CN107275551B - Lithium-sulfur battery, assembly thereof and application of functional material layer in lithium-sulfur battery - Google Patents
Lithium-sulfur battery, assembly thereof and application of functional material layer in lithium-sulfur battery Download PDFInfo
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Abstract
The invention provides a lithium-sulfur battery, comprising a sulfur-based positive electrode; a lithium-based negative electrode; a separator disposed between the sulfur-based positive electrode and the lithium-based negative electrode; and a functional material layer disposed between the sulfur-based positive electrode and the lithium-based negative electrode, a material of the functional material layer including a transition metal oxide having crystal water. The invention also provides the application of the composite diaphragm, the lithium-sulfur battery electrode assembly, the composite sulfur-based positive electrode, the composite lithium-based negative electrode and the functional material layer in the lithium-sulfur battery.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium-sulfur battery, a composite diaphragm, a lithium-sulfur battery electrode assembly, a composite sulfur-based positive electrode, a composite lithium-based negative electrode and application of a functional material layer in the lithium-sulfur battery.
Background
With the rapid development of the new energy automobile industry, the development of energy storage devices with high energy density becomes an important direction for research and development at present. The lithium-sulfur battery becomes one of the most promising power battery systems which can replace the traditional lithium ion battery and realize the remote cruising target (500 Wh/kg) by the theoretical specific capacity of 1675mAh/g and the theoretical energy density of 2500 Wh/kg. However, lithium-sulfur batteries still have a practical limit due to their low cycle life and poor safety and stability. How to effectively inhibit the shuttle effect of lithium polysulfide is a key factor for improving the electrochemical performance and safety performance of lithium sulfur batteries, and is also a hot spot of international research in recent years.
The shuttling effect of lithium polysulphides is mainly caused by two aspects, one being thermodynamically unavoidable diffusion and the second being the slower reaction kinetics leading to accumulation of lithium polysulphides in the electrolyte. Currently, the main methods for inhibiting the shuttling of lithium polysulfide are physical blocking, polar adsorption and storage, and promoting the conversion of lithium polysulfide, and the shuttling of lithium polysulfide is inhibited by coating a sulfur positive electrode or binding sulfur in a nanometer pore channel. While forming a protective layer or network on the surface of the sulfur can provide some barrier to lithium polysulfides, it is still difficult to achieve a long life cycle for the battery.
There have been a lot of studies to improve the capacity and cycle performance of lithium-sulfur batteries by coating some transition metal oxides or sulfides on a separator as a functional material layer. Some of the polar transition metal oxides or sulfide oxides, e.g. Fe2O3、Co3O4、Ti4O7、NiO、ZnO、V2O3、Cu2O and the like can store lithium polysulfide by adsorption through surface polar or acidic sites; other transition metal oxides, e.g. TiO2、MnO2、CuO、VO2And has the function of catalyzing lithium polysulfide. In addition, the nano material can be filled in the pores of the diaphragm, so that the nano material can play a role in physically blocking lithium polysulfide to a certain extent on the premise of ensuring the normal passing of lithium ions. However, in practice it has often been found that even with the above-mentioned transition metal oxides, the effect achieved in preventing shuttling of lithium polysulphides is still not ideal.
Disclosure of Invention
Based on this, in order to more effectively prevent the shuttling of lithium polysulfide, there is a need for a lithium sulfur battery, a composite separator, a lithium sulfur battery electrode assembly, a composite sulfur-based positive electrode, a composite lithium-based negative electrode, and an application of a functional material layer in the lithium sulfur battery.
A lithium sulfur battery comprising a sulfur-based positive electrode; a lithium-based negative electrode; a separator disposed between the sulfur-based positive electrode and the lithium-based negative electrode; and a functional material layer disposed between the sulfur-based positive electrode and the lithium-based negative electrode, a material of the functional material layer including a transition metal oxide having crystal water.
A composite separator for a lithium-sulfur battery, comprising a separator and a functional material layer disposed on at least one surface of the separator, wherein the material of the functional material layer comprises a transition metal oxide having crystal water.
A lithium-sulfur battery electrode assembly includes a sulfur-based positive electrode, a separator, and a functional material layer disposed between the sulfur-based positive electrode and the separator, the functional material layer including a transition metal oxide having crystal water.
A lithium-sulfur battery electrode assembly comprising a lithium-based negative electrode, a separator, and a functional material layer disposed on top of each other, the functional material layer being disposed between the lithium-based negative electrode and the separator, the functional material layer being made of a material including a transition metal oxide having crystal water.
The composite sulfur-based positive electrode comprises a positive electrode material layer, a positive electrode current collector and a functional material layer which are stacked mutually, wherein the positive electrode material layer is arranged between the functional material layer and the positive electrode current collector, and the material of the functional material layer comprises transition metal oxide with crystal water.
A composite lithium-based negative electrode includes metallic lithium and a functional material layer stacked on each other, the functional material layer including a transition metal oxide having crystal water.
