Patent Application
20240372132
This application claims the benefit of and priority to Korean Patent Application No. 10-2023-0058000, filed on May 3, 2023, the disclosures of which are incorporated herein by reference in their entirety.
The present disclosure relates to a lithium secondary battery, and more particularly, to a lithium-sulfur battery having a long lifespan.
As the range of application of lithium secondary batteries is extended to not only mobile electronic devices, but also electric vehicles (EV) and energy storage systems (ESS), there is a growing demand for lithium secondary batteries with high capacity, high energy density and long lifespan.
Among various types of lithium secondary batteries, lithium-sulfur batteries are a battery system using sulfur-based materials comprising sulfur-sulfur (S—S) bond as the positive electrode active material, and lithium-containing metals, carbon-based materials capable of intercalation/deintercalation of lithium ions, or silicon and tin that can be alloyed with lithium for the negative electrode active material.
In lithium-sulfur batteries, sulfur, the main material of the positive electrode active material has low atomic mass, is very abundant in nature and can be found around the world, is low in cost, and is non-toxic and eco-friendly.
Additionally, lithium-sulfur batteries have theoretical specific capacity of 1,675 mAh/g by conversion reaction (S8+16Li++16e−→8Li2S) of lithium ion and sulfur at the positive electrode, and when lithium metal is used in the negative electrode, the theoretical energy density is 2,600 Wh/kg. This value is much higher than the theoretical energy density of the other battery systems being studied now (Ni-MH batteries: 450 Wh/kg, Li—FeS batteries: 480 Wh/kg, Li—MnO2 batteries: 1,000 Wh/kg, Na—S batteries: 800 Wh/kg) and lithium ion batteries (250 Wh/kg), so among secondary batteries developed so far, lithium-sulfur batteries are gaining attention as lithium secondary batteries with high capacity, eco-friendliness and low cost.
During discharging, the lithium-sulfur batteries undergo reduction reaction in which sulfur accepts electrons at the positive electrode, and in this instance, lithium (poly)sulfide (Li2Sx, x=1 to 8) is produced at the positive electrode, and some of the lithium (poly)sulfide are easily dissolved in the electrolyte solution and completely reduced, and then precipitate on the negative electrode in a solid form of lithium sulfide (Li2S), or lithium (poly)sulfide reacts with the lithium-containing metal of the negative electrode, which causes surface contamination of the negative electrode, inducing sulfur (S) passivation on the negative electrode, resulting in irreversible loss of the active material, and this shuttle phenomenon impedes long life characteristics.
Accordingly, there is a need for development of lithium-sulfur batteries capable of suppressing passivation on the negative electrode caused by repeated charge and discharge and achieving long life characteristics.
The present disclosure is designed to solve the above-described problem, and therefore the present disclosure is directed to providing a lithium-sulfur battery having long life characteristics.
The present disclosure is further directed to providing a lithium-sulfur battery with high energy density.
To achieve the above-described objective, according to an aspect of the present disclosure, there is provided a lithium-sulfur battery of the following embodiments.
The lithium-sulfur battery according to a first embodiment comprises an electrode assembly which comprises a positive electrode including a sulfur-carbon composite, a negative electrode including a lithium-containing layer and a solid electrolyte interphase (SEI) layer formed on at least one surface of the lithium-containing layer, and a separator between the positive electrode and the negative electrode; and an electrolyte solution, wherein the negative electrode comprises sulfur element (S) in an amount of 3 weight % or less based on the total weight of the lithium-containing layer and the SEI layer at state of charge of 100% (SOC 100).
According to a second embodiment, in the first embodiment, the lithium-sulfur battery at SOC 100 may have a potential of 2.4 V to 2.7 V.
According to a third embodiment, in the first or second embodiment, the amount of the sulfur element (S) in the negative electrode may be 3 weight % or less based on the total weight of the sulfur element (S) and lithium element (Li) in the negative electrode.
According to a fourth embodiment, in any one of the first to third embodiments, the amount of the sulfur (S) in the negative electrode may be 2 weight % or less based on the total weight of the sulfur element (S) and the lithium element (Li) in the negative electrode.
According to a fifth embodiment, in any one of the first to fourth embodiments, the amount of the sulfur element (S) in the negative electrode may be 1 weight % or less based on the total weight of the sulfur element (S) and the lithium element (Li) in the negative electrode.
According to a sixth embodiment, in any one of the first to fifth embodiments, the negative electrode may have a thickness of 120 μm or less.
According to a seventh embodiment, in any one of the first to sixth embodiments, the negative electrode may have a thickness of 70 μm or less.
According to an eighth embodiment, in any one of the first to seventh embodiments, the sulfur-carbon composite may have a sulfur/carbon weight ratio (S/C weight ratio) of 5.0 or less. For example, the sulfur-carbon composite may have a sulfur/carbon weight ratio (S/C weight ratio) of 3.0 or less. For another example, the sulfur-carbon composite may have a sulfur/carbon weight ratio (S/C weight ratio) of 2.5 or less.
