WO2016047942A1 - 리튬-황 전지 및 이를 포함하는 전지 모듈 - Google Patents
리튬-황 전지 및 이를 포함하는 전지 모듈 Download PDFInfo
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- WO2016047942A1 WO2016047942A1 PCT/KR2015/009533 KR2015009533W WO2016047942A1 WO 2016047942 A1 WO2016047942 A1 WO 2016047942A1 KR 2015009533 W KR2015009533 W KR 2015009533W WO 2016047942 A1 WO2016047942 A1 WO 2016047942A1
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present specification relates to a lithium-sulfur battery including an anode, a cathode, and an electrolyte provided between the anode and the cathode, and a battery module including the same.
- the lithium-sulfur battery uses a sulfur-based compound having a sulfur-sulfur bond as a cathode active material, and a secondary material using a carbon-based material in which insertion and deintercalation of alkali metals such as lithium or metal ions such as lithium ions occurs. It is a battery.
- the reduction of sulfur-sulfur bonds during the reduction of the discharging reaction results in the reduction of sulfur oxides, and the oxidation-reduction reaction in which the sulfur-sulfur bonds are re-formed as the oxidation-response of sulfur increases during the oxidation reaction. .
- Lithium-sulfur batteries have an energy density of 3830 mAh / g when using lithium metal used as an anode active material and a energy density of 1675 mAh / g when using sulfur (S 8 ) used as a cathode active material.
- sulfur-based material used as the cathode active material has the advantage of being inexpensive and environmentally friendly material.
- the present specification is to provide a lithium-sulfur battery including an anode, a cathode and an electrolyte provided between the anode and the cathode and a battery module including the same.
- anode comprising an anode current collector and a lithium metal layer provided on the anode current collector;
- a cathode comprising a sulfur containing material;
- An electrolyte provided between the anode and the cathode;
- an insulating film provided to cover a boundary line between the anode current collector and the lithium metal layer.
- the present disclosure provides a battery module including the lithium-sulfur battery as a unit cell.
- Corrosion of the lithium metal may be reduced in the anode of the lithium-sulfur battery according to one embodiment of the present specification.
- FIG. 1 is a schematic diagram of the corrosion behavior of the lithium metal layer according to sulfur elution in a lithium-sulfur battery.
- FIG. 2 is a schematic view of a lithium-sulfur battery according to one embodiment of the present specification.
- FIG. 3 is a schematic diagram of an anode of a lithium-sulfur battery according to one embodiment of the present specification.
- 4 to 11 are schematic views of an insulating film provided in the lithium electrode having the structure of FIG.
- FIG. 12 is a structural diagram of a lithium-sulfur battery prepared in Experimental Example 1.
- FIG. 12 is a structural diagram of a lithium-sulfur battery prepared in Experimental Example 1.
- FIG. 13 is a photograph of a lithium-sulfur battery after driving of the lithium-sulfur battery of Experimental Example 1.
- FIG. 14 is a structural diagram of a lithium-sulfur battery prepared in Experimental Example 3.
- FIG. 14 is a structural diagram of a lithium-sulfur battery prepared in Experimental Example 3.
- FIG. 15 is a photograph of a lithium-sulfur battery after driving the lithium-sulfur battery of Experimental Example 3.
- FIG. 15 is a photograph of a lithium-sulfur battery after driving the lithium-sulfur battery of Experimental Example 3.
- FIG. 16 is a structural diagram of a lithium-sulfur battery of Example 1.
- 17 is a structural diagram of an anode on which a polymer protective layer is formed.
- FIG. 18 is a schematic diagram of an anode of a lithium-sulfur battery according to another exemplary embodiment of the present specification.
- 19 to 22 are schematic views of an insulating film provided in the lithium electrode having the structure of FIG. 18.
- FIG. 23 shows the results of Experimental Example 1.
- FIG. 24 shows the results of Experimental Example 2.
- anode comprising an anode current collector and a lithium metal layer provided on the anode current collector;
- a cathode comprising a sulfur containing material;
- An electrolyte provided between the anode and the cathode;
- an insulating film provided to cover a boundary line between the anode current collector and the lithium metal layer.
- covering means that the contact is provided in direct contact, for example, "an insulating film provided to cover the boundary between the anode current collector and the lithium metal layer” is a border between the anode current collector and the lithium metal layer. This means that the insulating film is in direct contact with each other, and further, that the insulating film seals the boundary line so that the boundary line between the anode current collector and the lithium metal layer is not exposed to the electrolyte solution.