Use of a functional material layer in a lithium-sulfur battery, comprising applying a solid-liquid mixture containing the transition metal oxide having water of crystallization to a surface of at least one of the sulfur-based positive electrode, a lithium-based negative electrode, and a separator, thereby forming the functional material layer between the sulfur-based positive electrode and the lithium-based negative electrode.
Compared with the transition metal oxide without crystal water, the transition metal oxide with crystal water has larger specific surface area, thereby providing more active sites, better playing a role in absorbing, storing and/or catalyzing lithium polysulfide, effectively playing a role in inhibiting lithium polysulfide shuttling, and improving the electrochemical performance of the lithium sulfur battery.
Drawings
FIG. 1 is a schematic structural view of a lithium-sulfur battery according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of an electrode assembly of a lithium sulfur battery according to an embodiment of the present invention;
FIG. 3 is an SEM image of the functional material layer of PP @ C & HTO-1 of example 1;
FIG. 4 is a graph comparing the cycle performance at 0.2C for a lithium sulfur cell using PP @ C & HTO-1 in example 1 and a lithium sulfur cell using PP in a comparative example;
FIG. 5 is a graph of cycling performance versus coulombic efficiency at 1C for a lithium sulfur cell using PP @ C & HTO-1 of example 1;
FIG. 6 is a graph of cycling performance versus coulombic efficiency at 1C for the comparative example lithium sulfur cell of example 1 using PP @ C & TO-1;
FIG. 7 is an SEM image of a PP @ C & HTO-2 functional material layer of example 2;
FIG. 8 is a graph comparing the cycling performance at 0.2C for a lithium sulfur cell using PP @ C & HTO-2 and PP in example 2;
FIG. 9 is a graph of cycling performance versus coulombic efficiency at 0.5C for a lithium sulfur cell made using the PP @ C & HTO-2 coating of example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1 and 2, a lithium-sulfur battery according to an embodiment of the present invention includes a sulfur-based positive electrode 10, a lithium-based negative electrode 20, and a separator 30 disposed between the sulfur-based positive electrode 10 and the lithium-based negative electrode 20, and the lithium-sulfur battery further includes a functional material layer 32 disposed between the sulfur-based positive electrode 10 and the lithium-based negative electrode 20. The material of the functional material layer 32 includes a transition metal oxide having crystal water. The transition metal oxide can adsorb storage and/or catalyze lithium polysulfide, and inhibit lithium polysulfide shuttling. In addition, because the material has crystal water, the crystal water can react with lithium ions to a certain degree or the lithium ions are uniformly distributed by adjusting the surface polarity, so that the function of inhibiting the growth of lithium dendrites is achieved.
The metal element of the transition metal oxide may be at least one selected from titanium (Ti), ruthenium (Ru), molybdenum (Mo), vanadium (V), tungsten (W), iron (Fe), and cobalt (Co).
The transition metal oxide having crystal water includes, but is not limited to, TiO2·xH2O、H2TinO2n+1·H2O、RuO2·xH2O、MoO3·xH2O、(H3O)xMoO3·xH2O、HyV4O10·xH2O、HzV2O5·xH2O、V2O5·xH2O、V2O4·xH2O、WO3·xH2O、Fe2O3·xH2O and Co2O3·xH2N is more than or equal to 2 and less than or equal to 9, x is more than or equal to 0.5 and less than or equal to 10, and 0<y≤1，0<z≤1。
The transition metal oxide having water of crystallization is preferably a nano-scale material, and the primary particle diameter of the transition metal oxide having water of crystallization is preferably 1 nm to 100 nm, more preferably 1 nm to 10 nm. When the particle size of the material is nano-scale, the material can be effectively filled in the pores of the separator and can also play a role in physically blocking lithium polysulfide from shuttling to a certain extent.
The transition metal oxide having water of crystallization has a larger specific surface area than the transition metal oxide obtained by removing the water of crystallization, and the value of the specific surface area of the transition metal oxide having water of crystallization is preferably 100m2G to 600m2/g。
The thickness of the functional material layer 32 is preferably 10nm to 200 μm, and the surface density is preferably 0.1 to 10 mg/cm.
Preferably, the material of the functional material layer 32 further includes an electron conductive material and a binder, and the electron conductive material and the binder are uniformly mixed with the transition metal oxide having crystal water. The content of the transition metal oxide having crystal water in the functional material layer 32 is preferably 5% to 99% by mass. The mass ratio of the electronic conductive material to the binder is preferably 1: 9-9: 1.
Preferably, the electron conductive material is at least one selected from the group consisting of activated carbon, graphene, carbon nanotubes, ketjen black, Super P, acetylene black, and graphite.
Preferably, the binder is selected from at least one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), lauric acid acrylate (LA), Polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), epoxy resin, polyacrylic acid (PAA), and sodium carboxymethyl cellulose (CMC).
The functional material layer 32 may be disposed on a surface of the sulfur-based positive electrode 10 facing the lithium-based negative electrode 20 (i.e., facing the separator 30), at least one surface of the separator 30, or a surface of the lithium-based negative electrode 20 facing the sulfur-based positive electrode 10 (i.e., facing the separator 30). In a preferred embodiment, the functional material layer 32 is disposed at least on a surface of the separator 30 facing the sulfur-based positive electrode 10. In one embodiment, the functional material layer 32 is disposed on both surfaces of the diaphragm 30.