According to a ninth embodiment, in any one of the first to eighth embodiments, the positive electrode may comprise the sulfur-carbon composite in an amount of 90 weight % or more based on the total weight of the positive electrode.
According to a tenth embodiment, in any one of the first to ninth embodiments, a weight ratio (El/S weight ratio) of the electrolyte solution to sulfur in the sulfur-carbon composite may be 3.5 or less.
According to an eleventh embodiment, in any one of the first to tenth embodiments, the electrolyte solution may comprise a nonaqueous solvent, a lithium salt and an additive.
According to a twelfth embodiment, in any one of the first to eleventh embodiments, the nonaqueous solvent may comprise noncyclic ether, cyclic ether and a mixture thereof.
According to a thirteenth embodiment, in any one of the first to twelfth embodiments, the nonaqueous solvent may comprise the mixture of the noncyclic ether and the cyclic ether at a volume ratio of 5:95 to 95:5 (v/v).
According to a fourteenth embodiment, in any one of the first to thirteenth embodiments, the additive may comprise a nitrogen compound.
According to a fifteenth embodiment, in any one of the first to fourteenth embodiments, the additive may comprise lithium nitrate (LiNO3).
According to a sixteenth embodiment, in any one of the first to eleventh embodiments, the lithium-sulfur battery may have a lifespan of 190 cycles or more over repeated charge and discharge cycles at 0.3 to 0.5 C rate in the range of from 1.8 V to 2.5 V at room temperature.
According to a seventeenth embodiment, in any one of the first to sixteenth embodiments, the room temperature may be 23° C. to 25° C.
According to an eighteenth embodiment, in any one of the first to seventeenth embodiments, the lithium-sulfur battery may have an energy density of 300 Wh/kg or more, or 400 Wh/kg or more.
According to a nineteenth embodiment, in any one of the first to eighteenth embodiments, the lithium-sulfur battery may be a coin type battery, a pouch type battery or a cylindrical battery.
According to another aspect of the present disclosure, there is provided a method for evaluating a lifespan of a lithium-sulfur battery.
The method for evaluating the lifespan of the lithium-sulfur battery according to a twentieth embodiment, the lithium-sulfur battery comprising an electrode assembly which includes a positive electrode comprising a sulfur-carbon composite, a negative electrode comprising a lithium-containing layer and a solid electrolyte interphase (SEI) layer formed on at least one surface of the lithium-containing layer, and a separator between the positive electrode and the negative electrode; and an electrolyte solution, comprises determining the lithium-sulfur battery having a sulfur (S) content of 3 weight % or less based on the total weight of the lithium-containing layer and the SEI layer at SOC 100 as a long life lithium-sulfur battery.
According to a twenty first embodiment, in the twentieth embodiment, the long life lithium-sulfur battery, for example, may have the lifespan of 190 cycles or more over repeated charge and discharge cycles at 0.3 to 0.5 C rate in the range of from 1.8 V to 2.5 V at 23° C. to 25° C.
According to a twenty second embodiment, in any one of the first to the twenty first embodiment, the lithium-sulfur battery may have an energy density of 300 Wh/kg or more.
According to a twenty third embodiment, in any one of the first to the twenty first embodiment, the lithium-sulfur battery may have an energy density of 400 Wh/kg or more.
According to further another aspect of the present disclosure, there is provided a method for manufacturing a lithium-sulfur battery.
The method for manufacturing a lithium-sulfur battery according to a twenty fourth embodiment comprises:
According to yet another aspect of the present disclosure, there is provided a lithium-sulfur battery which is manufactured based on a condition that the negative electrode at SOC 100 includes less than a certain amount of sulfur element.
The lithium-sulfur battery according to a twenty fifth embodiment comprises:
According to a twenty sixth embodiment, in the twenty fifth embodiment, the lithium-sulfur battery at SOC 100 may have a potential of 2.4 V to 2.7 V.
According to a twenty seventh embodiment, in any one of the twenty fifth and the twenty sixth embodiments, the electrolyte solution contains 1 weight % or more of a nitrogen compound based on the total weight of the electrolyte solution.
According to an aspect, the lithium-sulfur battery of the present disclosure may exhibit the outstanding capacity retention over repeated charge and discharge.
For example, the lithium-sulfur battery of the present disclosure may retain 80% or more of the initial capacity after 190 or more charge/discharge cycles.
According to an aspect, the lithium-sulfur battery of the present disclosure may have high energy density. In particular, the lithium-sulfur battery of the present disclosure may have the energy density of 300 Wh/kg or more. More particularly, the lithium-sulfur battery of the present disclosure may have the energy density of 400 Wh/kg or more.
Hereinafter, the present disclosure will be described in more detail.
It should be understood that the terms or words used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but rather interpreted based on the meanings and concepts corresponding to the technical aspects of the present disclosure on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.