- the anode emits electrons when the battery is discharged, and an oxidation reaction occurs to generate metal ions, and may serve as a cathode (reduction electrode) when the battery is charged.
- the anode may include an anode current collector and a lithium metal layer provided on the anode current collector.
- Lithium metal in the lithium metal layer is a metal having a standard reduction potential of -3.040 V, and is a metal that is highly prone to oxidation, and is a heterogeneous material that is prone to oxidation such as oxygen, sulfur, or polysulfide.
- oxidation corrosion
- a lithium metal having a lower potential than a high dissimilar metal is a high potential metal.
- sacrificial polarization reactions are consumed sacrificially. This sacrificial polarization reaction appears to occur at the junction between the metals, which serves as a relatively low energy state (unstable state) and a high reaction site rather than the surface of the lithium metal.
- the sacrificial polarization reaction of the lithium metal of the lithium metal layer provided on the anode current collector including a dissimilar metal having a higher potential than that of the lithium metal may occur at the edge bonded to the anode current collector.
- the lithium-sulfur battery of the present disclosure may prevent or reduce corrosion of the lithium metal layer due to the sacrificial anodization reaction.
- the anode current collector may be any material having electrical conductivity as the current collector of the anode, and for example, one or two or more selected from the group consisting of carbon, stainless steel, nickel, aluminum, iron, and titanium. It may be used, and more specifically, a carbon-coated aluminum current collector may be used.
- the use of an aluminum substrate coated with carbon has an advantage in that the adhesion to the active material is excellent, the contact resistance is low, and the corrosion of polysulfide of aluminum is prevented, compared with the non-carbon coated aluminum substrate.
- the shape of the current collector may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, or a nonwoven fabric.
- the lithium metal layer means an anode active material layer containing a lithium metal element.
- the material of the lithium metal electrode may be lithium alloy, lithium metal, oxide of lithium alloy or lithium oxide. In this case, a part of the lithium metal layer may be altered by oxygen or moisture or include impurities.
- the lithium metal layer may generate lithium ions while emitting electrons when the battery is discharged.
- the insulating layer may be provided to cover a boundary line between the anode current collector and the lithium metal layer.
- lithium polysulfide may be prevented from reacting with sulfur existing on the electrolyte at the boundary line between the anode current collector and the lithium metal layer.
- the boundary line between the anode current collector and the lithium metal layer refers to a line formed at a boundary thereof by providing a lithium metal layer on the anode current collector. Referring to FIGS. 3 and 18, the anode cross section of FIGS. The boundary line between the anode current collector and the lithium metal layer means “10”.
- the insulating layer is not limited to the shape of the insulating layer as long as it covers the boundary line between the anode current collector and the lithium metal layer.
- the insulating layer may be any one of the insulating layers shown in FIGS. 4 to 11 and 19 to 22. .
- the insulating film 100 may cover only the boundary line 10 between the anode current collector and the lithium metal layer. Specifically, as shown in FIG. 4, a part of the upper surface of the current collector and a part of the side of the lithium metal layer may be covered together, or as shown in FIG. 19, the side of the current collector and the side of the lithium metal layer adjacent to the boundary line together. Can be covered
- the insulating layer may be provided to cover a surface where the anode current collector and the lithium metal layer are in contact with each other and a surface of the anode current collector which is not in contact with the lithium metal layer.
- the anode current collector is isolated so as not to come into contact with an electrolyte in which sulfur may exist, and thus, the anode current collector does not accelerate lithium to react with sulfur to generate lithium polysulfide.
- the loss of the sulfur-containing active material can be reduced and the corrosion of the lithium metal layer can be reduced.
- the insulating film is not limited to the form provided if it covers the surface not in contact with the lithium metal layer of the boundary line between the anode current collector and the lithium metal layer and the surface provided with the lithium metal layer of the anode current collector, for example, FIGS. It may be one of the forms of the insulating film shown in 11.
- the insulating film 100 may have a boundary line 10 between the anode current collector and the lithium metal layer and a surface that is not in contact with the lithium metal layer among the surfaces provided with the lithium metal layer of the anode current collector 20. ) Can be covered only.
- the insulating layer may be further provided on the side of the lithium metal layer. Specifically, the insulating layer may be provided on a boundary line between the anode current collector and the lithium metal layer, on the surface not in contact with the lithium metal layer and on the side of the lithium metal layer.