The sulfur-based positive electrode 10 includes a positive electrode material layer 12 and a positive electrode current collector 14, and the positive electrode current collector 14 is used for carrying the positive electrode material layer 12 and conducting current and may be in the shape of a foil or a mesh. The material of the positive electrode collector 14 may be selected from aluminum, titanium, or stainless steel. The positive electrode material layer 12 is disposed on at least one surface of the positive electrode collector 14. The material of the positive electrode material layer 12 includes a sulfur-containing positive electrode active material, and further optionally includes a conductive agent and a binder. The conductive agent and the binder may be uniformly mixed with the sulfur-containing cathode active material. The sulfur-containing cathode active material is a sulfur-based material with electrochemical lithium storage capacity, such as at least one of elemental sulfur, sulfur-based composite materials and vulcanized conductive polymers. The sulfur-based composite material may be, for example, a core-shell structure composite material obtained by coating a conductive carbon layer on the surface of elemental sulfur particles, or a porous composite material obtained by disposing elemental sulfur particles in a porous carbon material. The sulfur-based conductive polymer may be selected from one or more of, for example, vulcanized polypyridyl, vulcanized polystyrene, vulcanized polyethylene oxide, vulcanized polyvinyl alcohol, vulcanized polyvinylidene chloride, vulcanized polyvinylidene fluoride, vulcanized polyvinyl chloride, vulcanized polyvinyl fluoride, vulcanized poly-1, 2-dichloroethylene, vulcanized poly-1, 2-difluoroethylene, vulcanized polymethyl methacrylate, and vulcanized phenol resin.
The functional material layer 32 may be disposed on a surface of the positive electrode material layer 12 facing the lithium-based negative electrode 20 (i.e., facing the separator 30). The positive electrode material layer 12 is disposed between the functional material layer 32 and the positive electrode current collector 14.
The functional material layer 32 is preferably in direct contact with the positive electrode material layer 12 or in direct contact with the separator 30. More preferably, both surfaces of the functional material layer 32 are disposed in direct contact with the positive electrode material layer 12 and the separator 30, respectively. However, in some embodiments, another material layer, such as an adhesive layer, a conductive layer or an ion-conducting layer, may be interposed between the functional material layer 32 and the cathode material layer 12, or between the functional material layer 32 and the separator 30, as long as the functional material layer 32 is not affected to perform at least one of the above functions (1) to (3).
The lithium-based anode 20 may include an anode active layer 22, such as a metallic lithium layer or a lithium alloy layer, for example a lithium tin alloy layer or a lithium aluminum alloy layer, and may further include an anode current collector 24. The negative electrode collector 24 serves to support the negative electrode active layer 22 and conduct current, and may be in the shape of a foil or a mesh. The material of the negative electrode collector 24 may be selected from copper, nickel, or stainless steel.
The separator 30 may be a conventional lithium battery separator, which is capable of isolating electrons and allowing lithium ions to pass between the sulfur-based positive electrode 10 and the lithium-based negative electrode 20, and may be any one of an organic polymer separator and an inorganic separator, for example, may be selected from, but not limited to, any one of a polyethylene porous membrane, a polypropylene porous membrane, a polyethylene-polypropylene double-layer porous membrane, a polypropylene-polyethylene-polypropylene triple-layer porous membrane, a glass fiber porous membrane, a non-woven porous membrane, an electrospun porous membrane, a PVDF-HFP porous membrane, and a polyacrylonitrile porous membrane. Examples of the nonwoven fabric separator include polyimide nanofiber nonwoven fabrics, polyethylene terephthalate (PET) nanofiber nonwoven fabrics, cellulose nanofiber nonwoven fabrics, aramid nanofiber nonwoven fabrics, nylon nanofiber nonwoven fabrics, and polyvinylidene fluoride (PVDF) nanofiber nonwoven fabrics. Examples of the electrospun porous membrane include a polyimide electrospun membrane, a polyethylene terephthalate electrospun membrane, and a polyvinylidene fluoride electrospun membrane.
The lithium-sulfur battery further includes a nonaqueous electrolytic solution 40, and the nonaqueous electrolytic solution 40 is disposed between the sulfur-based positive electrode 10 and the lithium-based negative electrode 20, and may be, for example, impregnated in the separator 30. The non-aqueous electrolyte 40 includes a solvent and a solute of lithium salt dissolved in the solvent, and the solvent may be selected from one or more of, but not limited to, cyclic carbonates, chain carbonates, cyclic ethers, chain ethers, nitriles and amides, such as one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, diethyl ether, acetonitrile, propionitrile, anisole, butyrate, glutaronitrile, adiponitrile, γ -butyrolactone, γ -valerolactone, tetrahydrofuran, 1, 2-dimethoxyethane, and acetonitrile and dimethylformamide. The lithium salt solute may be selected from, but is not limited to, lithium chloride (LiCl), lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium methanesulfonate (LiCH)3SO3) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium hexafluoroarsenate (LiAsF)6) Lithium perchlorate (LiClO)4) And lithium bis (oxalato) borate (LiBOB).
