing a solution comprising a group VI transition metal sulfide precursor and a solvent; the carbon fiber material is immersed in the solution to form a mixture, and an elevated temperature of 200 ℃ to 300 ℃ is applied to the mixture to enable the transition metal sulfide to be supported on the carbon fiber material. The supported carbon fiber material is then dried to obtain a transition metal sulphide based supported carbon fiber material.
As used herein, group VI transition metal sulfides include those selected from the group consisting of chromium (Cr), molybdenum (Mo), tungsten (W), and
(seborgium, Sg) group VI transition metal sulfide.
In one embodiment, the group VI transition metal sulfide precursor is ammonium tetrathiomalate selected from the group consisting of ammonium tetrathiomolybdate and ammonium tetrathiotungstate. The solvent used to dissolve the precursor can be any suitable solvent or combination of solvents so long as the solvent or combination of solvents is capable of completely dissolving the precursor. Examples of suitable solvents include, but are not limited to, Dimethylformamide (DMF), deionized water, or a combination thereof.
In one embodiment, the carbon fiber material is a woven material having multiple interwoven carbon fibers. Any suitable type of carbon fiber and any suitable type of process may be used to prepare the carbon fiber material. Examples of such carbon fibers include, but are not limited to, carbon fibers produced from extruded polyacrylonitrile or from carbonization of other polymeric materials. Carbon fibers resulting from carbonization of extruded polyacrylonitrile are preferred because of their high electrical conductivity (comparable to graphite, about 102S/m to 105S/m). Other suitable methods include, but are not limited to, electrospinning followed by carbonization. In one embodiment, the woven material is prepared by weaving individual carbon fibers into a porous cloth-like material. The porosity of the porous cloth-like material may vary, provided that the cloth-like material is capable of substantially absorbing the precursor solution, if the cloth-like material is not capable of completely absorbing the precursor solution. The cloth-like material may be in the form of a cloth, screen, mat or net. In one embodiment, the carbon fiber material is a porous carbon cloth.
In some embodiments, the carbon fibers have an average filament diameter of 5 μm to 10 μm. Finer filaments having an average diameter of at least 100nm may also be used. Preferably, the total thickness of the carbon fiber material is from 100 μm to 500 μm, with an upper limit of about 1mm, since any thickness exceeding 1mm may prevent a uniform loading of the metal sulfide throughout the carbon fiber material. It will be appreciated that the carbon fiber material may have any suitable size and shape. In an exemplary embodiment, the carbon fiber material has dimensions of 5cm by 10 cm. Although each size is typically less than 15cm, one skilled in the art will appreciate that other sizes of carbon fiber material may be used as long as the carbon fiber material is fully immersed in the solution when contained in the autoclave apparatus used for synthesis.
In one embodiment, the carbon fiber material is immersed in the solution for a sufficient time to enable complete wetting of the carbon fiber material in the solution. The carbon fiber material is then transferred to an autoclave apparatus with the solution. In an autoclave apparatus, a high temperature of 200 ℃ to 300 ℃ is applied to the mixture for a predetermined period of time to enable the transition metal sulfide to be supported on the carbon fiber material. Under high temperature processes, transition metal sulfide precursors decompose and deposit themselves as metal sulfides on the surface of the carbon fiber material. The deposited metal sulfide forms a coating on the carbon fiber material. The mixture is then allowed to cool, the loaded carbon fiber material is removed and rinsed, and the material is then dried to obtain the desired transition metal sulfide-based loaded carbon material.
In one embodiment, the transition metal sulfide is selected from the group consisting of molybdenum disulfide and tungsten disulfide. The transition metal sulfide deposited or supported on the carbon fiber material is crystalline in nature, and the crystals may be in the form of edge or basal orientation.
As used herein, the term "edge orientation" refers to an orientation in which the crystal structure of the transition metal sulfide is aligned in a vertical position substantially perpendicular to the surface of the carbon fiber material.
As used herein, the term "basal plane orientation" refers to an orientation in which the crystal structure of the transition metal sulfide is aligned in a horizontal position parallel to the surface of the carbon fiber material.
In some embodiments, the transition metal sulfide based loaded carbon material is loaded with edge oriented molybdenum disulfide or basal oriented molybdenum disulfide. In other embodiments, the transition metal sulfide based loaded carbon fiber material is loaded with edge oriented tungsten disulfide or basal oriented tungsten disulfide.
The supported carbon material may be dried using any suitable method. Drying is carried out to remove the residual solvent. Some examples of such drying methods include, but are not limited to, heating the supported carbon material at an elevated temperature in an oven at ambient pressure, or heating the supported carbon material in a vacuum at reduced pressure, or heating the supported carbon material at a combination of elevated temperature and reduced pressure. In one embodiment, the supported carbon material is dried under vacuum at a temperature in the range of about 40 ℃ to 100 ℃, preferably 50 ℃ to 70 ℃.
In another embodiment, the carbon fiber material is immersed in a solvent contained in the solution prior to the step of providing the solution comprising the group VI transition metal sulfide precursor and the solvent. In this embodiment, the solvent comprises cetyltrimethylammonium bromide dissolved in deionized water. The supported carbon material based on a transition metal sulfide obtained in this embodiment is loaded with basal plane oriented molybdenum disulfide.