- the insulating film is further provided on the side surface of the lithium metal layer, the side surfaces of the lithium metal layer and the anode current collector are separated from the electrolyte solution to suppress the rapid corrosion reaction and to suppress the side reaction having lower energy than the upper surface of the lithium metal layer. In this case, a uniform electrochemical reaction can be induced in the lithium metal layer.
- the insulating layer is not limited to the form provided if the boundary between the anode current collector and the lithium metal layer covers the surface of the anode current collector, the surface not in contact with the lithium metal layer and the side surface of the lithium metal layer. 6 to 11 and 20 to 22 may be any one of the forms of the insulating film.
- the insulating film 100 may not be in contact with the lithium metal layer among the boundary line 10 between the anode current collector and the lithium metal layer and the surface of the anode current collector. It may cover only the surface 20 and the side surface 30 of the lithium metal layer. Specifically, the thickness of the insulating film may not be constant from each surface as shown in FIG. 6, and the thickness of the insulating film may be similar or the same from each surface as shown in FIG. 7.
- the insulating layer 100 may cover only the boundary line 10 between the anode current collector and the lithium metal layer, the side surface of the anode current collector, and the side surface 30 of the lithium metal layer.
- the insulating layer may be further provided to cover the edge of the lithium metal layer.
- the insulating film may be provided to cover a boundary line between the anode current collector and the lithium metal layer, a surface not in contact with the lithium metal layer, a side surface of the lithium metal layer, and an edge of the lithium metal layer among the surfaces provided with the lithium metal layer of the anode current collector. have.
- a rapid corrosion reaction of the lithium metal layer may be suppressed to induce a uniform reaction of the lithium metal layer, and the process of coating an insulating film provided to cover the boundary line between the anode current collector and the lithium metal layer has an advantage of being easy.
- the insulating layer does not limit the form provided if the boundary between the anode current collector and the lithium metal layer covers the surface of the anode current collector, which is not in contact with the lithium metal layer, the side surface of the lithium metal layer, and the edge of the lithium metal layer. However, for example, it may be one of the forms of the insulating film shown in FIGS. 8 to 11 and 21 to 22.
- the insulating film 100 may include a boundary line 10 between the anode current collector and the lithium metal layer, and a surface not in contact with the lithium metal layer among the surfaces of the anode current collector. ), Only the side surface 30 of the lithium metal layer and the corner 40 of the lithium metal layer may be covered. Specifically, the thickness of the insulating film may not be constant from each surface as shown in FIG. 8, and the thickness of the insulating film may be similar or the same from each surface as shown in FIG. 9.
- the insulating film 100 includes a boundary line 10 in which an anode current collector and a lithium metal layer contact each other, and a surface 20 that does not contact a lithium metal layer among lithium metal layers of the anode current collector. It may cover only the side surface 30 of the metal layer, the edge 40 of the lithium metal layer and the side surface of the anode current collector.
- the insulating film 100 includes a boundary line 10 in which an anode current collector and a lithium metal layer contact each other, and a surface 20 that does not contact a lithium metal layer among lithium metal layers of the anode current collector and lithium. It may cover only the side surface 30 of the metal layer, the edge 40 of the lithium metal layer, the side surface of the anode current collector and the opposite side of the surface provided with the lithium metal layer of the anode current collector.
- the insulating film 100 may cover the boundary line 10 between the anode current collector and the lithium metal layer, the side surface 30 of the lithium metal layer, the corner 40 of the lithium metal layer, and the side surface of the anode current collector. Can be.
- the insulating film 100 includes a boundary line 10 between an anode current collector and a lithium metal layer, a side surface 30 of a lithium metal layer, a corner 40 of a lithium metal layer, a side surface of an anode current collector, and an anode.
- the current collector may cover only a surface opposite to a surface on which a lithium metal layer is provided.
- a chemical layer may be formed using an electrolyte component on the surface of the lithium metal.
- an additive ex. LiNO 3
- the viscosity of the electrolyte may be increased and the ion conductivity of the electrolyte may be reduced due to the addition of the additive.
- an additive that forms a chemical layer may not be added or the content of the additive may be reduced, thereby increasing the viscosity of the electrolyte and reducing the ion conductivity of the electrolyte due to the addition of the additive.
- a polymer protective layer for suppressing dendritic growth of lithium metal is formed on the surface of the lithium metal as shown in FIG. 17.
