CN107546357B - 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 PDF

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CN107546357B
CN107546357B CN201710656252.3A CN201710656252A CN107546357B CN 107546357 B CN107546357 B CN 107546357B CN 201710656252 A CN201710656252 A CN 201710656252A CN 107546357 B CN107546357 B CN 107546357B
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lithium
material layer
functional material
sulfur
sulfur battery
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CN107546357A (en
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唐子龙
王诗童
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Tsinghua University
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Tsinghua University
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • 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
    • 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
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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 invention provides a lithium-sulfur battery, which comprises a sulfur-based positive electrode, a lithium-based negative electrode, a diaphragm arranged between the sulfur-based positive electrode and the lithium-based negative electrode, and a functional material layer arranged between the sulfur-based positive electrode and the lithium-based negative electrode, wherein the material of the functional material layer comprises a Li-H-M-O system compound with Li, H, M and O elements, wherein M is a transition metal element. 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

Lithium-sulfur battery, assembly thereof and application of functional material layer in lithium-sulfur battery
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 has been a great deal of researchSome transition metal oxides (M-O), transition metal sulfides (M-S), and lithium transition metal oxides (Li-M-O) are coated on the separator as a functional material layer to improve the capacity and cycle performance of the lithium sulfur battery. Some of which are transition metal compounds Co3O4、Ti4O7、NiO、V2O3、Li4Ti5O12And the like can store lithium polysulfide by adsorption through surface polar or acidic sites; other transition metal compounds, e.g. TiO2、MnO2、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 compounds, the effect achieved in preventing shuttling of lithium polysulfides is still not optimal.
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 Li-H-M-O system compound having Li, H, M, and O elements, wherein M is a transition metal element.
In one embodiment, H in the Li-H-M-O system compound is present in the form of crystal water or structural water.
In one embodiment, the transition metal element M is at least one selected from titanium, manganese, vanadium, tungsten, molybdenum, nickel, and cobalt.
In one embodiment, the Li-H-M-O system compound has a formula of Li(0.01～4)H(0.01～8)MO(1-σ～6-σ)And 0. ltoreq. sigma. ltoreq.1, where sigma is the amount of oxygen vacancies.
In one embodiment thereof, the primary particles of the Li-H-M-O system compound have a particle size of 1 nm to 800 nm.
In one embodiment, the specific surface area of the Li-H-M-O system compound is 1M2G to 600m2/g。
In one embodiment thereof, the Li-H-M-O system compound has a layered crystal structure.
In one embodiment, the thickness of the functional material layer is 10nm to 200 μm, and the surface density is 0.1 to 30mg/cm2。
In one embodiment, the material of the functional material layer further includes an electron conductive material and a binder, and the electron conductive material and the binder are uniformly mixed with the Li-H-M-O system compound.
In one embodiment, 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.
In one embodiment, the functional material layer is disposed on both surfaces of the diaphragm.
In one embodiment, the Li-H-M-O system compound is 5 to 99% by mass of the functional material layer.
A composite separator for a lithium-sulfur battery includes a separator and a functional material layer disposed on at least one surface of the separator, the functional material layer including a Li-H-M-O system compound having Li, H, M, and O elements, wherein M is a transition metal element.
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 being made of a Li-H-M-O system compound having Li, H, M, and O elements, wherein M is a transition metal element.
A lithium-sulfur battery electrode assembly includes a lithium-based negative electrode, a separator, and a functional material layer stacked on each other, the functional material layer including a Li-H-M-O system compound having Li, H, M, and O elements, wherein M is a transition metal element.
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, the functional material layer is made of a Li-H-M-O system compound containing Li, H, M and O elements, and M is a transition metal element.
A composite lithium-based negative electrode comprises metallic lithium and a functional material layer which are mutually stacked, wherein the material of the functional material layer comprises a Li-H-M-O system compound containing Li, H, M and O elements, wherein M is a transition metal element.
Use of a functional material layer in a lithium sulfur battery, comprising:
applying a solid-liquid mixture of a Li-H-M-O system compound having Li, H, M, and O elements to a surface of at least one of the sulfur-based positive electrode, the lithium-based negative electrode, and the separator, thereby forming the functional material layer between the sulfur-based positive electrode and the lithium-based negative electrode.
In one embodiment, the method further comprises:
and drying at the temperature of 30-120 ℃ to remove the solvent in the coating formed by the solid-liquid mixture.