The supported carbon material based on transition metal sulfides formed by the process of the present invention is a metallic phase. The carbon material supporting the metal phase may be converted to a semiconducting phase and the conversion process accomplished by annealing the transition metal sulfide based supported carbon material under suitable conditions to form a transition metal sulfide based supported semiconducting carbon material. Any suitable annealing conditions may be employed in this step. In one embodiment, annealing comprises thermally annealing the transition metal sulfide based supported carbon material in a furnace under a flow of argon, heating at a rate of 0.5 ℃/min to 10 ℃/min, preferably at a rate of 3 ℃/min. In various embodiments, the thermal annealing is performed at a temperature in the range of 250 ℃ to 400 ℃, preferably 280 ℃ to 350 ℃, for about 1 hour to 3 hours, preferably 1.5 hours to 2.5 hours, to form a semiconductor phase.
The method of the present invention may further comprise preparing an electrode for a lithium sulfur battery using the transition metal sulfide-based supported carbon material synthesized by the method of the present invention. The preparation involves mixing sulfur and carbon black and heating at a temperature of 150 ℃ to 180 ℃, preferably 155 ℃ to 160 ℃, to form a sulfur-carbon black mixture. The sulfur-carbon black mixture is further mixed with an organic solvent and a binder to form a sulfur-containing slurry. Any suitable organic solvent may be used to prepare the sulfur-containing slurry. Suitable solvents include, but are not limited to, N-methyl-2-pyrrolidone or similar solvents. Any suitable binder may be used to prepare the sulfur-containing slurry. Examples of such binders include, but are not limited to, polymers such as polyvinylidene fluoride. While polyvinylidene fluoride and N-methyl-2-pyrrolidone are the preferred binder/solvent combinations, other binder/solvent combinations can be used as long as the binder is soluble in the solvent.
The method further comprises depositing a sulfur-containing slurry onto the transition metal sulfide-based supported carbon material; and drying the transition metal sulfide-based supported carbon material to obtain a transition metal sulfide-based sulfur-supported carbon electrode. In one embodiment, a transition metal sulfide-based sulfur-loaded carbon electrode is used as a cathode in a lithium sulfur battery.
The method may further comprise a further heating step of removing excess surface sulfur from the sulfur-carbon black mixture prior to producing and depositing a sulfur-containing slurry onto the transition metal sulfide-based supported carbon material. In one embodiment, excess surface sulfur is removed by heating the sulfur-carbon black mixture in a stream of argon at a temperature of 160 ℃ to 300 ℃ for about 2 hours to 4.5 hours.
The method further includes repeating the depositing and drying steps several times to achieve a desired amount of sulfur on-surface. This step enables the surface sulfur loading to be adjusted to a desired level. In the present invention, the surface sulfur loading amount can be adjusted to 1.5mg cm by increasing the number of deposition-drying cycles-2To 5.5 mg.cm-2。
In a second aspect of the present invention, there is provided a transition metal sulphide based carbon material produced by a method according to the first aspect. The transition metal sulfide-based carbon material comprises a carbon fiber material and a group VI transition metal sulfide selected from the group consisting of molybdenum disulfide and tungsten disulfide, wherein the transition metal sulfide is supported on the carbon fiber material. The transition metal sulfide is supported on the carbon fiber material by forming nanocrystals on the surface of the carbon fiber material.
In various embodiments, the carbon fiber material is a woven material having multiple interwoven carbon fibers. The woven material is porous. In one embodiment, the woven material is a porous cloth-like material. The cloth-like material may be in the form of a cloth, screen, mat or net. In one embodiment, the carbon fiber material is a porous carbon cloth.
In some embodiments, the transition metal sulfide based carbon material is loaded with edge oriented molybdenum disulfide or basal oriented molybdenum disulfide. In other embodiments, the transition metal sulfide based carbon material is loaded with edge oriented tungsten disulfide or basal oriented tungsten disulfide. Transition metal sulfide-based carbon materials are useful as electrodes in energy storage devices, such as batteries or battery cells.
In a third aspect, a transition metal sulfide-based carbon electrode is provided. The transition metal sulfide-based carbon electrode comprises the transition metal sulfide-based carbon material of the present invention loaded with sulfur.
In a fourth aspect, there is provided a lithium sulfur battery comprising the transition metal sulfide-based carbon material of the present invention. The lithium-sulfur battery includes an anode and a cathode, wherein the cathode contains the transition metal sulfide-based carbon material of the present invention supporting sulfur.
The process of the present invention was developed for the controlled synthesis of group VI transition metal disulfides on carbon fiber materials using a "bottom-up" approach. The transition metal sulfide-based carbon material produced by the method of the present invention can be used as a cathode material in a lithium sulfur battery or a battery cell for increasing the surface sulfur loading amount and the surface capacity. In the process of the present invention, three main properties of the material are controllable, including: (1) a phase (metal phase or semiconductor phase) of a carbon material; (2) morphology (edge orientation or basal orientation of the transition metal disulfide relative to the surface of the carbon fiber material); and (3) elemental composition (based on molybdenum sulphide or on tungsten sulphide) supported on a carbon fibre material.