- the protective layer is different from the position at which the anode and the film of the present specification, in which an insulating film is formed to cover the edges of the lithium metal and the anode current collector, is formed and cannot form lithium polysulfide through the protective layer.
- the thickness of the insulating layer may be 1 nm or more and 500 ⁇ m or less.
- the thickness of the insulating film means the shortest distance from the surface provided to the upper portion of the insulating film.
- the thickness from each surface may be the same or different.
- the thickness of the insulating film may be 1 nm or more and 500 ⁇ m or less, and specifically, 100 nm or more and 5 ⁇ m or less.
- the thickness of the insulating film may be 1 nm or more and 500 ⁇ m or less, and specifically, 50 nm or more and 10 ⁇ m or less.
- the surface of the laminate that is, the entire surface except the interface where the anode current collector and the lithium metal layer contact each other. At least 0.1% or more of the area may be covered with an insulating film.
- the insulating film covers all the boundary lines between the anode current collector and the lithium metal layer, and at least 10% or more of the area of the entire surface of the lithium metal layer except for the interface between the anode current collector and the lithium metal layer should not be covered with the insulating film. do.
- the laminate at least 0.1% or more and 90% or less of an area of the surface of the laminate, that is, the surface of the surface other than the interface where the anode current collector and the lithium metal layer contact each other may be covered with an insulating film.
- the insulating film covers all the boundary lines between the anode current collector and the lithium metal layer, and at least 10% or more of the area of the entire surface of the lithium metal layer except for the interface between the anode current collector and the lithium metal layer should not be covered with the insulating film. do.
- the insulation resistance of the insulating film may be 10 6 ⁇ ⁇ m (Deionized water) or more.
- the insulation resistance is less than 10 6 ⁇ ⁇ m (when the electrical conductivity is increased)
- lithium metal may be precipitated from the insulating film by the reduction of lithium ions as the charge and discharge are repeated.
- the material of the insulating film is not particularly limited as long as the insulation resistance of the prepared insulating film is 10 6 ⁇ ⁇ m (Deionized water) or more.
- the insulating film may include at least one of a ceramic insulating material and an insulating polymer.
- the ceramic insulating material may include at least one of an oxide ceramic insulating material and a nitride ceramic insulating material, but is not limited thereto.
- the ceramic oxide insulating material is aluminum oxide, antimony trioxide, antimony tetroxide, antimony pentoxide, arsenic trioxide, arsenic pentoxide, barium oxide, bismuth (III) oxide, bismuth (V) oxide, Calcium oxide, Chromium (II) oxide, Chromium (III) oxide, Chromium (IV) oxide, Chromium (VI) oxide, Cobalt (II) oxide, Cobalt (II, III) oxide, Cobalt (III) oxide, Copper (I) oxide, Copper (II) oxide, Iron (II) oxide, black, Iron (II, III) oxide, Iron (III) oxide, Lead (II) oxide, Lead (II, IV) oxide, Lead (IV) oxide, Lithium oxide, Magnesium oxide, Manganese ( II) oxide, Manganese (III) oxide, Manganese (IV) oxide, Manganese (VII) oxide, Mercury (II) oxide, Nickel (II) oxide, Nickel (III)
- the ceramic nitride insulating material is aluminum gallium nitride, aluminum nitride, aluminum oxynitride, Beryllium nitride, Beta carbon nitride, Boron nitride, Calcium nitride, Chromium nitride, Gallium nitride, Germanium nitride, Graphitic carbon nitride, Indium gallium aluminum nitride, Indium gallium nitride, Indium nitride, Iron nitride, Lithium nitride, Magnesium nitride, Niobium nitride, Phosphoryl nitride, Silicon nitride, Silicon oxynitride, Silver azide, Silver nitride, Sodium nitride, Strontium nitride, Tantalum nitride, Tetrasulfur tetranitride, Titanium aluminum nitride, Titan
- the insulating polymer is Epoxy, Nitrile (rubber), enol-formalehyde, Polyacrylonitrile, Polyamide (Nylon 66), Polybutadiene, Polybutylene terephthalate, Polycarbonate (PC), Polyester, Polyetheretherketone (PEEK), Polyethylene (PE), Polyethylene terephalate (PET) , Polyimide, Polymethyl methacrylate (PMMA), Polymethylpentene (TPX), Polypropylene (PP), Polysulfone (PSF), Polystyrene (PS), Polytetrafluoroethylene (PTFE), Polyvinyl acetate, Polyvinylidene fluoride (PVDF),, Polyvinyl chloride (PVC), It may include at least one of silicone (rubber) and styrene butadiene (rubber).