Compared with the Li-M-O system material which is calcined at high temperature to remove the hydrogen component, the Li-H-M-O system material has larger specific surface area, thereby providing more active sites, better playing a role in adsorbing, storing and/or catalyzing lithium polysulfide, effectively playing a role in inhibiting shuttle of the lithium polysulfide 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 in PP @ C & LHTO-1 of example 1;
FIG. 4 is a graph comparing the cycle performance at 0.2C for a lithium sulfur battery using PP @ C & LHTO-1 in example 1 and a lithium sulfur battery using PP in a comparative example;
FIG. 5 is a graph of cycling performance versus coulombic efficiency at 1C for a lithium sulfur battery using PP @ C & LHTO-1 of example 1;
FIG. 6 is a graph comparing rate performance of lithium sulfur batteries using PP @ C & LHTO-1 in example 1 and PP @ C & LTO-1 in comparative example.
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. 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 Li-H-M-O system compound. The Li-H-M-O system compound has Li, H, M and O elements, wherein M is one or more transition metal elements.
The Li-H-M-O system compound can adsorb, store and/or catalyze lithium polysulfide and inhibit lithium polysulfide shuttling. In addition, due to the hydrogen component in the compound, a certain degree of reaction with lithium ions may exist or the lithium ions are uniformly distributed through surface polarity adjustment, so that the effect of inhibiting the growth of lithium dendrites is achieved.
Preferably, the Li-H-M-O system compound has a layered crystal structure, does not influence the transmission of lithium ions while inhibiting the shuttling of lithium polysulfide, and provides a fast conduction channel for the lithium ions. It is understood that the "layered" crystal structure is distinguished from the nanosheet shape of the apparent morphology of the primary particles of the compound, where the layered crystal structure is the arrangement of atoms in the unit cell.
The transition metal may be at least one selected from titanium (Ti), molybdenum (Mo), vanadium (V), tungsten (W), manganese (Mn), nickel (Ni), and cobalt (Co).
The H in the Li-H-M-O system compound can exist in the form of crystal water or structural water in the compound molecule. In addition, the Li-H-M-O system compound may also have an oxygen vacancy. The preferable general formula of the Li-H-M-O system compound may be Li(0.01～4)H(0.01～8)MO(1-σ～6-σ)0 is less than or equal to sigma and less than or equal to 1, wherein sigma is the amount of oxygen vacancies. The Li-H-M-O system compound is preferably a nano-scale material, and the particle diameter of the primary particle is preferably 1 nm to 800 nm, more preferably 1 nm to 100 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 specific surface area of the Li-H-M-O system compound is preferably 1M2G to 600m2G, more preferably 100m2G to 600m2/g。
M in the Li-H-M-O system compound is preferably Ti. In the Li-H-Ti-O compound, the mass fraction of Li is preferably 3% to 10%, the mass fraction of H is preferably 0.3% to 8%, the mass fraction of Ti is preferably 46% to 53%, and the mass fraction of O is preferably 30% to 50%. The general formula of the Li-H-Ti-O compound may be Li(0.43～1.44)H(0.29～7.93)Ti(0.96～1.11)O(1.88-σ～3.13-σ)Wherein sigma is more than or equal to 0 and less than or equal to 1.81. Sufficient crystalline and/or structural water is present in the Li-H-Ti-O compound to enable the Li-H-Ti-O compound to maintain a layered crystal structure.
In a more preferred embodiment, the Li-H-Ti-O compound contains LiThe amount fraction is preferably 4 to 12%, the mass fraction of H is preferably 0.1 to 5%, the mass fraction of Ti is preferably 48 to 56%, and the mass fraction of O is preferably 28 to 47%. The general formula of the Li-H-Ti-O compound may be Li(0.58～1.73)H(0.10～4.96)Ti(1.00～1.17)O(1.75-σ～2.93-σ)Wherein sigma is more than or equal to 0 and less than or equal to 1.73. In this embodiment, a portion of the Li, Ti, and O elements may be nanostructured Li4Ti5O12And TiO2Are present, these nanostructures are homogeneously dispersed in the Li-H-Ti-O layered crystal structure.