The synthetic transition metal sulfide-based carbon materials can be used as cathodes in lithium sulfur batteries or cells, wherein the phase, morphology, and composition of the transition metal disulfide host material exhibits an overall positive effect on polysulfide capture, thereby improving long-term cyclability of the battery or cell. Rate stability can also be maintained at increased currents due to the high conductivity of the metal phase. Batteries or battery cells prepared using the transition metal sulfide-based carbon materials of the invention (molybdenum sulfide (MoS) for metal edge orientation2) Exhibits excellent long-term cycle performance at 0.2mA cm-2Having a coulombic efficiency of more than 95% and 930mAh g after 100 cycles-1The capacity of (c). The battery or battery cell can also maintain stability under higher current loads, wherein the current load is 2.0mA cm-2When the specific capacity is higher than 1000 mAh.g-1. According to the method of the present invention, the sulfur loading can be increased to increase the dough capacity, and the dough capacity can be increased to 4mg(S)·cm-2Capacity of (2) and 1mA · cm-2Discharge of current to obtain 4.0mAh cm-2The capacity of (c). The process of the present invention is unique in that the Transition Metal Disulfide (TMD) host is distinct from the sulfur loaded. This is in contrast to those systems available in the prior art, where exfoliated TMD nanosheets are physically mixed with sulfur and used directly as a cathode on aluminum foil, or molybdenum disulfide (MoS) is used2) The nanosheets are used to physically coat the sulfur particles. Furthermore, the use of carbon fiber materials ensures long distance conduction paths for both electrons and Li ions, thus avoiding sulfur and Li2The insulating properties of S, while the flexibility of the carbon material fibers prevents structural damage during expansion (discharge) cycles. This highlights the ever most important paradigm shift for physical encapsulation of sulfur.
Advantageously, the techniques proposed in the present invention combine and exploit the following respective benefits: (1) using a metal sulfide host for trapping polysulfides and thereby improving the life and performance of a lithium sulfur battery cathode; (2) porous carbon fiber materials are used as a means to increase the amount of sulfur on the face, thereby increasing the face capacity, over conventional methods for slurry-based cathodes on aluminum foil. The method is suitable for large-scale industrial production of the carbon fiber material based on the transition metal sulfide by means of a bottom-up solvent thermal synthesis method. The process of the present invention gives full control and adjustment of physical properties (phase, morphology and composition) in the synthesis of transition metal sulfides, whereas the same level of control cannot be achieved using top-down approaches known in the art.
In order that the invention may be more readily understood, the following specific examples are given. The following examples should in no way be construed as limiting or restricting the full scope of the invention. Those skilled in the art will recognize that the examples set forth below are not exhaustive of embodiments of the invention.
Examples
Example 1
Synthesis of metal phase edge oriented Transition Metal Disulfides (TMD)
Synthesis of metallic 1T-edge oriented molybdenum disulfide (MoS) by one pot solvothermal synthesis2) Sample and 1T-edge oriented tungsten disulfide (WS)2) Samples (see FIG. 1, schemes 1a-1 b).
Ammonium tetrathiomolybdate ((NH) was stirred4)2MoS4375mg) was dissolved in a 2:1(v/v) mixture of Dimethylformamide (DMF) and deionized water (70mL) to give a reddish brown solution. A5 cm by 10cm piece of carbon cloth was immersed in the solution with a brief sonication. The solution was stirred slowly for 30 minutes to ensure complete wetting of the carbon cloth by the solution. The mixture was then transferred to a PTFE-lined stainless steel autoclave and the mixture was held at a temperature of 200 ℃ for about 12 hours. Naturally cooling to room temperature, and taking out the MoS on the metal edge2Carbon cloth, rinsed five times with deionized water and ethanol, then dried under vacuum at 60 ℃ overnight. The samples obtained were labeled as MoS 21T-edge.
For the synthesis of metal-edged tungsten disulphide (WS)2) Ammonium tetrathiotungstate ((NH)4)2WS4375mg) instead of ammonium tetrathiomolybdate in DMF (70mL) and all other steps were takenRemain unchanged. Marking the obtained sample as WS 21T-edge.
For MoS2And WS2Average mass of about 2mg cm-2. Prior to synthesis, all carbon cloths were first washed sequentially in ethanol, deionized water and acetone, sonicated for about 10 minutes each, and vacuum dried at 60 ℃ overnight.
Example 2
Synthesis of semiconductor phase edge oriented TMD
FIG. 1, schemes 1b-1c show the phase transition of transition metal sulfide based carbon materials from the metallic 1T-edge polytype to the semiconductor polytype (denoted as the 2H-edge).
Example 3
Synthesis of metal phase basal plane oriented TMD
MoS assisted by surfactants2Hydrothermal synthesis of (1T-basal plane oriented molybdenum disulfide) (MoS)2)。
Cetyl trimethylammonium bromide (CTAB, 1.275g, 50mmol L)-1) Dissolved in deionized water (70mL) with rapid stirring. A 5cm x 10cm piece of carbon cloth was immersed in the solution and stirred slowly for 30 minutes for uniform coverage. Ammonium tetrathiomolybdate ((NH) was then added4)2MoS4375mg) and dissolved with stirring. Finally, hydrazine monohydrate (N) is added dropwise2H4·H2O, 1.6mL) and stirred for a further 30 minutes. The mixture was then transferred to a PTFE-lined stainless steel autoclave and held at 200 ℃ for about 12 hours. The mixture was cooled to room temperature and,it was then rinsed five times with deionized water and ethanol and then dried under vacuum at 60 ℃ overnight. The samples obtained were labeled as MoS 21T-basal plane.
Preparation of metallic 1T-basal oriented tungsten disulfide (WS) by modified one-pot solvothermal synthesis2). For the synthesis of 1T-basal surfaces WS2Only ammonium tetrathiotungstate ((NH)4)2WS4375mg) was dissolved in a 2:1 volume mixture of DMF: water (70mL) and a 5cm by 10cm piece of carbon cloth was then introduced into the solution. The mixture was similarly transferred to a PTFE-lined autoclave and held at 200 ℃ for about 12 hours, then the mixture was cooled, rinsed five times with deionized water and ethanol, and the mixture was dried at 60 ℃. Marking the obtained sample as WS 21T-basal plane.