The lithium sulfur battery further includes a hermetic case 50, and the sulfur-based positive electrode 10, the lithium-based negative electrode 20, the separator 30, the functional material layer 32, and the nonaqueous electrolytic solution 40 are disposed in the hermetic case 50.
The embodiment of the invention also provides a composite diaphragm, which is used for the lithium-sulfur battery and comprises the diaphragm 30 and a functional material layer 32 arranged on at least one surface of the diaphragm 30. In a preferred embodiment, a functional material layer 32 is disposed on the surface of separator 30 facing sulfur-based positive electrode 10 in a lithium sulfur battery.
The embodiment of the invention also provides a lithium-sulfur battery electrode assembly, which comprises the sulfur-based positive electrode 10, a separator 30 and the functional material layer 32 which are arranged in a mutually laminated mode, wherein the functional material layer 32 is arranged between the sulfur-based positive electrode 10 and the separator 30.
The embodiment of the invention also provides a lithium-sulfur battery electrode assembly, which comprises a lithium-based negative electrode 20, a diaphragm 30 and a functional material layer 32, wherein the lithium-based negative electrode 20, the diaphragm 30 and the functional material layer 32 are arranged in a mutually laminated mode, and the functional material layer 32 is arranged between the lithium-based negative electrode 20 and the diaphragm 30.
The embodiment of the invention also provides a composite sulfur-based positive electrode, which comprises a positive electrode material layer 12, a positive electrode current collector 14 and a functional material layer 32, wherein the positive electrode material layer 12 is arranged between the functional material layer 32 and the positive electrode current collector 14.
The embodiment of the invention also provides a composite lithium-based negative electrode, which comprises the metallic lithium 22 and the functional material layer 32 which are mutually stacked.
Embodiments of the present invention provide a use of the functional material layer 32 in the lithium-sulfur battery, including applying a solid-liquid mixture containing the transition metal oxide having crystal water to a surface of at least one of the sulfur-based positive electrode 10 and the separator 30, thereby forming the functional material layer 32 between the sulfur-based positive electrode 10 and the lithium-based negative electrode 20.
The solid phase in the solid-liquid mixture includes the transition metal oxide having crystal water, and may further include the electron-conductive material and the binder; the liquid phase is preferably a solvent. The transition metal oxide having crystal water, the electron conductive material, the binder and the solvent are uniformly mixed in the solid-liquid mixture. The solvent serves as a carrier for the transition metal oxide having water of crystallization, and therefore, it is necessary to select a solvent which is incapable of dissolving the transition metal oxide having water of crystallization, does not chemically react with the transition metal oxide having water of crystallization, and can be completely removed at a relatively low temperature (e.g., 30 to 120 ℃), for example, a low molecular weight volatile organic solvent which may be one or more selected from N-methyl pyrrolidone, water, methanol, ethanol, propanol, isopropanol, acetonitrile, acetone, and diethyl ether.
The solid-liquid mixture can be mixed liquid or slurry, the mixed liquid and the slurry are only distinguished in the proportion of the solid phase and the liquid phase, the slurry is used when the solid phase is relatively large, and the mixed liquid is used when the liquid phase is relatively large. The selection of the ratio of the slurry to the mixed liquid and the solid to liquid can be performed according to actual needs, for example, according to the coating mode. Of course, in order to make the coating easy, the slurry preferably has appropriate fluidity; for more efficient coating, the solid phase in the mixed solution is preferably in a suitable ratio. The coating method may be any one of, for example, a dipping method, a spin coating method, a blade coating method, a casting coating method, a suction filtration (filtration) coating method, a uniaxial stretching method, and a biaxial stretching method. After the solid-liquid mixture is coated to form the coating layer through the coating step, the solvent in the coating layer is removed to obtain the functional material layer 32. Thus, the solid-liquid mixture can be applied to the desired surface of the component. When the solid-liquid mixture is applied to the sulfur-based positive electrode 10, it may be applied to a surface of the positive electrode material layer 12 facing the separator 30. When the solid-liquid mixture is applied to the separator 30, it may be applied to one side or both sides of the separator 30.
After applying the solid-liquid mixture to the surface of at least one of the sulfur-based positive electrode 10 and the separator 30, drying to remove the solvent in the coating layer may be further included. The drying method is, for example, vacuum drying at 30-120 ℃ for 4-24 hours. It is understood that the drying step is only for removing the liquid phase solvent and the adsorbed water in the coating layer, and the temperature of the drying step is low, so that the transition metal oxide in the functional material layer 32 still has crystal water after drying, and water molecules still exist in the functional material layer 32 in the form of crystal water.
After the functional material layer 32 is formed on a desired surface, for example, on the surface of the positive electrode material layer 12 of the sulfur-based positive electrode 10 and/or on at least one surface of the separator 30, the method further includes the step of stacking the sulfur-based positive electrode 10 and the separator 30.