In one embodiment, the Li-H-M-O system compound can be obtained by reacting a Li-M-O nanomaterial with an acidic aqueous solution. The Li-M-O nanomaterial may be, for example, Li4Ti5O12、LiMn2O4、LiMnO2、LiCoO2、LiNiO2、Li2MoO4And Li3VO4At least one of (1). The Li-M-O nano material can be reacted with an acid water solution at normal temperature and normal pressure, and can also be subjected to a hydrothermal reaction with acid at 80-200 ℃. The acid may be at least one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, oxalic acid and hydrofluoric acid, and the concentration may be 0.1-0.8 mol/L. The powder obtained after the reaction can be further separated, purified and dried to obtain Li-H-M-O nano material powder, and the drying temperature is preferably below 120 ℃. The thickness of the functional material layer 32 is preferably 10 nm-200 μm, and the surface density is preferably 0.1-30 mg/cm2。
Preferably, the material of the functional material layer 32 further includes an electron conductive material and a binder, which are uniformly mixed with the Li-H-M-O system compound. The Li-H-M-O system compound is preferably contained in the functional material layer 32 in a mass percentage of 5% to 99%. 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 Li-H-M-O system compound to a surface of at least one of the sulfur-based positive electrode 10, the lithium-based negative electrode 20, 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 Li-H-M-O system compound, and may further include the electron conductive material and the binder. The solid phase and the liquid phase in the solid-liquid mixture are preferably solvents, and the Li-H-M-O system compound, the electronic conductive material, the binder and the solvents are uniformly mixed. The solvent is used as a carrier of the Li-H-M-O system compound, so that the solvent which can not dissolve the Li-H-M-O system compound, does not react with the Li-H-M-O system compound and can be completely removed at a lower temperature (such as 30-120 ℃), such as water or a low molecular weight volatile organic solvent, and can be selected from one or more of N-methyl pyrrolidone, water, methanol, ethanol, propanol, isopropanol, acetonitrile, acetone and diethyl ether, is required to be selected.
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 Li-H-M-O system compound in the functional material layer 32 after drying is maintained to have the hydrogen component.
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 the Li-H-M-O system compound has the functions of adsorbing, storing and/or catalyzing lithium polysulfide in the lithium-sulfur battery, and the diversity of the crystal structure and the nanometer dimension of the Li-H-M-O system compound in the functional material layer 32 is improved and the ionic conductivity of the functional material layer 32 is improved through the introduction of a hydrogen component. The specific surface area of the material can be improved by introducing the hydrogen component, and the larger specific surface area can provide more active sites, so that the effect of inhibiting lithium polysulfide shuttling is efficiently exerted, and the electrochemical performance and the safety performance of the lithium-sulfur battery are improved.
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 hydrogen component 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-sulfur batteries and the like in electric vehicles, energy storage power stations and high-capacity electronic products.
In addition, most methods for preparing compounds of Li-H-M-O system are wet chemical methods (such as hydrothermal synthesis method or sol-gel method), the products obtained by the methods are often hydrates, and the hydrogen components in the products are removed through medium-high temperature heat treatment which is conventionally carried out. The Li-H-M-O system compound 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 Li-H-M-O system compound-based functional material layer: mixing Li1.81H0.19Ti2O5-σ(sigma represents oxygen vacancy), Super P and PVDF are added into N-methyl pyrrolidone according to the mass ratio of 8:1:1 to be mixed into slurry, then the slurry is coated on one side of a polypropylene diaphragm by using a tape casting method, and the slurry is dried in vacuum at 60 ℃ for 10 hours to obtain the composite diaphragm (hereinafter referred to as PP @ C) with the Li-H-Ti-O system compound-based functional material layer&LHTO-1)。PP@C&A Scanning Electron Microscope (SEM) view of the functional material layer in LHTO-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&LHTO-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). 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.
Comparative example 1
The same 2032 type button cell as in example 1 was assembled by replacing PP @ C & LHTO-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, except that PP @ C & LHTO-1 was replaced with PP.
Comparative example 2
Same as example 1 except for Li in example 11.81H0.19Ti2O5-σHeating and dehydrating at 350 ℃ to obtain Li4Ti5O12-TiO2(LTO-1 hereinafter) andli in the functional material layer preparation step in example 11.81H0.19Ti2O5-σReplacing the material with LTO-1 to obtain the composite diaphragm (hereinafter referred to as PP @ C) with a Li-Ti-O system material coating&LTO-1), assemble a 2032 type button cell identical to example 1, except for PP @ C&LHTO-1 is replaced by PP @ C&LTO-1。
Testing of electrochemical cell Performance
The electrochemical cycle characteristics of the button cells of example 1 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 tables 1 and 2. FIG. 4 is a graph comparing the cycle performance at 0.2C for lithium sulfur batteries using PP @ C & LHTO-1 in example 1 and PP in comparative example 1. FIG. 5 is a graph of cycling performance versus coulombic efficiency at 1C for the lithium sulfur battery of example 1 using PP @ C & LHTO-1. FIG. 6 is a graph comparing rate performance of lithium sulfur batteries using PP @ C & LHTO-1 in example 1 and PP @ C & LTO-1 in comparative example 2.