Example 4
Button cell production and electrochemical testing
Thus, MoS having different morphologies to be prepared2And WS2The polytype was applied as a sulfur host in an all-lithium sulfur battery cell and tested.
Sulfur was first added to carbon black (Ketjenblack) using a melt diffusion process at 160 ℃ to form a sulfur-carbon black mixture. Excess sulfur on the surface of the sulfur-carbon black mixture was removed by further heating the sulfur-carbon black mixture to 200 ℃ for 4 hours in a stream of argon. Then, a sulfur-carbon black mixture consisting of 90 wt% of sublimed sulfur in conductive carbon black (Ketjenblack) was used to prepare a sulfur-containing slurry. A sulfur-containing slurry was prepared by mixing the sulfur-carbon black mixture with N-methyl-2-pyrrolidone (NMP) and 10 wt% polyvinylidene fluoride (PVDF).
By this first loading of sulfur into porous carbon black (Ketjenblack) rather than directly into MoS2Or WS2The unique approach above, enables the proper study of their true polysulfide adsorption/catalysis since dissolved polysulfides are chemisorbed on exposed TMD surfaces rather than physically constrained by TMD.
Then directly connected with the carbon cloth materialDoctor blade deposition of the contacted sulfur-containing slurry formed a sulfur-loaded TMD-carbon cloth cathode (5 cm. times.5 cm), dried at 60 ℃ and then in dynamic vacuum overnight. The surface sulfur loading can be adjusted to 1.5 mg-cm by increasing the number of deposition-drying cycles-2To 5.5 mg.cm-2. The final sulfur-loaded carbon cloth material was then cut to fix a 12.7mm diameter cathode.
Standard 2032 type coin cells were used for cycling and stability testing of the cells. The assembly was carried out in an argon-filled glove box using TMD-carbon cloth material (diameter 12.7mm) each loaded with sulphur directly as the cathode, pure lithium foil as the anode/reference electrode, separated by a Celgard membrane, and an electrolyte of 1M LiTFSI dissolved in a 1:1 volume mixture of 1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME) and containing 2% by weight of LiNO3. The minimum amount of electrolyte was 12. mu.L mg(S) -1To 15 μ L mg(S) -1To ensure complete wetting. Constant current charge-discharge cycles were performed at 1.6V to 2.8V (vs. Li/Li +) using a bond CT2001 battery tester (Lanhe), and the obtained results are shown in fig. 4 (a). At 0.05mV s-1The cyclic voltammogram was obtained at the scanning rate of (a), and the obtained result is shown in fig. 4 (b). Electrochemical impedance spectroscopy was performed at 10mV amplitude at open circuit potential on an M204 Autolab potentiostat (Metrohm) equipped with a frequency response analyzer module, in the frequency range of 1MHz to 0.01 Hz.
Adsorption of lithium polysulphides
Using 1mM Li2S4The solution was subjected to lithium polysulfide (LipS) adsorption studies, the Li2S4The solution is prepared by reacting a stoichiometric amount (1:3) of Li at 60 ℃ in an inert atmosphere2S and elemental sulphur were reacted in a 1:1(v/v) mixture of DOL and DME, prepared by stirring the solution for one week to ensure complete dissolution. Each TMD/carbon cloth cathode (each 12.7mm in diameter) was then immersed in 2mL aliquots of Li2S4To the solution and left overnight.
Example 5
Structural characterization and Performance testing
Energy dispersive X-ray spectroscopy (EDS) (Oxford Instruments) was obtained at an acceleration voltage of 30kV using a field emission Scanning Electron Microscopy (SEM) performed on JSM-7400f (jeol). X-ray diffraction (XRD) was performed on D8 advance (bruker) with a Cu K α source, thermo-gravimetric analysis (TGA) was performed on Pyris 1 TGA (perkinelmer), and full scan (surfey) and high resolution nuclear grade X-ray photoelectron spectroscopy (XPS) were performed on ESCALAB220i-xl (vg scientific) with an Al K α X-ray source, calibrating the carbon 1s signal to 284.4 eV.
X-ray diffraction (XRD)
Characterization was performed to confirm that the correct TMD phase was obtained, first X-ray diffraction (XRD) was performed as a standard for identification of the exact polytype. FIG. 2a shows the MoS prepared2XRD pattern of (1), its peak is identical to natural 2H-MoS2(JCPDS card No. 37-1492). The unmodified carbon cloth shows two broad peaks at 2 θ ═ 25 ° and 44 °, corresponding to the (002) and (100)/(101) planes of graphite, respectively, which is shown as a mixture of the original graphite planes interspersed with a small amount of disordered carbon. X-ray photoelectron spectroscopy (XPS) further confirmed that most of the carbon was sp2 hybridized carbon at 284.4eV and that there was a very small amount of surface oxygen (table 1). 1T-edge MoS2A sharp (002) peak is shown at 9.1 deg., corresponding to about
Is different from that previously reported
To
1T-MoS2The materials were very consistent. This peak appears with the (004) second order diffraction peak at about 18.2 °. More importantly, the intensity of the (002) peak also indicates MoS2Strong vertical orientation of the edges of the lamellae.