In one embodiment, the step of stacking provides for the functional material layer 32 to be stacked between the sulfur-based positive electrode 10 and the separator 30. For example, after the functional material layer 32 is formed on the surface of the positive electrode material layer 12 of the sulfur-based positive electrode 10, the separator 30 may be applied to the surface of the functional material layer 32. Alternatively, after the functional material layer 32 is formed on at least one surface of the separator 30, the surface of the separator 30 having the functional material layer 32 may be laid on the surface of the cathode material layer 12 so as to face the cathode material layer 12.
In another embodiment, the step of stacking provides for the functional material layer 32 to be stacked on the surface of the separator 30 remote from the sulfur-based positive electrode 10. In this embodiment, the functional material layer 32 may also be disposed between the sulfur-based positive electrode 10 and the lithium-based negative electrode 20 by further laminating the lithium-based negative electrode 20 on the surface of the separator 30 having the functional material layer 32.
After the sulfur-based positive electrode 10, the functional material layer 32, the separator 30, and the lithium-based negative electrode 20 are stacked on one another, the stacked structure may be encapsulated in the hermetic case 50 according to a conventional lithium-sulfur battery manufacturing process; and injecting the electrolyte 40 into the hermetic case 50.
The functional material layer 32 based on a transition metal oxide having crystal water has the function of adsorbing and/or catalyzing lithium polysulfide in a lithium-sulfur battery and passes through crystal water H2The introduction of O improves the crystal structure and the nanometer dimension diversity of the transition metal oxide in the functional material layer 32, and improves the ionic conductivity of the functional material layer 32. By crystallization of water H2The introduction of O can improve the specific surface area of the material, and the larger specific surface area can provide more active sites, thereby effectively playing the role of inhibiting lithium polysulfide shuttling and improving the electrochemical performance of the lithium-sulfur batteryChemical properties and safety properties.
The technical scheme of the application breaks through the concept that water is considered to be harmful to the electrochemical performance and safety of the lithium-sulfur battery in the prior art, and finds and proves that the performance of the lithium-sulfur battery cannot be influenced by introducing the crystal water into the functional material layer 32 through experiments, and meanwhile, the lithium-sulfur battery can have excellent rate capacity and cycle stability. The lithium-sulfur battery using the functional material layer 32 has a wide application prospect in the energy storage fields of lithium ion batteries and the like in electric vehicles, energy storage power stations and high-capacity electronic products.
In addition, most methods for preparing transition metal oxides are wet chemical methods (such as hydrothermal synthesis or sol-gel method), and the products obtained by these methods are often hydrates, and the crystal water in the products is removed by medium-high temperature heat treatment which is conventionally performed. The transition metal oxide with crystal water is directly used for the functional material layer 32, so that the step of heat treatment for removing water is omitted, the energy consumption and pollution in the traditional method are effectively reduced, the material preparation process is mild and controllable, and the method has important influence and significance in the fields of new energy, new materials and energy-saving and environment-friendly industries.
Example 1
1) Preparation of a layer of transition metal oxide based functional material with water of crystallization: adding TiO into the mixture2·xH2Adding O, Super P and PVDF into N-methyl pyrrolidone according to the mass ratio of 8:1:1 to mix into slurry, then coating the slurry on one side of a polypropylene diaphragm by using a tape casting method, and drying the slurry in vacuum at 60 ℃ for 10 hours to obtain the composite diaphragm of the transition metal oxide based functional material layer with crystal water (hereinafter referred to as PP @ C)&HTO-1)。PP@C&A Scanning Electron Microscope (SEM) view of the functional material layer in HTO-1 is shown in FIG. 3.
2) Assembling the lithium-sulfur battery: preparing a sulfur anode from sublimed sulfur, preparing a metal lithium sheet as a cathode, and preparing PP @ C&HTO-1 is a diaphragm, and the electrolyte is LiTFSI and LiNO3A mixed solution formed in a mixed solvent of DME and DOL (volume ratio of DME to DOL is 1:1, concentration of LiTFSI is 1mol/L, LiNO3The concentration of (3) is 0.2 mol/L). In water and oxygen contentA 2032 type button cell was assembled in a glove box with a high purity argon atmosphere, all below 1 ppm.
Comparative example 1
The same 2032 type button cell as in example 1 was assembled by replacing PP @ C & HTO-1 in example 1 with a commercial polypropylene separator for lithium battery (hereinafter referred to as PP) with the same difference as in example 1, and the PP @ C & HTO-1 was replaced with PP with the difference.
Comparative example 2
Same as example 1, except for TiO in example 12·xH2Heating and dehydrating O at 350 ℃ to obtain TiO2(hereinafter abbreviated as TO-1) material, and TiO in the step of preparing the functional material layer in example 12·xH2Replacing O with TO-1 TO obtain the composite diaphragm (hereinafter referred TO as PP @ C) with the transition metal oxide coating&TO-1), assemble a 2032 type button cell identical TO that of example 1, except that PP @ C is used&Replacement of HTO-1 with PP @ C&TO-1。
Example 2
Same as example 1, except for TiO in example 12·xH2Replacement of O by H2Ti3O7And replacing the tape casting method with a doctor blade coating method to obtain the composite diaphragm (hereinafter referred to as PP @ C) with the transition metal oxide coating&HTO-2), assembling a 2032 type button cell identical to that of example 1, except that PP @ C is used&Replacement of HTO-1 with PP @ C&HTO-2。
A Scanning Electron Microscope (SEM) image of the functional material layer in PP @ C & HTO-2 is shown in FIG. 7.