The terminology as used herein is used to describe a specific embodiment and is not intended to limit the present disclosure. The singular form includes the plural form unless the context clearly indicates otherwise. It should be further understood that ‘comprise’ or ‘include’ when used in the specification, specifies the presence of stated features, integers, steps, operations, elements, components or a combination thereof, and unless expressly stated otherwise, does not preclude the presence or addition of one or more other functions, integers, steps, operations, elements, components or a combination thereof.
Additionally, the terms “about” and “substantially” as used herein are used in the sense of at, or nearly at, when given the manufacturing and material tolerances inherent in the stated circumstances and are used to prevent the unscrupulous infringer from unfairly taking advantage of the present disclosure where exact or absolute FIGURES are stated as an aid to understanding the present disclosure.
Throughout the specification, “A and/or B” refers to either A or B or both.
The term “composite” as used herein refers to a material with physically⋅chemically different phases and more effective functions, formed by combining two or more materials.
The term “(poly)sulfide” as used herein is the concept that covers “(poly)sulfide ion (Sx2−, 1≤x≤8)” and “lithium (poly)sulfide (Li2Sx or Li2Sx−, 1≤x≤8)”.
The term “polysulfide” as used herein is the concept that covers “polysulfide ion (Sx2−, 1<x≤8)” and “lithium polysulfide (Li2Sx or Li2Sx− 1<x≤8)”.
The unit “mgs/cm2” as used herein, unless otherwise specified, represents weight of sulfur per unit area, and may be used together with other expressions such as mg(s)/cm2 or mAh/cm2 as a loading amount.
Lithium-sulfur batteries exhibit lower battery capacity than the theoretical capacity due to the elution of lithium (poly)sulfide produced by reduction reaction of sulfur (S8) from the positive electrode into the electrolyte solution during charging⋅discharging.
According to an aspect of the present disclosure, there is provided a lithium-sulfur battery having long lifespan, to be specific, the outstanding capacity retention after the repeated charge/discharge.
The lithium-sulfur battery according to an aspect of the present disclosure comprises an electrode assembly comprising a positive electrode comprising a sulfur-carbon composite, a negative electrode and a separator interposed between the positive electrode and the negative electrode; an electrolyte solution; and a battery housing accommodating the electrode assembly.
In this instance, the negative electrode comprises a lithium-containing layer; and a solid electrolyte interphase (SEI) layer on at least one surface of the lithium-containing layer, and the negative electrode comprises sulfur (S) in an amount of 3 weight % or less based on the total weight of the lithium-containing layer and the SEI layer at the state of charge (SOC) 100.
In another instance of the present disclosure, the negative electrode comprises a lithium foil; and the solid electrolyte interphase (SEI) layer on at least one surface of the lithium-containing layer, and the electrolyte solution contains 1 weight % or more of a nitrogen compound based on the overall weight of the electrolyte solution.
It has been surprisingly found that, when the above-described amount of a nitrogen compound is included in electrolyte solution, a lithium-sulfur battery having long life characteristics is provided. Without being bound by any theory, the above-described amount of a nitrogen compound has been found to minimize the formation of sulfur compounds at the negative electrode, especially when the lithium-sulfur battery has been used for a higher number of charge and discharge cycles, like 190 or more cycles, preferable 195 or more cycles. It is believed that through the minimized formation of sulfur at the negative electrode, the lifespan of the lithium sulfur battery can be enhanced.
Furthermore, the nitrogen compound included in the above-described amount may improve the electrical conductivity of the electrolyte solution comprising the lithium salt and increase the lifespan of the lithium-sulfur battery.
Specifically, the efficacy of the nitrogen compound is not limited thereto, but for example, the nitrogen compound included in the above-described amount may suppress the reduction reaction of polysulfide produced during charging/discharge of the lithium-sulfur battery, thereby preventing irreversible consumption of (poly)sulfide, leading to improved performance of the lithium-sulfur battery.
Furthermore, when the nitrogen compound is included in the above-described amount, the nitrogen compound may improve the electrical conductivity of the electrolyte solution and suppress the reduction reaction of (poly)sulfide, especially at the negative electrode, when used in the lithium-sulfur battery, but the present disclosure is not limited thereto.
As described above, the lithium-sulfur battery comprises inorganic sulfur (S8) as the positive electrode active material. In the lithium-sulfur battery, lithium (poly)sulfide is produced through reduction reaction at the positive electrode during discharging. When the produced lithium (poly)sulfide is dissolved by the electrolyte solution and eluted into the electrolyte solution from the positive electrode, and the eluted lithium (poly)sulfide reacts with the lithium-containing metal of the negative electrode, causing lithium sulfide precipitation on the surface of the negative electrode, inducing sulfur (S) passivation. It may cause damage to the negative electrode, resulting in life reduction of the lithium-sulfur battery.