- the cathode receives a cation transferred from the anode when the battery is discharged, and a reduction reaction occurs, and may serve as an anode (anode) during charging of the battery.
- the cathode may include a sulfur-containing material as a cathode active material, in which case the reduction reaction of the cathode may occur while the lithium cation delivered from the anode reacts with sulfur of the cathode to form a sulfur-lithium metal complex.
- sulfur or lithium polysulfide may be eluted into the electrolyte, and sulfur or lithium polysulfide, which is leaked into the electrolyte, may move to the anode.
- the cathode may include a cathode current collector and a sulfur-containing active material layer provided on the cathode current collector.
- the cathode may include a cathode current collector.
- the cathode current collector may be any material having electrical conductivity as the current collector of the cathode. For example, at least one selected from the group consisting of carbon, stainless steel, nickel, aluminum, iron, and titanium may be used. It may be used, and more specifically, a carbon-coated aluminum current collector may be used.
- the use of an aluminum substrate coated with carbon has an advantage in that the adhesion to the active material is excellent, the contact resistance is low, and the corrosion of polysulfide of aluminum is prevented, compared with the non-carbon coated aluminum substrate.
- the shape of the current collector may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, or a nonwoven fabric.
- the sulfur-containing active material layer refers to a layer including a sulfur-containing compound having a sulfur-sulfur bond, and the sulfur-sulfur bond is broken during discharge to reduce the oxidation number of sulfur, and the sulfur-containing oxide increases during charging. Oxidation-reduction reactions in which oxidation reactions in which sulfur bonds are formed again can be used to store and generate electrical energy.
- the sulfur-containing compound having a sulfur-sulfur bond may use a material known in the art, and is not particularly limited.
- the sulfur-containing compound having a sulfur-sulfur bond may be an elemental sulfur (S 8 ) or a sulfur compound having a sulfur-sulfur bond.
- the sulfur compound having a sulfur-sulfur bond is a metal sulfide compound such as CuS, CuS 2 , FeS and FeS 2 ; Sulfur-carbon complexes; And sulfur-containing polymers.
- the cathode active material may be manufactured by a method such as wrapping, coating, or impregnation with a material capable of imparting conductivity to sulfur. desirable.
- the cathode active material may use a sulfur-carbon composite.
- the sulfur-containing active material layer may further include a conductive material.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical changes in the battery, but may include graphite-based materials such as KS6; Carbon blacks such as Super-P, Denka Black, Acetylene Black, Ketjen Black, Channel Black, Furnace Black, Lamp Black, Summer Black, Carbon Black; Carbon derivatives such as fullerene; Carbon nanotubes; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Or conductive polymers such as polyaniline, polythiophene, polyacetylene, and polypyrrole may be used alone or in combination.
- the sulfur-containing active material layer may further include an amphiphilic material.
- the amphiphilic material may trap polysulfides generated from a cathode active material such as a sulfur-carbon composite to prevent the polysulfides from moving to the electrolyte and the anode.
- the amphiphilic material is a material having affinity for both polar and nonpolar solvents, and specific examples thereof may include at least one of polyvinylpyrrolidone (PVP), polyethylene oxide, gelatin, and the like. no.
- the electrolyte may be provided between the anode and the cathode. Specifically, the electrolyte may be provided only between the anode and the cathode to minimize contact with the current collectors of the anode and the cathode. In this case, it is possible to reduce or prevent corrosion by sulfur or lithium polysulfide which may elute the electrolyte.
- the electrolyte may include a lithium salt and an organic solvent.
- the concentration of the lithium salt is 0.2M to 2M, depending on several factors such as the exact composition of the electrolyte solvent mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and discharging conditions of the cell, the operating temperature and other factors known in the lithium battery art. For example, it may be 0.6M to 2M, more specifically 0.7M to 1.7M. In this case, the conductivity of the electrolyte is appropriate to maintain the electrolyte performance, there is an advantage that does not interfere with the movement of lithium ions due to the viscosity of the electrolyte.