Testing of electrochemical cell Performance
The electrochemical cycle characteristics of the button cells of examples 1-2 and comparative examples 1-2 were tested using a LAND cell test system with constant current charge-discharge cycling at charge-discharge cut-off voltages in the voltage ranges of 2.7V and 1.8V, respectively, and the test data for the cells are shown in Table 1. FIG. 4 is a graph comparing the cycling performance at 0.2C for lithium sulfur cells using PP @ C & HTO-1 and PP, respectively. FIG. 5 is a graph of cycling performance versus coulombic efficiency at 1C for a lithium sulfur cell using PP @ C & HTO-1. FIG. 6 is a plot of cycling performance versus coulombic efficiency at 1C for a lithium sulfur battery of comparative example 2 using PP @ C & TO-1. FIG. 8 is a graph comparing the cycling performance at 0.2C for lithium sulfur cells using PP @ C & HTO-2 and PP, respectively. FIG. 9 is a graph of cycling performance versus coulombic efficiency at 0.5C for a lithium sulfur cell using PP @ C & HTO-2.
As can be seen from the comparison of cycle performance in FIG. 4, the first discharge capacity of the lithium-sulfur battery using PP @ C & HTO-1 was as high as 1735mAh/g, while the first discharge capacity of the control battery using PP was only 979 mAh/g. After 400 cycles, the lithium-sulfur battery using PP @ C & HTO-1 still maintained a stable specific capacity of 671mAh/g, which is 2.5 times the specific capacity of the control battery using PP. As can be seen from fig. 5, at a large rate of 1C, the lithium-sulfur battery using PP @ C & HTO-1 still has a reversible specific capacity of 420mAh/g after 1400 cycles, the coulombic efficiency is close to 100%, the "shuttle effect" of lithium polysulfide is significantly reduced, and the battery exhibits very excellent large rate capacity and cycle stability.
Using PP @ C&TO-1 and PP @ C&The HTO-1 comparison examines the advantages of crystalline water-containing materials in lithium sulfur batteries. As can be seen from FIG. 6, PP @ C is used&The first discharge capacity of the TO-1 lithium-sulfur battery was only 650 mAh/g. The specific capacity of the battery is continuously reduced in 1400 cycles, and the specific capacity is reduced to 420mAh/g by 250 cycles. In FIG. 5, PP @ C is shown under the same conditions&The lithium sulfur battery of HTO-1 was still above 420mAh/g after 1400 cycles. PP @ C after 1400 cycles&The specific capacity of the TO-1 lithium-sulfur battery was only 130mAh/g remaining. This is because of the nano TiO2·xH2The O crystal structure is often coarsened and agglomerated in the high-temperature dehydration process, the size of material particles is increased, the specific surface area is greatly reduced, and further the adsorption storage and catalytic action of active sites in the material on lithium polysulfide are reduced, so that the electrochemical performance is unsatisfactory.
As can be seen from the above experiments, in the preparation method of nano-oxide, a wet chemical method (e.g., hydrothermal reaction or sol-gel reaction) prepares a hydrate of the obtained oxide, which has crystal water. Whereas the hydrates with water of crystallization traditionally thought needed to be removed by high temperature calcination to give the final product. The present inventors have found that the material after high temperature water removal is not an ideal condition for a functional material layer for a lithium sulfur battery. In the application, the inventor of the application avoids high-temperature calcination, retains crystal water in the material, avoids coarsening and agglomeration of a nanocrystal structure in a high-temperature dehydration process, enables a transition metal oxide to have a large number of active sites, and adsorbs and/or catalyzes lithium polysulfide through the large number of active sites. And when the oxide has smaller grain size, the oxide can be more easily filled in the pores of the organic diaphragm to physically block lithium polysulfide, so that the effect of better inhibiting the lithium polysulfide shuttle of the lithium-sulfur battery is achieved.
As can be seen from the comparison of cycle performance in FIG. 8, the first discharge capacity of the lithium-sulfur battery using PP @ C & HTO-2 was as high as 1536mAh/g, while the first discharge capacity of the control battery using PP was only 979 mAh/g. After 400 cycles, the lithium-sulfur battery using PP @ C & HTO-2 still maintained a stable specific capacity of 639mAh/g, which is 2.5 times the specific capacity of the control battery using PP. At a rate of 0.5C (FIG. 9), the lithium-sulfur battery using PP @ C & HTO-2 still has a reversible specific capacity of 442mAh/g after 1200 cycles, the coulombic efficiency is close to 100%, the "shuttle effect" of lithium polysulfide is obviously weakened, and the battery shows very excellent high-rate capacity and cycling stability.