Referring to this mechanism, the “sulfur-based compound” as used herein refers collectively to any material containing sulfur (S) derived from the positive electrode active material of the lithium-sulfur battery. The sulfur-based compound may comprise, for example, any sulfur containing compound that may be formed through reduction reaction of inorganic sulfur (S8) or oxidation reaction of lithium sulfide (Li2S), and more specifically, may comprise at least one of inorganic sulfur (S8), lithium polysulfide (Li2Sx, 1<x≤8), disulfide compounds, carbon-sulfur polymer ((C2Sy)n, y=2.5 to 50, n≥2) or lithium sulfide (Li2S).
According to an aspect of the present disclosure, the range of sulfur (S) content in the negative electrode at SOC 100, i.e., when the lithium-sulfur battery is fully charged is newly proposed.
Specifically, according to an aspect of the present disclosure, there is provided the lithium-sulfur battery having the sulfur (S) content of 3 weight % or less, preferably in a range of from 0 weight % to 3 weight %, more preferably from 0.1 weight % to 3 weight %, even more preferably from 0.1 weight % to 2 weight %, especially more preferably from 0.1 weight % to 1 weight %, or even especially more preferably from 0.1 weight % to 0.5 weight %, based on the total weight of the negative electrode at SOC 100.
The negative electrode comprises the lithium-containing layer; and the SEI layer on at least one surface of the lithium-containing layer, and to achieve long life characteristics of the lithium-sulfur battery, the sulfur (S) content is limited to 3 weight % or less, preferably in a range of from 0 weight % to 3 weight %, more preferably from 0.1 weight % to 3 weight %, even more preferably from 0.1 weight % to 2 weight %, especially more preferably from 0.1 weight % to 1 weight %, or even especially more preferably from 0.1 weight % to 0.5 weight %, based on the total weight of the lithium-containing layer and the SEI layer.
In an embodiment of the present disclosure, the lithium-containing layer may comprise the negative electrode active material of the lithium-sulfur battery, for example, a lithium metal or lithium alloy, and its thickness may be, for example, 140 μm or less.
In an embodiment of the present disclosure, the lithium-containing layer may comprise a lithium foil.
In an embodiment of the present disclosure, the lithium alloy may contain an element capable of alloying with lithium, and specifically the lithium alloy may be an alloy of lithium and one or more selected from the group consisting of Si, Sn, C, Pt, Ir, Ni, Cu, Ti, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Sb, Pb, In, Zn, Ba, Ra, Ge, and Al.
In an embodiment of the present disclosure, the lithium alloy may contain the element capable of alloying with lithium in an amount of 5 weight % or less of the total weight of the lithium alloy.
In an embodiment of the present disclosure, the thickness of the lithium-containing layer may be 140 μm or less, specifically 100 μm or less, and more specifically 80 μm or less, or 70 μm or less. For example, the thickness of the lithium-containing layer may be 20 μm to 140 μm, 20 μm to 100 μm, specifically 30 μm to 80 μm, 40 μm to 70 μm, 50 μm to 70 μm, 50 μm to 65 μm, or 55 μm to 60 μm.
In an embodiment of the present disclosure, when the thickness of the lithium-containing layer is in the above-described range, there may be an advantage in terms of the weight and energy density of the battery.
In the present disclosure, the thickness of the lithium-containing layer may be measured through known means for measuring the thickness of each component of the battery, and for example, may be measured using Mitutoyo's thickness measurement machine, but is not limited thereto. In the present disclosure, the thickness of the lithium foil may be measured by laser scan micrometer according to ASTM D374.
In an embodiment of the present disclosure, the SEI layer is a thin passivation layer formed on the surface of the lithium-containing layer during charging in the activation process of the lithium-sulfur battery, and may protect the lithium-containing layer and suppress the electrolyte decomposition, but the present disclosure is not limited thereto.
In an embodiment of the present disclosure, the total thickness of the negative electrode comprising the lithium-containing layer and the SEI layer may be 150 μm or less, specifically 120 μm or less, 100 μm or less, and more specifically 70 μm or less.
For example, the total thickness of the negative electrode may be in a range of from 40 μm to 120 μm, more preferably from 40 μm to 70 μm, or even more preferably from 55 μm to 65 μm.
In the present disclosure, the total thickness of the negative electrode may be measured through known means for measuring the thickness of each component of the battery, and for example, may be measured using Mitutoyo's thickness measurement machine, but is not limited thereto. In one embodiment, In the present disclosure, the thickness of the negative electrode may be measured according to ASTM D374.