Then, after annealing at 300 ℃, a semiconductor 2H-polytype was obtained which showed a complete disappearance of the 9.1 ° peak and a new (002) peak at 13.9 ° was produced. This confirms the conversion to the 2H-polytype with an interlayer spacing of
Approaching the expected bulk 2H MoS2Of (2) is
In contrast, the 1T-basal plane material exhibited a discrete (002) peak centered at 8.6 deg., indicating that the lamellar arrangement was more disordered and was
A slightly larger interlayer spacing.
Likewise, structured WS is similarly structured2XRD pattern and 2H-WS of material2(JCPDS card No.08-0237) the 1T-edge and 1T-basal polytypes each exhibited a (002) peak at about 9.2 ° and the second order diffraction peak of these peaks was at 18.3 °. Therefore, the interlayer spacing is estimated as
This is in contrast to previously reported 1T-WS2Is/are as follows
And (4) approximation. Furthermore, the intensity of the (002) peak of the 1T-edge material was enhanced compared to the 1T-basal material, indicating greater edge orientation. Annealing was similarly performed in an inert atmosphere to convert the 1T-edge polytype to the 2H-edge polytype, with the (002) peak moving to 11.6 °. In this case, the interval is
This is clearly greater than 2H-WS2Is expected to be spaced apart
And the wide FWHM may also be due to increased slice stacking randomness.
Further analysis is then performed to determine the chemical nature of the synthesized material. First, broad scan XPS was performed to obtain surface element compositions, and their values are listed in table 1 below. It is interesting to note that in all materials with a metal to sulfur ratio slightly below the theoretical stoichiometry 1:2, the surface is slightly sulfur-poor. However, this phenomenon is also observed in other prepared TMDs and may be beneficial in several electrocatalytic reactions previously reported. Unlike the surface-specific sensitivity of XPS technology, energy dispersive X-ray spectroscopy (EDS) is also used to study bulk composition. In this case, the materials all show a stoichiometry close to the expected 1:2 ratio, indicating that sulfur deficiency is limited to only the exposed top surface.
EDS spectra further confirmed that the synthesized TMD was well distributed on the carbon fibers. High resolution XPS scanning of the Mo3d region shows5/2And 3d3/2Bulk 2H-MoS with binding energies of 229.4eV and 232.5eV, respectively2In contrast, the 1T-polytype MoS23d of the Material5/2And 3d3/2The binding energy was slightly lower, about 228.6eV and 231.9eV, respectively. The binding energy was again raised to 229.1eV and 232.3eV for the 2H-polytype using annealing. After annealing, similarly, 2p of sulfur3/2The peak experienced a small lift from the initial 161.5 eV. XPS for both 1T-polytypes for tungsten sulfide shows W4 f at about 31.8eV and 33.9eV7/2And 4f7/2Peaks, which approximate the reported position of the 1T-phase. However, less than expected increase in binding energy was observed to occur upon annealing. Another pair of oxidized W (VI) peaks was noted at 35.5eV and 37.8 eV. This for exfoliated WS2Nanosheet or synthetic WS2Nanosheets are not uncommon because they have a high surface sensitivity to oxidation and thus may be the reason for the lack of significant lift-off after annealing.
Table 1: structured MoS based on X-ray photoelectron spectroscopy2And WS2The surface element composition of the carbon cloth cathode.
Scanning electronMicroscopy (SEM)
By confirming the composition and TMD polytype based on three characterization methods, we subsequently determined the morphology of the material using Scanning Electron Microscopy (SEM). The bare unmodified carbon fibers have thin longitudinal ridges along the surface as shown in fig. 3a, but the rest is smooth and interwoven in a grid structure as shown in the upper right drawing. In contrast, 1T-edge MoS2Polytype and 1T-edge WS2The polytypes (fig. 3b, fig. 3e) all appear as vertically oriented angled lamellae, whose growth is perpendicular to the surface of the carbon fiber material, which correlates well with the strong (002) XRD peak observed previously. Also note that MoS is a relatively small and dense network2In contrast, a single WS2Platelets are large, with a length of about 200nm to 300 nm. No significant morphological changes were observed after annealing to the 2H-edge (fig. 3c, fig. 3 f). This is in contrast to MoS2And WS2In contrast to the 1T-basal plane polytype, the 1T-basal plane polytype has a preferred lamellar/platelet orientation parallel to the carbon fiber surface (fig. 3d, fig. 3 g). Interestingly, a single WS2The platelets become larger, spanning up to 300nm, relative to MoS2Is usually 100nm or less.
2 2Performance and characterization of 1T-edge polytype MoS-Sulfur and WS-Sulfur cathodes
First, the MoS is compared2Sulfur cathode and WS2The 1T-edge polytype of the sulfur cathode (see results in fig. 4). Constant current charge and discharge measurement results (FIG. 4a) prove that the current density is 0.2mA cm-2At a current density of (1.5 mg (S) cm in terms of sulfur content)-2To a C rate of about 0.1C; molecular weight based on sulfur, 1C 1673mA · g-1) For 1T-edge MoS2And 1T-edge WS2The measured values were 1410mAh g, respectively-1And 1320mAh g-1Stable average specific capacity of (2). A representative characteristic dual-plateau discharge curve for the lithium sulfur system was observed at 2.3V (vs. Li/Li)+) Is sulfur/Li2S8Conversion to Li2S4Then a second plateau at 2.10V. The capacities of the two platforms are also closeTheoretical ratio 25:75, indicating complete discharge and conversion of the dissolved intermediate polysulfides to the final solid Li2And (4) obtaining an S product.