TABLE 1
| Multiplying factor of current | Specific capacity of initial discharge | Discharge specific capacity of Nth cycle | |
| Example 1 | 0.2C | 1735mAh/g | 671mAh/g,N＝400 |
| Example 1 | 1C | 958mAh/g | 420mAh/g,N＝1400 |
| Comparative example 1 | 0.2C | 979mAh/g | 263mAh/g,N＝400 |
| Comparative example 2 | 1C | 650mAh/g | 130mAh/g,N＝1400 |
| Example 2 | 0.2C | 1536mAh/g | 639mAh/g,N＝400 |
| Example 2 | 0.5C | 694mAh/g | 442mAh/g,N＝1200 |
Example 3
1) Preparation of a layer of transition metal oxide based functional material with water of crystallization: adding MoO3·xH2Adding O, Ketjen black and PVDF into an ethanol solvent according to the mass ratio of 7:2:1 to mix into slurry, and then using the rotary coating method to coat the two sides of a polyethylene diaphragmCoating the slurry, and vacuum drying the slurry at 80 ℃ for 10 hours to obtain the composite diaphragm (hereinafter referred to as PE @ C) with the crystal water transition metal oxide-based functional material layer&HMO-3)。
2) Assembling the lithium-sulfur battery: as in example 1, the only difference is that PP @ C & HTO-1 is replaced with PE @ C & HMO-3.
Example 4
1) Preparation of a layer of transition metal oxide based functional material with water of crystallization: will V2O5·xH2Adding O, acetylene black and LA into deionized water according to the mass ratio of 85:15:5 to mix into slurry, then coating the slurry on one side of a polyethylene-polypropylene double-layer membrane by using a suction filtration (filtration) coating method, and drying the slurry in vacuum at 80 ℃ for 10 hours to obtain the composite membrane (hereinafter referred to as PE/PP @ C) with the crystal water transition metal oxide-based functional material layer&HVO-4)。
2) Assembling the lithium-sulfur battery: as in example 1, the only difference was that the sublimed sulfur was replaced with a sulfur-carbon composite and PP @ C & HTO-1 was replaced with PE/PP @ C & HVO-4.
Example 5
1) Preparation of a layer of transition metal oxide based functional material with water of crystallization: mixing WO3·xH2Adding O, carbon nano tubes and PTFE into methanol according to the mass ratio of 6:3:1 to mix into slurry, then coating the slurry on the surface of a positive electrode material layer made of sublimed sulfur by using a tape casting method, and drying the slurry in vacuum at 80 ℃ for 10 hours to obtain the sulfur-based positive electrode (hereinafter referred to as S @ C) with a transition metal oxide-based functional material layer with crystal water&HWO-5)。
2) Assembling the lithium-sulfur battery: s @ C & HWO-5 is used as a positive electrode, a metal lithium sheet is used as a negative electrode, the diaphragm is a commercial polypropylene-polyethylene-polypropylene diaphragm for the lithium battery, and the electrolyte is a solution of LiTFSI in a mixed solvent of DME and DOL (the volume ratio of DME to DOL is 1:1, and the concentration of LiTFSI is 1 mol/L). A 2032 type button cell was assembled in a glove box under a high purity argon atmosphere with both water and oxygen content below 1 ppm.
Example 6
1) Preparation of a layer of transition metal oxide based functional material with water of crystallization: mixing Fe2O3·xH2Adding O, graphene and polyvinylidene fluoride into ethanol according to the mass ratio of 70:15:15 to mix into slurry, then coating the slurry on one side of the PAN porous membrane by using a doctor blade method, and drying the slurry at 60 ℃ for 10 hours in vacuum to obtain the composite diaphragm (hereinafter referred to as PAN C) with the crystal water transition metal oxide-based functional material layer&HFO-6)。
2) Assembly of lithium-sulfur cell As in example 1, except that the sublimed sulfur was replaced with a sulfur-carbon composite and PP @ C & HTO-1 was replaced with PE/PP @ C & HVO-6.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. A lithium sulfur battery comprising:
a sulfur-based positive electrode;
a lithium-based negative electrode;
a separator disposed between the sulfur-based positive electrode and the lithium-based negative electrode; and
a functional material layer disposed between the sulfur-based positive electrode and the lithium-based negative electrode, a material of the functional material layer including a transition metal oxide having crystal water, a metal element in the transition metal oxide being selected from at least one of titanium, ruthenium, molybdenum, vanadium, tungsten, iron, and cobalt.
2. The lithium sulfur cell of claim 1 wherein the transition metal oxide with water of crystallization comprises TiO2·xH2O、H2TinO2n+1·H2O、RuO2·xH2O、MoO3·xH2O、(H3O)xMoO3·xH2O、HyV4O10·xH2O、HzV2O5·xH2O、V2O5·xH2O、V2O4·xH2O、WO3·xH2O、Fe2O3·xH2O and Co2O3·xH2N is more than or equal to 2 and less than or equal to 9, x is more than or equal to 0.5 and less than or equal to 10, and 0<y≤1，0<z≤1。
3. The lithium sulfur battery as claimed in claim 1 wherein the transition metal oxide having water of crystallization has a primary particle size of 1 to 100 nm.