- lithium salts for use in the present application include LiSCN, LiBr, LiI, LiPF 6 , LiBF 4 , LiSO 3 CF 3 , LiClO 4 , LiSO 3 CH 3 , LiB (Ph) 4 , LiC (SO 2 CF 3 ) 3 And LiN (SO 2 CF 3 ) 2 may be included.
- the organic solvent may be a single solvent or a mixture of two or more organic solvents.
- the weak polar solvent is defined as a solvent having a dielectric constant of less than 15 which is capable of dissolving elemental sulfur among aryl compounds, bicyclic ethers, and acyclic carbonates, and strong polar solvents include acyclic carbonates, sulfoxide compounds, and lactone compounds.
- the lithium metal protective solvent is a saturated ether compound, unsaturated ether compound, N, It is defined as a solvent having a charge / discharge cycle efficiency of 50% or more that forms a stable solid interface (SEI) on a lithium metal such as a heterocyclic compound including O, S, or a combination thereof.
- the weak polar solvent examples include xylene, dimethoxyethane, 2-methyltetrahydrofuran, diethyl carbonate, dimethyl carbonate, toluene, dimethyl ether, diethyl ether, diglyme or tetraglyme. .
- the strong polar solvent examples include hexamethyl phosphoric triamide, ⁇ -butyrolactone, acetonitrile, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, 3-methyl-2-oxazoli Don, dimethyl formamide, sulfolane, dimethyl acetamide, dimethyl sulfoxide, dimethyl sulfate, ethylene glycol diacetate, dimethyl sulfite, or ethylene glycol sulfite.
- lithium protective solvent examples include tetrahydrofuran, ethylene oxide, dioxolane, 3,5-dimethyl isoxazole, furan, 2-methyl furan, 1,4-oxane or 4-methyldioxolane.
- the lithium-sulfur battery may further include a separator provided between the cathode and the anode.
- the separator may be made of a porous non-conductive or insulating material to separate or insulate the cathode and the anode from each other, and to allow lithium ion transport between the cathode and the anode.
- the separator may be an independent member such as a film, or may be a coating layer added to the cathode and / or the anode.
- the material constituting the separator includes, for example, polyolefins such as polyethylene and polypropylene, glass fiber filter paper, and ceramic materials, but is not limited thereto, and the thickness thereof is about 5 ⁇ m to 50 ⁇ m, and in detail, about 5 ⁇ m to 25 ⁇ m. May be ⁇ m.
- the present specification provides a battery module including the lithium-sulfur battery as a unit cell.
- the battery module may be formed by stacking a bipolar plate provided between two or more lithium-sulfur batteries according to one embodiment of the present specification.
- the battery module may be used as a power source for an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage device.
- an anode composition was prepared by preparing an insulating film composition including high density polyethylene (HDPE) and forming an insulating film in the form of FIG. 11 on the lithium metal layer.
- HDPE high density polyethylene
- the anode of Experimental Example 1 or Comparative Example 1 was composed of a lithium-sulfur battery together with a sulfur cathode, a polypropylene (PP) gasket, and a polyethylene separator.
- an electrolyte solution (TEGDME: DOL: DME 1: 1: 1, v / v, 1.0M LiTFSI, 0.1M LiNO 3 ) was injected to carry out an experiment.
- TEGDME: DOL: DME Tetraethylene glycol dimethyl ether: Dioxolane: Dimethoxy ethane)
- each battery After 10 days of injecting the electrolyte into the lithium-sulfur battery, each battery showed the following change as shown in FIG. 23.
- Example 1 a small amount of lithium polysulfide (Li 2 S 8 ) was formed, and the formed lithium polysulfide was rapidly reduced to Li 2 S 4 to have a yellow color.
- Comparative Example 1 a large amount of lithium polysulfide (Li 2 S 8 ) was formed to have a dark red color.
- Example 1 is more effective in suppressing the formation of lithium polysulfide than the anode prepared in Comparative Example 1.
- Li 2 S 8 lithium polysulfide
- the anode prepared in Comparative Example 1 was installed on the bottom of the planet as shown in FIG. 12, and the electrolyte solution (TEGDME: DOL: DME (1: 1: 1, v / v), 1M LiTFSI, 0.1M LiNO 3 ) was injected to prepare a lithium-sulfur battery without a separator.
- TEGDME: DOL: DME Tetraethylene glycol dimethyl ether: Dioxolane: Dimethoxy ethane
- the lithium polysulfide formation reaction is actively performed at the boundary between the anode current collector and the lithium metal layer instead of simply forming lithium polysulfide in the lithium metal.