Further characterization by cyclic voltammetry is shown in fig. 4b, which demonstrates a representative sulfur reduction (discharge) and subsequent Li for polysulfide electrocatalysis2S Oxidation (charging) Process, 1T-edge MoS2And WS2The peak current of the two is larger than that of the unmodified carbon cloth. MoS was also observed2Comparing WS2The peak current of (a) is larger. Each having a single MoS2And WS2Polysulfide adsorption testing of edge-grown cathodes (fig. 4c) demonstrated Li2S4The solution became clear, compared to a yellowish brown solution of unmodified carbon cloth. It is also important to emphasize that no oxidation-reduction reaction of polysulfides was shown for additional control experiments with TMD cathodes not loaded with sulfur. Referring to fig. 7, there is shown no peak corresponding to sulfur-polysulfide conversion. Since no response to intercalation (e.g. MoS) was observed2Intercalation) and conversion reactions (which occur thermodynamically outside the potential range of LSB) and therefore no intrinsic activity of the TMD material is seen. Thus, these demonstrate that the TMD body itself does not contribute in any way to the capacity obtained, which is only generated by the sulfur/polysulfide redox reaction. The cycling stability of the cathode was also investigated, where 1T-edge MoS2The cathode maintained 927mAh g after 100 cycles-1Specific capacity of, and WS2After 100 cycles, the product maintains 830mAh g-1The specific capacity of (A). This compares to a specific capacity of only 611mAh g for the unmodified carbon cloth after 100 cycles-1(FIG. 4d) in contrast, and the unmodified carbon cloth experiences a large capacity loss after the first discharge cycle due to the lack of any polysulfide confining capability on the carbon surface. Furthermore, note the 1T-edge MoS2The cathode reached a stable capacity after about forty cycles, while for WS2The capacity continues to gradually decrease. The coulombic efficiency is also kept high throughout the cycle, MoS2Is higher than 95%, and WS2The coulomb efficiency of (a) is slightly lower, 93%. Although both voltammetry and cycling studies indicate a 1T-edge MoS2W therein2The counterpart has a weak performance advantage. However, this can be well explained by the observation of a 1T-edge MoS as seen from the Nyquist plot (see FIG. 8) of the electrochemical impedance spectrum2Charge transfer resistance (R) ofct(ii) a Width of the semicircle) is lower, typically below 10 Ω, in comparison to WS2Has a charge transfer resistance of 18 Ω. 1T-edge MoS2Lower R ofctThe values in turn correlate well with their smaller wafer size and larger edge site (edge site) density, which is reported to be more selective for polysulfide adsorption/electrocatalysis.
Effect of both TMD phase and morphology on Lithium Sulfur Battery (LSB) Performance
After the determination of the 1T-edge MoS2And WS2With the different properties of the cathode, we now turn our attention to the significant impact of both TMD phase and morphology on LSB performance.
FIG. 5a illustrates MoS2The cathode is based on very different rate stability of the phases and morphology. 2.0mA cm at approximately 1C-2At the highest area current density of (1T-edge MoS)2Has best performance and specific capacity of 1024 mAh.g-1(ii) a The unmodified carbon control material provided only 645mAh g-1The specific capacity of (A). In addition, when the current density decreased back to 0.2mA cm-2Then, the capacity was restored to 1205mAh g-1High order of (1). In contrast, at the same high current density, 2H-edge MoS2The cathode shows 359mAh · g-1Although a reasonable capacity (at 0.2mA cm) was obtained at a low current density-2When the water content is 1038mAh g-1) Slightly below the 1T-edge polytype. Given the similarity of edge-oriented morphologies of these cathodes, we can conclude that the lower conductivity of the 2H-semiconductor polytype necessarily leads to a drastic drop in capacity at high current densities. In fact, comparison of the impedance spectra confirms a charge transfer resistance (19 Ω) twice as large as the 2H-polytype, anduncompensated resistance/solution resistance that can be increased due to increased dissolution of polysulfides in the electrolyte. This negative effect is at the 2H-edge MoS2Even more pronounced in the cyclic voltammogram of (a), which shows a significant increase in the initial and peak potentials of all redox processes (fig. 5 b). Notably, the initial sulfur/Li2S8The overpotential for the discharge is significantly greater. Sustained redox fluctuations, increased overpotentials, and reduced peak currents are all characteristic of kinetically slower reactions, caused by slow heterogeneous electron transfer at the semiconductor surface. In contrast, the 1T-basal plane MoS2The cathode is at 2.0mA cm-2Shows 791mAh g at the highest current density-1Is moderately lower than 1T-edge materials, thus reiterating the importance of achieving high conductivity through phase design. The two 1T-polytypes further show similar R due to their similar metallic propertiesctThe value is obtained. According to 1T-basal plane MoS2Is only slightly larger than the peak current of unmodified carbon, we reach the second conclusion that edge morphology takes precedence. After an extended cycle (FIG. 5e), at the 100 th cycle, 1T-edge MoS 21T-base MoS2And 2H-edge MoS2927 mAh.g are obtained in sequence-1、872mAh·g-1And 742mAh · g-1The capacity of (c). It is also noted that the 1T-base MoS2The capacity of (a) decreases most slowly. Thus, the observed "electrocatalysis" can be attributed to the 1T-edge MoS2And the overall trend of the LSB performance in descending order is 1T-edge > 1T-basal > 2H-edge.