TABLE 1
Multiplying factor of current Specific capacity of initial discharge Discharge specific capacity of Nth cycle
Example 1 0.2C 1714mAh/g 823mAh/g,N＝200
Example 1 1C 765mAh/g 300mAh/g,N＝2400
Comparative example 1 0.2C 979mAh/g 285mAh/g,N＝200
TABLE 2
Multiplying factor of current Example 1 specific discharge capacity Comparative example 2 specific discharge capacity
0.1C 1212mAh/g 1062mAh/g
0.2C 1066mAh/g 886mAh/g
0.5C 786mAh/g 593mAh/g
1C 646mAh/g 454mAh/g
2C 527mAh/g 333mAh/g
5C 358mAh/g 202mAh/g
As can be seen from the comparison of cycle properties in FIG. 4, the first discharge capacity of the lithium-sulfur battery using PP @ C & LHTO-1 was as high as 1714mAh/g, while the first discharge capacity of the control battery using PP was only 979 mAh/g. After 200 cycles, the lithium-sulfur battery using PP @ C & LHTO-1 still can maintain the stable specific capacity of 823mAh/g, which is 2.9 times of the specific capacity of a control battery using PP. As can be seen from fig. 5, at a high rate of 1C, the lithium-sulfur battery using PP @ C & LHTO-1 still has a reversible specific capacity of 300mAh/g after 2400 cycles, the coulombic efficiency is close to 100%, the "shuttle effect" of lithium polysulfide is significantly reduced, and the battery exhibits very excellent high rate capacity and cycle stability.
Using PP @ C&LTO-1 and PP @ C&The LHTO-1 comparison examines the advantages of hydrogen-containing components in lithium sulfur batteries. As can be seen from FIG. 6, compared to PP @ C&LTO-1，PP@C&LHTO-1 can respectively improve the specific capacity of the battery by 14.1 percent (0.1C), 20.3 percent (0.2C), 32.5 percent (0.5C), 42.3 percent (1C) and 58.3 percent (2C), and particularly can still maintain 358mAh g under the large multiplying power of 5C-1The specific capacity of (A) is PP @ C&Approximately 2 times that of LTO-1. This is due to the nano Li1.81H0.19Ti2O5-σCoarsening and agglomeration often occur in the crystal structure in the high-temperature dehydration process, the size of material particles is increased, the specific surface area is greatly reduced, and the adsorption storage and catalytic action of active sites in the material on lithium polysulfide are further reduced; furthermore, Li1.81H0.19Ti2O5-σThe two-dimensional layered structure disappears at any time, and is converted into a three-dimensional structure, and the ion migration capability of the materialAnd finally leads to unsatisfactory electrochemical performance.
Example 2
1) Preparation of a functional Material layer with a Li-H-M-O System Compound: mixing Li0.71H0.49Mn1.73O3.88Adding Ketjen black and PVDF into an ethanol solvent according to the mass ratio of 7:2:1 to mix into slurry, then coating the slurry on the two sides of a polyethylene diaphragm by using spin coating, and drying the slurry at 80 ℃ in vacuum for 10 hours to obtain the composite diaphragm (hereinafter referred to as PE @ C) with the Li-H-Mn-O system compound-based functional material layer&LHMO-2)。
2) Assembling the lithium-sulfur battery: as in example 1, the only difference is that PP @ C & LHTO-1 is replaced by PE @ C & LHMO-2.
Example 3
1) Preparation of a functional Material layer with a Li-H-M-O System Compound: mixing 7Li2WO4·4H2Adding 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 Li-H-W-O system compound-based functional material layer&LHWO-3)。
2) Assembling the lithium-sulfur battery: as in example 1, the only difference is that the sublimed sulfur is replaced by a sulfur-carbon composite and the PP @ C & LHTO-1 is replaced by PE/PP @ C & LHWO-3.
Example 4
1) Preparation of a functional Material layer with a Li-H-M-O System Compound: LiVO (lithium ion vanadium oxide)3·0.5H2Adding 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 composite sulfur-based positive electrode (hereinafter referred to as S @ C) with the Li-H-V-O system compound-based functional material layer&LHVO-4)。
2) Assembling the lithium-sulfur battery: s @ C & LHVO-4 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 5
1) Preparation of a functional Material layer with a Li-H-M-O System Compound: mixing LiMoO3·H2Adding 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 (PAN @ C for short) with the Li-H-Mo-O system compound-based functional material layer&LHMO-5)。
2) Assembly of lithium-sulfur Battery As in example 1, except that the sublimed sulfur was replaced with a sulfur-carbon composite and PP @ C & LHTO-1 was replaced with PAN @ C & LHMO-5.