In an embodiment of the present disclosure, the lithium-sulfur battery may achieve long life characteristics when the sulfur (S) content in the negative electrode is 3 weight % or less at SOC 100, i.e., when it is fully charged. Specifically, the negative electrode may have the sulfur (S) content of 3 weight % or less based on the sum of weights of sulfur (S) and lithium (Li) in the negative electrode. For example, the negative electrode may have the sulfur (S) content of 3 weight % or less, 2 weight % or less, 1 weight % or less, 0.5 weight % or less or 0 weight % based on the sum of weights of sulfur (S) and lithium (Li) in the negative electrode. More specifically, the negative electrode may have the sulfur (S) content in a range of from 0 weight % to 3 weight %, more preferably from 0.1 weight % to 3 weight %, even more preferably from 0.1 weight % to 2 weight %, especially more preferably from 0.1 weight % to 1 weight %, or even especially more preferably from 0.1 weight % to 0.5 weight %, based on the total weight of sulfur (S) and lithium (Li) in the negative electrode at SOC 100, i.e., when it is fully charged.
In this instance, 0 weight % indicates not only that no sulfur element (S) is included, but also trace amount of sulfur is measured to be 0 weight % due to the limit of quantifiable measurements or measurement error. Accordingly, the measurement value of 0 weight % may include the actual result of 0.1 weight % based on the total weight of the negative electrode.
In an embodiment of the present disclosure, the amount of the lithium (Li) in the negative electrode is 96 weight % or more, preferably 99 weight % or more, for example, in a range of from 96 weight % to 100 weight %, preferably from 96 weight % to 99.9 weight %, or more preferably from 99 weight % to 99.9 weight % based on the total weight of sulfur (S) and the lithium (Li) in the negative electrode. The lithium-sulfur battery may achieve long life characteristics when the lithium content in weight % based on the total amount of sulfur (S) and lithium (Li) in the negative electrode is in the above indicated weight % range at SOC 100, i.e., when it is fully charged.
In an embodiment of the present disclosure, the SEI layer may change in composition depending on the composition of a lithium salt and an additive used in the electrolyte solution of the lithium-sulfur battery, and is not limited to a particular composition.
In an embodiment of the present disclosure, the SEI layer may contain, for example, a Li—F functional group.
In an embodiment of the present disclosure, the element contained in the negative electrode comprising the lithium-containing layer and the SEI layer at SOC 100 in the lithium-sulfur battery may comprise sulfur (S), lithium (Li) and fluorine (F).
In an embodiment of the present disclosure, the lithium-sulfur battery may have the sulfur (S) content of 3 weight % or less, 2 weight % or less, 1 weight % or less, 0.5 weight % or less or 0 weight % based on the sum of weights of sulfur (S), lithium (Li) and fluorine (F) in the negative electrode at SOC 100, i.e., when it is fully charged. In this instance, 0 weight % indicates not only that no sulfur element (S) is included, but also trace amount of sulfur is measured to be 0 weight % due to the limit of quantifiable measurements or measurement error.
In an embodiment of the present disclosure, the SEI layer may comprise, for example, a composite formed by chemical reaction of an additive of the electrolyte solution as described below and the lithium-containing metal. In this instance, the additive of the electrolyte solution may be, for example, a material comprising nitrogen (N), and accordingly, the SEI layer may comprise nitrogen (N).
Accordingly, in an embodiment of the present disclosure, the lithium-sulfur battery may have the sulfur (S) content of 3 weight % or less, 2 weight % or less, 1 weight % or less, 0.5 weight % or less or 0 weight % based on the sum of weights of sulfur (S), lithium (Li) and nitrogen (N) in the negative electrode at SOC 100, i.e., when it is fully charged. In this instance, 0 weight % indicates not only that no sulfur element (S) is included, but also trace amount of sulfur is measured to be 0 weight % due to the limit of quantifiable measurements or measurement error.
In another embodiment of the present disclosure, the lithium-sulfur battery may have the sulfur (S) content of 3 weight % or less, 2 weight % or less, 1 weight % or less, 0.5 weight % or less or 0 weight % based on the sum of weights of sulfur (S), lithium (Li), fluorine (F) and nitrogen (N) in the negative electrode at SOC 100, i.e., when it is fully charged.
Subsequently, a method for measuring the sulfur (S) content in the negative electrode will be described.
In an embodiment of the present disclosure, the SOC 100 may indicate, for example, the state of charge with the potential of 2.4 V to 2.7 V. Specifically, the SOC 100 may indicate the state of charge with the potential of 2.5 V.
Specifically, the sulfur (S) content in the negative electrode at SOC 100 may be measured through elemental analysis after disassembling the lithium-sulfur battery fully charged, for example, charged up to 2.4 V to 2.7 V, specifically 2.5 V and cleaning to remove the electrolyte solution from the negative electrode.
In an embodiment of the present disclosure, the elemental analysis may be performed, for example, using Ion chromatography (IC) analysis, Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) analysis, Elemental Analyzer (EA) analysis, ONH analysis or the like, but the elemental analysis method is not limited thereto. Thus, the sulfur (S) content in the negative electrode based on the total weight of the negative electrode at the state of charge (SOC) 100 or based on the total weight of sulfur (S) and lithium (Li) in the negative electrode at the state of charge (SOC) 100 may be measured by elemental analysis, preferably measured by ICP-OES.