Structured WS2The general trend of the cathode is similar to MoS2General trend of (1). 1T-edge WS2Capacity at maximum current density 1019mAh g-1And returns to 1232mAh g when the current is reduced-1(FIG. 5 c). However, for WS2In the case of the cathode, the negative effects of the 2H-semiconductor polytype are less pronounced. 2H-edge WS2At 0.2mA · cm-2Has a capacity of 743mAh g at the maximum current-1(ii) a After the temperature is recovered to 0.2mA cm-2The specific capacity was 1045mAh · g-1. Although still present with MoS2Larger overpotential and reduced peak current similar to the case but using the semiconductor WS2The hazard is less (fig. 5 d). However, this may be from WS2R corresponding to both 1T polytype and 2H polytypectTo a large extent (see fig. 8 b). Most importantly, from these results we can still find that polytype is a more important factor for rate stability than morphology, similar to MoS2. The inventors also observed from the cycle data in FIG. 5f that WS was for the 1T-edge2Polytype, 1T-base surface WS2Polytype and 2H-edge WS2For the polytype, the capacity after 100 cycles was 830mAh g-1About 820 mAh.g-1And 729mAh · g-1。
Surface volume
The face capacity aspect of the TMD-carbon fiber material system was also investigated in view of the practical considerations required to employ LSB. FIG. 6 shows the best performing 1T-edge MoS2The surface sulfur loading of the polytype is 4.1mg(S)·cm-2In the graph of (1), as shown in fig. 6, the higher the surface sulfur content, the higher the obtainable surface capacity. 1200mAh g is obtained-1(4.9mAh·cm-2) And at a high initial specific capacity of 1.0mA cm-2(0.15C) after forty cycles, the capacity was still stable at about 900mAh g-1. The obtained equivalent stable surface capacity is 3.7mAh cm-2Compared with the surface capacity of about 2mAh cm of a conventional lithium ion battery-2And the surface capacity of the full-cell lithium ion battery system reported recently is 3.1mAh cm-2To 3.4mAh cm-2. Although the present invention also provides a sulfur-carrying amount of more than 5mg (S) cm-2Realizes 6 mAh.cm on the current system-2But it is observed that the upper limit of the applied current can be obtained from the battery cell, and thus it can be determined that the initial area capacity is about 4.5mg(s) cm-2To 5.0mg (S) · cm-2With the amount of sulfur loading, a reasonable compromise between total surface capacity and current/C rate can be achieved (see fig. 9).
In the present invention, the inventors propose a method of structuring a group VI transition metal sulfide (MoS)2And WS2) A systematic method for application to carbon fiber materials for use as cathodes in lithium sulfur batteries. First, the effect of phase, morphology and composition on polysulfide confinement and electrocatalytic observations previously reported was investigated. In the examples given above, the inventors have determined MoS2And WS2There is a clear trend in both, where polytype/phase is the dominant factor, followed by their lamellar orientation. The 1T-edge polytype is superior to all other polytypes due to a combination of its metallic properties and preferential edge orientation morphology. It was also found that the best performing 1T-edge MoS2W therein2The counterpart had a stronger battery cycling performance, which the inventors attributed to the 1T-edge MoS2Higher catalytically active edge density. Considering the potential use of lithium sulfur cathodes in larger scale battery systems, they also exhibit higher area capacities, with a stable area capacity of about 4 mAh-cm-2Higher than average commercial lithium ion batteries. Thus, it can be seen from the above results that higher area capacity required for commercial applications of lithium sulfur batteries can be achieved with supported carbon fiber materials based on transition metal sulfides. The important insights gained from the above studies also contribute to the possibility of tailoring the sulfur cathode design based on the morphology and phase design of the selected elemental composition.
While embodiments of the invention have been illustrated and described, the invention is not limited to the described embodiments. Rather, those skilled in the art will appreciate that changes may be made to the embodiments without departing from the scope of the invention, which is set forth in the claims below.
Claims (26)
1. A method of synthesizing a transition metal sulfide-based carbon material for use as an electrode in a lithium sulfur battery, the method comprising:
providing a solution comprising a group VI transition metal sulfide precursor and a solvent;
immersing a carbon fiber material in the solution to form a mixture;
applying a temperature of 200 ℃ to 300 ℃ to the mixture to load the transition metal sulfide onto the carbon fiber material; and
drying the supported carbon fiber material to obtain a supported carbon material based on a transition metal sulfide.
2. The method of claim 1, wherein the transition metal sulfide precursor is selected from the group consisting of ammonium tetrathiomolybdate and ammonium tetrathiotungstate.
3. The method of claim 2, wherein the transition metal sulfide is selected from the group consisting of molybdenum disulfide and tungsten disulfide.
4. The method of claim 1, wherein the carbon fiber material is a woven material having multiple interwoven carbon fibers.
5. The method of claim 1, wherein the carbon fiber material is a porous carbon cloth.
6. The method of claim 1, wherein the solvent is selected from the group consisting of dimethylformamide, deionized water, and combinations thereof.
7. The method of claim 1, wherein prior to the step of providing a solution comprising a group VI transition metal sulfide precursor and a solvent, the carbon fiber material is immersed in the solvent contained in the solution.
8. The method of claim 7, wherein the solvent comprises cetyltrimethylammonium bromide dissolved in deionized water.
9. The method of claim 3, wherein the transition metal sulfide is molybdenum disulfide and the transition metal sulfide based supported carbon material is loaded with edge-oriented molybdenum disulfide.