As can be seen from the above experiments, in the preparation method of the nano oxide, the precursor prepared by a wet chemical method (such as a hydrothermal reaction or a sol-gel reaction) often has a hydrogen component (crystal water or structural water). The compound with crystal water is traditionally considered to be dehydrated by high-temperature calcination to be used in a lithium ion battery or a lithium sulfur battery of a high-voltage organic electrolyte system. 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 hydrogen components in the material, avoids coarsening and agglomeration of a nanocrystal structure in a high-temperature dehydration process, enables a Li-H-M-O system compound to have a large number of active sites, and inhibits lithium polysulfide shuttling of a lithium-sulfur battery by adsorbing, storing and/or catalyzing lithium polysulfide through the large number of active sites. The introduction of hydrogen elements can promote the diversity of the microscopic morphology of the material (such as 2D nano-sheets, 1D nano-tubes/wires and 0D nano-particles), and can also keep a relatively 'loose' crystal structure in the rapid ion insertion/extraction process (the ion close packing degree in the crystal structure is low, which is beneficial to ion diffusion), and the diversity of the microscopic morphology of the Li-H-M-O system compound (such as two-dimensional lamellar) can greatly improve the ionic conductivity of the material, thereby effectively improving the electrochemical performance of the lithium-sulfur battery. In addition, when the compound has a smaller grain size, the compound 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 shuttling of the lithium sulfur battery is achieved.
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 (15)

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, the functional material layer including a Li-H-M-O system compound having Li, H, M, and O elements, wherein M is a transition metal element, H in the Li-H-M-O system compound being present in the form of crystal water or structural water, and the transition metal element M being selected from at least one of titanium, manganese, vanadium, tungsten, molybdenum, nickel, and cobalt.
2. The lithium sulfur battery of claim 1 wherein the Li-H-M-O system compound has a formula of Li(0.01～4)H(0.01～8)MO(1-σ～6-σ)And 0. ltoreq. sigma. ltoreq.1, where sigma is the amount of oxygen vacancies.
3. The lithium sulfur battery as defined in claim 1 wherein the primary particles of the Li-H-M-O system compound have a particle size of 1 to 800 nm.
4. The lithium sulfur battery of claim 1, wherein the Li-H-M-O system compound has a specific surface area of 1M2G to 600m2/g。
5. The lithium sulfur battery of claim 1 wherein the Li-H-M-O system compound has a layered crystal structure.
6. 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 30mg/cm2。
7. The lithium sulfur battery as claimed in claim 1 wherein the material of the functional material layer further comprises an electron conductive material and a binder, the electron conductive material and the binder being uniformly mixed with the Li-H-M-O system compound.
8. 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.
9. The lithium sulfur battery according to claim 1, wherein the functional material layer is provided on both surfaces of the separator.
10. The lithium sulfur battery according to claim 1, wherein the Li-H-M-O system compound is contained in the functional material layer in an amount of 5 to 99% by mass.
11. The composite diaphragm is used for a lithium-sulfur battery and is characterized by comprising a diaphragm and a functional material layer arranged on at least one surface of the diaphragm, wherein the material of the functional material layer comprises a Li-H-M-O system compound containing Li, H, M and O elements, wherein M is a transition metal element, H in the Li-H-M-O system compound exists in the form of crystal water or structural water, and the transition metal element M is selected from at least one of titanium, manganese, vanadium, tungsten, molybdenum, nickel and cobalt.
12. A lithium-sulfur battery electrode assembly, comprising a lithium-based negative electrode, a separator, and a functional material layer, wherein the functional material layer is disposed between the lithium-based negative electrode and the separator, the functional material layer is made of a Li-H-M-O system compound containing Li, H, M, and O elements, wherein M is a transition metal element, H in the Li-H-M-O system compound is present in the form of crystal water or structural water, and the transition metal element M is at least one selected from titanium, manganese, vanadium, tungsten, molybdenum, nickel, and cobalt.
13. 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 Li-H-M-O system compound containing Li, H, M and O elements, wherein M is a transition metal element, H in the Li-H-M-O system compound exists in the form of crystal water or structural water, and the transition metal element M is at least one selected from titanium, manganese, vanadium, tungsten, molybdenum, nickel and cobalt.
14. Use of a functional material layer in a lithium-sulfur battery, comprising:
applying a solid-liquid mixture of a Li-H-M-O system compound having Li, H, M, and O elements, wherein M is a transition metal element, in which H is present in the form of crystal water or structural water, 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, the transition metal element M being selected from at least one of titanium, manganese, vanadium, tungsten, molybdenum, nickel, and cobalt.
15. The use of the functional material layer of claim 14 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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