- the electrolyte used in this experiment contains LiNO 3 , which is an additive capable of reacting with lithium metal to form a chemical protective layer on the surface, but even when the additive is included, lithium is bounded between the anode current collector and the lithium metal layer. It can be seen that the formation of polysulfide is active.
- lithium polysulfide cannot be prevented from being formed at the boundary between the anode current collector and the lithium metal layer. It can be seen that there is a need to isolate the boundary of the lithium metal layer from the electrolyte.
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Abstract
Description
Claims (8)
- 애노드 집전체 및 상기 애노드 집전체 상에 구비된 리튬금속층을 포함하는 애노드;황함유 물질을 포함하는 캐소드;상기 애노드 및 캐소드 사이에 구비된 전해질; 및상기 애노드 집전체와 리튬금속층이 접하는 경계선을 덮도록 구비된 절연막을 포함하는 것인 리튬-황 전지.
- 청구항 1에 있어서, 상기 절연막은 상기 애노드 집전체와 리튬금속층이 접하는 경계선 및 상기 애노드 집전체의 리튬금속층이 구비된 면 중 리튬금속층과 접하지 않는 표면 상에 구비된 것인 리튬-황 전지.
- 청구항 1에 있어서, 상기 절연막은 상기 애노드 집전체와 리튬금속층이 접하는 경계선, 상기 애노드 집전체의 리튬금속층이 구비된 면 중 리튬금속층과 접하지 않는 표면 및 리튬금속층의 측면을 덮도록 구비된 것인 리튬-황 전지.
- 청구항 1에 있어서, 상기 절연막은 상기 애노드 집전체와 리튬금속층이 접하는 경계선, 상기 애노드 집전체의 리튬금속층이 구비된 면 중 리튬금속층과 접하지 않는 표면, 리튬금속층의 측면 및 리튬금속층의 모서리를 덮도록 구비된 것인 리튬-황 전지.
- 청구항 1에 있어서, 상기 절연막의 두께는 1 nm 이상 500 ㎛이하인 것인 리튬-황 전지.
- 청구항 1에 있어서, 상기 절연막은 산화세라믹계 절연물질 및 질화세라믹계 절연물질 중 적어도 하나를 포함하는 것인 리튬-황 전지.
- 청구항 1에 있어서, 상기 절연막의 절연 저항은 106 Ω·m(Deionized water) 이상인 것인 리튬-황 전지.
- 청구항 1 내지 7 중 어느 한 항의 리튬-황 전지를 단위 전지로 포함하는 전지 모듈.
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US15/509,644 US10615462B2 (en) | 2014-09-26 | 2015-09-10 | Lithium-sulfur battery and battery module including same |
CN201580050255.1A CN106716702B (zh) | 2014-09-26 | 2015-09-10 | 锂-硫电池和包含其的电池模块 |
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US11450876B2 (en) * | 2016-09-30 | 2022-09-20 | LiBama, LLC | Porous electrode for electrochemical cells |
US10770727B2 (en) | 2016-11-28 | 2020-09-08 | Lg Chem, Ltd. | Cathode active material for lithium-sulfur battery, comprising metal sulfide nanoparticles, and method for producing same |
KR102138693B1 (ko) | 2017-07-11 | 2020-07-28 | 한양대학교 산학협력단 | 전해질 및 이를 포함하는 리튬 황 전지 |
KR102423680B1 (ko) | 2017-09-08 | 2022-07-21 | 삼성디스플레이 주식회사 | 표시 장치 |
KR20190047593A (ko) | 2017-10-27 | 2019-05-08 | 주식회사 엘지화학 | 리튬 금속 음극 구조체의 제조방법 및 리튬 금속 음극 구조체 |
US11631896B2 (en) * | 2018-11-23 | 2023-04-18 | Lg Energy Solution, Ltd. | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
CN110137573A (zh) * | 2019-05-31 | 2019-08-16 | 中国科学院金属研究所 | 一种以金属锂为负极的锂二次电池用电解液 |
CN110400970B (zh) * | 2019-06-04 | 2023-09-05 | 江西力能新能源科技有限公司 | 一种电解质材料及其在高温锂电池上的应用 |
KR102663587B1 (ko) * | 2019-06-14 | 2024-05-03 | 주식회사 엘지에너지솔루션 | 바이폴라 리튬 이차전지 |
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