10. The method of claim 8, wherein the transition metal sulfide is molybdenum disulfide and the transition metal sulfide based loaded carbon material is loaded with basal plane oriented molybdenum disulfide.
11. The method of claim 3, wherein the transition metal sulfide is tungsten disulfide and the transition metal sulfide based supported carbon material is loaded with edge oriented tungsten disulfide or basal oriented tungsten disulfide.
12. The method of claim 1, further comprising:
annealing the transition metal sulfide based supported carbon material to form a transition metal sulfide based supported semiconducting carbon material.
13. The method of claim 1, further comprising:
preparing an electrode for a lithium-sulfur battery using a transition metal sulfide-based supported carbon fiber material, wherein the preparing comprises:
mixing and heating sulfur and carbon black to obtain a sulfur-carbon black mixture;
mixing the sulfur-carbon black mixture with a binder and a solvent to obtain a sulfur-containing slurry;
depositing the sulfur-containing slurry onto the transition metal sulfide-based supported carbon material; and
drying the transition metal sulfide-based supported carbon material to obtain a transition metal sulfide-based sulfur-supported carbon electrode.
14. The method of claim 13, wherein the electrode is a cathode.
15. The method of claim 13, further comprising:
the deposition and drying steps were repeated to obtain 1.5 mg-cm-2To 5.5 mg.cm-2The surface sulfur loading of (2).
16. The method of claim 13, further comprising:
heating the sulfur-carbon black mixture to remove excess surface sulfur from the sulfur-carbon black mixture prior to mixing the sulfur-carbon black mixture with the binder and the solvent.
17. A transition metal sulfide-based carbon material comprising a carbon fiber material and a group VI transition metal sulfide selected from the group consisting of molybdenum disulfide and tungsten disulfide, wherein the transition metal sulfide is supported on the carbon fiber material.
18. The transition metal sulfide-based carbon material according to claim 17, wherein the transition metal sulfide is supported on the carbon fiber material by forming nanocrystals on a surface of the carbon fiber material.
19. The transition metal sulfide-based carbon material as claimed in claim 17, wherein the carbon fiber material is a woven material having carbon fibers multiply interwoven.
20. The transition metal sulfide-based carbon material according to claim 17, wherein the carbon fiber material is a porous carbon cloth.
21. The transition metal sulfide-based carbon material according to claim 17, wherein the transition metal sulfide is molybdenum disulfide.
22. The transition metal sulfide-based carbon material of claim 21, wherein the molybdenum disulfide is edge-oriented molybdenum disulfide or basal-oriented molybdenum disulfide.
23. The transition metal sulfide-based carbon material according to claim 17, wherein the transition metal sulfide is tungsten disulfide.
24. The transition metal sulfide-based carbon material of claim 23, wherein the tungsten disulfide is edge-oriented tungsten disulfide or basal-oriented tungsten disulfide.
25. A transition metal sulfide-based carbon electrode comprising the transition metal sulfide-based carbon material according to any one of the preceding claims 17 to 24 loaded with sulfur.
26. A lithium sulfur battery comprising an anode and a cathode, wherein the cathode comprises the transition metal sulfide-based carbon material according to any one of the preceding claims 17 to 24 loaded with sulfur.
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| CN113403030A (en) * | 2021-06-21 | 2021-09-17 | 黑龙江工程学院 | Preparation method of small-size multi-element transition metal sulfide/carbon black powder nano composite material |
| CN115986125A (en) * | 2023-03-15 | 2023-04-18 | 中国华能集团清洁能源技术研究院有限公司 | Two-dimensional transition metal sulfide catalyst and lithium-sulfur battery based on same |
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| CN110783542A (en) * | 2019-10-22 | 2020-02-11 | 济南大学 | Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery |
| CN113972375B (en) * | 2021-10-21 | 2023-03-21 | 合肥工业大学 | Preparation method and application of porous carbon fiber/tungsten oxide self-supporting lithium-sulfur battery positive electrode material |
| CN114177287A (en) * | 2021-12-10 | 2022-03-15 | 长春工业大学 | Application of programmable immune active carbon fiber-molybdenum disulfide composite material in preparation of wound healing medicine |
| CN114538519A (en) * | 2022-04-13 | 2022-05-27 | 景德镇陶瓷大学 | Preparation method of phosphorus-doped amorphous carbon-coated 1T-phase molybdenum disulfide/carbon lithium ion battery composite anode material |
| CN114678508A (en) * | 2022-04-13 | 2022-06-28 | 电子科技大学长三角研究院(湖州) | Carbon-based supported metal sulfide composite material and preparation method and application thereof |
| CN114613973B (en) * | 2022-04-13 | 2024-04-12 | 景德镇陶瓷大学 | Preparation method of phosphorus-doped 1T-phase molybdenum disulfide/carbon lithium ion battery composite anode material |
| CN114784244A (en) * | 2022-04-21 | 2022-07-22 | 陕西科技大学 | Three-dimensional hollow WS2/C composite electrode material and preparation method and application thereof |
| CN115036480B (en) * | 2022-06-17 | 2023-05-19 | 湘潭大学 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
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| CN113403030B (en) * | 2021-06-21 | 2023-08-11 | 黑龙江工程学院 | Preparation method of small-size multi-element transition metal sulfide/carbon black powder nanocomposite |
| CN115986125A (en) * | 2023-03-15 | 2023-04-18 | 中国华能集团清洁能源技术研究院有限公司 | Two-dimensional transition metal sulfide catalyst and lithium-sulfur battery based on same |
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