4. The lithium sulfur battery according to claim 1, wherein the functional material layer has a thickness of 10nm to 200 μm and an areal density of 0.1 to 10 mg/cm.
5. The lithium sulfur battery according to claim 1, wherein the material of the functional material layer further comprises an electron conductive material and a binder, and the electron conductive material and the binder are uniformly mixed with the transition metal oxide having crystal water.
6. The lithium sulfur battery of claim 1, wherein the functional material layer is disposed on a surface of the sulfur-based positive electrode facing the lithium-based negative electrode, at least one surface of the separator, or a surface of the lithium-based negative electrode facing the sulfur-based positive electrode.
7. The lithium sulfur battery according to claim 1, wherein the functional material layer is provided on both surfaces of the separator.
8. The lithium sulfur battery according to claim 1, wherein the transition metal oxide having water of crystallization is contained in the functional material layer in an amount of 5 to 99% by mass.
9. The composite membrane is used for a lithium-sulfur battery and is characterized by comprising a membrane and a functional material layer arranged on at least one surface of the membrane, wherein the material of the functional material layer comprises a transition metal oxide with crystal water, and a metal element in the transition metal oxide is selected from at least one of titanium, ruthenium, molybdenum, vanadium, tungsten, iron and cobalt.
10. A lithium-sulfur battery electrode assembly comprising a lithium-based negative electrode, a separator, and a functional material layer disposed on top of each other, the functional material layer being disposed between the lithium-based negative electrode and the separator, the functional material layer being made of a material including a transition metal oxide having crystal water, wherein a metal element in the transition metal oxide is at least one selected from the group consisting of titanium, ruthenium, molybdenum, vanadium, tungsten, iron, and cobalt.
11. The composite lithium-based negative electrode is characterized by comprising metallic lithium and a functional material layer which are stacked mutually, wherein the material of the functional material layer comprises a transition metal oxide with crystal water, and a metal element in the transition metal oxide is selected from at least one of titanium, ruthenium, molybdenum, vanadium, tungsten, iron and cobalt.
12. Use of a functional material layer in a lithium-sulfur battery, comprising applying a solid-liquid mixture containing a transition metal oxide having crystal water, wherein a metal element is selected from at least one of titanium, ruthenium, molybdenum, vanadium, tungsten, iron, and cobalt, to a surface of at least one of a lithium-based negative electrode and a separator, thereby forming the functional material layer between a sulfur-based positive electrode and the lithium-based negative electrode.
13. The use of the functional material layer of claim 12 in a lithium sulfur battery, further comprising:
and drying at the temperature of 30-120 ℃ to remove the solvent in the coating formed by the solid-liquid mixture.
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| KR102229449B1 (en) * | 2017-10-26 | 2021-03-17 | 주식회사 엘지화학 | Seperator and lithium sulfur battery comprising the same |
| US20190221812A1 (en) * | 2018-01-16 | 2019-07-18 | Academia Sinica | Method for Manufacturing Fast Charging and Long Life Li-S Batteries |
| CN108461694B (en) * | 2018-04-24 | 2020-09-22 | 清华大学 | Double-effect composite diaphragm for lithium-sulfur battery and preparation method thereof |
| KR102415167B1 (en) * | 2018-10-26 | 2022-07-01 | 주식회사 엘지에너지솔루션 | Functional separator, method for preparing the same and lithium secondary battery including the same |
| CN109360926B (en) * | 2018-11-06 | 2020-03-24 | 长沙矿冶研究院有限责任公司 | Functionalized diaphragm for lithium-sulfur battery, preparation method of functionalized diaphragm and lithium-sulfur battery |
| CN110165124B (en) * | 2019-05-16 | 2022-02-22 | 华南师范大学 | Double-coating diaphragm applied to lithium-selenium disulfide battery and preparation method and application thereof |
| CN110098367A (en) * | 2019-05-31 | 2019-08-06 | 长春理工大学 | A kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm and preparation method thereof |
| CN110233225B (en) * | 2019-06-28 | 2020-07-21 | 电子科技大学 | Modified diaphragm for lithium-sulfur battery and preparation method thereof |
| CN110676442B (en) * | 2019-08-23 | 2020-10-20 | 浙江理工大学 | Method for preparing sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing atomic layer deposition technology |
| CN111403662A (en) * | 2020-03-27 | 2020-07-10 | 清华大学深圳国际研究生院 | Composite diaphragm, preparation method thereof and lithium battery |
| CN111416089B (en) * | 2020-04-10 | 2022-06-10 | 吉林师范大学 | Composite diaphragm for inducing and inhibiting growth of lithium dendrite, preparation method and lithium ion battery using diaphragm |
| CN115275525B (en) * | 2022-08-23 | 2023-08-22 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttle effect, preparation process thereof and lithium sulfur battery using diaphragm |
| CN117548105B (en) * | 2024-01-09 | 2024-03-19 | 西南石油大学 | alpha-MnO 2 Nanorod-loaded RuO 2 Positive electrode catalyst of lithium-sulfur battery and preparation method thereof |
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