In one embodiment of the present disclosure, the lithium-sulfur battery may be activated prior to the measurement of the sulfur (S) content by discharging at a 0.5 C discharge rate and charging at a 0.3 C charge rate in a range of from 1.8 V to 2.5 V at room temperature, wherein the room temperature is from 23° C. to 25° C., for at least one cycle, preferably for at least 5 cycles, more preferably for at least 10 cycles, and even more preferably for 10 cycles.
As described above, the conventional lithium-sulfur battery degrades over the repeated charge/discharge cycles due to sulfur (S) passivation on the negative electrode by the sulfur-based compound derived from the positive electrode during discharging, but according to an aspect of the present disclosure, it may be possible to provide the lithium-sulfur battery having long lifespan by limiting the upper limit of the sulfur (S) content in the negative electrode at SOC 100, i.e., when fully charged, to 3 weight % or less, specifically 2 weight % or less, 1 weight % or less, or 0.5 weight % or less.
Subsequently, each component of the lithium-sulfur battery other than the negative electrode will be described in detail.
In an embodiment of the present disclosure, the positive electrode may comprise a positive electrode current collector and a positive electrode active material layer coated on one or two surfaces of the positive electrode current collector.
The positive electrode current collector is not limited to a particular type and may include those which support the positive electrode active material, and have high conductivity without causing a chemical change to the battery. For example, the positive electrode current collector may include copper, stainless steel, aluminum, nickel, titanium, palladium, sintered carbon or copper or stainless steel treated with carbon, nickel or silver on the surface, and an aluminum-cadmium alloy.
The positive electrode current collector may have microtexture on the surface to enhance the bonding strength with the positive electrode active material, and may come in various forms, for example, a film, a sheet, a foil, a mesh, a net, a porous body, a foam and a nonwoven.
The positive electrode active material layer comprises the positive electrode active material, and may further comprise a conductive material, a binder and an additive.
In an embodiment of the present disclosure, the positive electrode active material comprises the sulfur-carbon composite.
In an embodiment of the present disclosure, the sulfur-carbon composite may comprise a porous carbon material; and a sulfur-based compound loaded onto at least one of the inside of the pores of the porous carbon material or the outer surface of the porous carbon material. Since sulfur used as the positive electrode active material does not have electrical conductivity itself, sulfur may be used in combination with a conductive material such as a carbon material, and the porous carbon material may be used as a sulfur host. Additionally, the sulfur-based compound may be added as the positive electrode active material, and may comprise, for example, at least one of inorganic sulfur (S8), lithium polysulfide (Li2Sx, 1<x≤8), disulfide compounds, carbon-sulfur polymer ((C2Sy)n, y=2.5 to 50, n≥2) or lithium sulfide (Li2S). Preferably, the sulfur-based compound may be inorganic sulfur (S8).
In an embodiment of the present disclosure, the porous carbon material is not limited to a particular type and may include any type of porous carbon material that can load the sulfur-based compound as the positive electrode active material, provide the skeleton for immobilizing the sulfur-based compound uniformly and stably, and improve the conductivity of the positive electrode.
In general, the porous carbon material may be manufactured by carbonizing precursors of various carbon materials. The porous carbon material may include irregular pores. The average diameter of the pores may be in a range of from 1 to 200 nm, and the porosity may be in a range of from 10 to 90 volume % of the total volume of the porous carbon material. In case that the average diameter of the pores is less than the above-described range, the pore size is at molecular level, which makes sulfur infiltration impossible, and on the contrary, in case that the average diameter of the pores is beyond the above-described range, the porous carbon material has low mechanical strength, which is unfavorable to use in the electrode manufacturing process.
In an embodiment of the present disclosure, the ‘average diameter of the pores’ may be measured by known methods for measuring the pore diameter of porous materials, and the measurement method is not limited to a particular method. For example, the pore diameter may be measured by scanning electron microscopy (SEM), field-emission microscopy (FEM), the laser diffraction method or the Brunauer-Emmett-Teller (BET) method. The measurement using the laser diffraction method may use, for example, commercially available laser diffraction particle size measurement machine (for example Microtrac MT 3000). Additionally, the measurement by the BET method may, for example, use BEL Japan's BELSORP series analyzer, but is not limited thereto.
In an embodiment of the present disclosure, the ‘porosity’ refers to a fraction of voids in a structure over the total volume and is indicated in %, and may be used interchangeably with void fraction, degree of porosity or the like. In the present disclosure, the porosity measurement is not limited to a particular method, and according to an embodiment of the present disclosure, for example, the porosity may be measured by the BET method using nitrogen gas or Hg porosimeter and ASTM D2873.
The shape of the porous carbon material may be spherical, rod-like, needle-like, platy, tubular or bulky, and may include, without limitation, any shape commonly used in the lithium-sulfur battery.
The porous carbon material may include any carbon material having a porous structure or a high specific surface area commonly used in the corresponding technical field. For example, the porous carbon material may include at least one selected from the group consisting of graphite; graphene; carbon black including denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black; carbon nanotubes (CNT) including single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT); carbon fibers including graphite nanofibers (GNF), carbon nanofibers (CNF) and activated carbon fibers (ACF); graphite including natural graphite, artificial graphite, expandable graphite and activated carbon, but is not limited thereto. Preferably, the porous carbon material may be carbon nanotubes.
In an embodiment of the present disclosure, the porous carbon material may comprise, for example, carbon nanotubes (CNT).
In an embodiment of the present disclosure, the porous carbon material may be prepared by a manufacturing method including a step of centrifugally milling a porous carbon material; and a step of filtering the centrifugally milled porous carbon material through a sieve, wherein a mesh size of the sieve is 2.8 to 4 times of a target D50 particle size of the porous carbon material.
In an embodiment of the present disclosure, the porous carbon material may satisfy one or more of the following conditions: (1) a sum of particle size D10 and particle size D90 is 60 μm or less; and (2) a broadness factor (BF) according to the following equation is 0.7 or lower:
Broadness factor (BF)=(D90 particle size of the porous carbon material)/[(D10 particle size of the porous carbon material)×10].
In an embodiment of the present disclosure, the sulfur-carbon composite may, for example, have a sulfur/carbon weight ratio (S/C weight ratio) of 5 or less, and more specifically 3.0 or less. For example, the sulfur-carbon composite may have the S/C weight ratio of 2.4. The S/C weight ratio may be calculated from the weight of sulfur in gram (g) of the sulfur-carbon composite and from the weight of carbon in gram (g) of the sulfur-carbon composite. Alternatively, the S/C weight ratio may be calculated from the weight % of sulfur based on the total amount of the sulfur-carbon composite and from the weight % of carbon based on the total amount of the sulfur-carbon composite. The sulfur/carbon weight ratio (S/C weight ratio) may be dimensionless.
In a preferred embodiment of the present disclosure, the sulfur-carbon composite may have a sulfur/carbon weight ratio (S/C weight ratio) in a range of from 0.5 to 5.0.
In another preferred embodiment of the present disclosure, the sulfur-carbon composite may have a sulfur/carbon weight ratio (S/C weight ratio) in a range of from 0.5 to 4.0, from 1.0 to 3.0, from 1.5 to 2.5, from 2.0 to 2.45, from 2.25 to 2.35, or from 2.3 to 3. The S/C weight ratio may be obtained from the weight ratio of S8/porous carbon material, wherein the porous carbon material is preferably CNT, as discussed below. The S/C weight ratio may be obtained from the amount used when the lithium-sulfur battery is manufactured.
When the S/C ratio of the sulfur-carbon composite is in the above-described range, it may be desirable in terms of the sulfur-carbon composite's ability to transport electrons (conductivity) and electrochemical specific surface area, and for example, the larger surface area of the sulfur-carbon composite may suppress the elution of sulfur from the positive electrode more effectively, but the present disclosure is not limited thereto.
The method for manufacturing the sulfur-carbon composite is not limited to a particular method in the present disclosure and may include methods commonly used in the corresponding technical field. For example, the sulfur-carbon composite may be manufactured by simply mixing the sulfur with the porous carbon material and performing thermal treatment to create a composite.
In addition to the above-described composition, the positive electrode active material may further comprise at least one selected from transition metals, Group IIIA elements, Group IVA elements, sulfur compounds of these elements, or alloys of these elements and sulfur.
The transition metals may comprise Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Os, Ir, Pt, Au or Hg, the Group 13 elements may comprise Al, Ga, In, Ti, and the Group 14 elements may comprise Ge, Sn, Pb.
In an embodiment of the present disclosure, the sulfur-carbon composite may be included in an amount of 50 weight % or more based on the total weight of the positive electrode. Specifically, the sulfur-carbon composite may be, for example, included in an amount of 80 weight % or more, 90 weight % or more, or 95 weight % or more based on the total weight of the positive electrode active material layer. Specifically, the sulfur-carbon composite may be included in an amount of 80 weight % to 100 weight %, more specifically 85 weight % to 99 weight %, 90 weight % to 99 weight %, 95 weight % to 98 weight %, or 95 weight % to 97 weight %, or 96 weight % based on the total weight of the positive electrode active material layer. The above-described amount of sulfur-carbon composite may refer to the amount thereof when the lithium-sulfur battery is manufactured. The above-described amount of sulfur-carbon composite maybe measured when the lithium sulfur battery is disassembled at a SOC100 and the positive electrode is analyzed by elemental analysis, similar to the measurement of the sulfur (S) content in the negative electrode. When the amount of the sulfur-carbon composite is less than the above-described range, the larger amount of the subsidiary material such as the conductive material and the binder and the smaller amount of the sulfur-carbon composite makes it difficult to realize the battery with high capacity and high energy density, and on the contrary, when the amount of the sulfur-carbon composite is above the above-described range, the amount of the conductive material or the binder as described below is relatively insufficient, resulting in degradation of the physical properties of the electrode.
The conductive material may be a material that serves as a movement pathway of electrons from the current collector to the positive electrode active material by electrically connecting the electrolyte to the positive electrode active material, and may include, without limitation, any material having conductive properties as a constituent component of the electrode that is physically different from carbon contained in the sulfur-carbon composite.
In an embodiment of the present disclosure, the conductive material may include, for example, carbon black such as Super-P, denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon black; carbon derivatives such as carbon nanotubes or fullerene; conductive fibers such as carbon fibers or metal fibers; metal powder such as fluorocarbon, aluminum, nickel powder; or conductive polymer such as polyaniline, polythiophene, polyacetylene, polypyrrole, either used alone or in combination.
In an embodiment of the present disclosure, the amount of the conductive material may be in a range of from 0 to 40 weight %, for example, from 1 to 40 weight %, from 15 to 40 weight %, from 20 to 40 weight %, or from 25 to 35 weight %, based on the total weight of the positive electrode active material.
When the amount of the conductive material is less than the above-described range, voltage and capacity reduces due to poor electron transport between the positive electrode active material and the current collector. On the contrary, when the amount of the conductive material is more than the above-described range, a ratio of the positive electrode active material decreases, resulting in reduced total energy (amount of electric charge) of the battery, and thus it is desirable to determine an optimal amount in the above-described range.
In an embodiment of the present disclosure, the binder may be used to bind the positive electrode active material to the positive electrode current collector, and connect the positive electrode active material in an organic manner to improve the bonding strength, and may include any binder commonly used in the corresponding technical field.
For example, the binder may include one selected from the group consisting of a fluororesin-based binder including polyvinylidene fluoride-based polymer comprising at least one repeat unit of polyvinylidene fluoride (PVdF), vinylidene fluoride, polytetrafluoroethylene (PTFE) or a mixture thereof; a rubber-based binder including styrene butadiene rubber (SBR), acrylonitrile-butadiene rubber, styrene-isoprene rubber; an acrylic binder; a cellulose-based binder including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose; a polyalcohol-based binder; a polyolefin-based binder including polyethylene, polypropylene; a polyimide-based binder; a polyester-based binder; a silane-based binder; a polyacrylic acid-based binder; and a polyacrylonitrile-based binder, or a mixture or a copolymer thereof. In a preferred embodiment, the binder is polyacrylate (PAA).
In an embodiment of the present disclosure, the amount of the binder may be 1 to 10 weight % based on the total weight of the positive electrode active material layer. When the amount of the binder is less than the above-described range, the positive electrode active material and the conductive material may be debonded due to weak physical properties of the positive electrode, and when the amount of the binder is more than the above-described range, the lower ratio of the positive electrode active material and the conductive material in the positive electrode may reduce the battery capacity, and thus it is desirable to determine an optimal amount in the above-described range.
In the present disclosure, the method for manufacturing the positive electrode for the lithium secondary battery is not limited to a particular method, and may include methods known to those skilled in the art or a variety of modified methods.
For example, the positive electrode for the lithium secondary battery may be manufactured by preparing a positive electrode slurry composition comprising the above-described composition, and coating the composition on at least one surface of the positive electrode current collector to form the positive electrode active material layer.
The positive electrode slurry composition comprises the above-described positive electrode active material, and may further comprise the binder, the conductive material and a solvent.
The solvent includes any solvent that may uniformly disperse the positive electrode active material. The solvent may be preferably an aqueous solvent, most preferably, water, and in this instance, water may be distilled water, deionized water. The solvent is not limited thereto, and if necessary, may include lower alcohol that easily mixes with water. The lower alcohol may include methanol, ethanol, propanol, isopropanol and butanol, and preferably, they may be used in combination with water.
The solvent may be included in such an amount to ensure a sufficient level of viscosity to facilitate coating, and the amount of the solvent may change depending on the coating method and device.
The positive electrode slurry composition may further comprise a material commonly used to improve the function in the corresponding technical field, if necessary. For example, the positive electrode slurry composition may further comprise a viscosity adjusting agent, a glidant, fillers or the like.
The method for coating the positive electrode slurry composition is not limited to a particular method in the present disclosure, and for example, may include doctor blade, die casting, comma coating, screen printing. Additionally, the positive electrode slurry may be coated on the positive electrode current collector by forming on a substrate and pressing or lamination.
After the coating, a drying process may be performed to remove the solvent. The drying process may be performed at a sufficient level of temperature and time to remove the solvent, and the conditions may change depending on the type of the solvent and the present disclosure is not limited to a particular condition. For example, a drying method may include drying by warm air, hot air and low humidity air, vacuum drying, and drying by (far) infrared radiation and electromagnetic radiation. The drying speed is adjusted to remove the solvent as quickly as possible within a speed range for preventing cracking in the positive electrode active material layer or preventing the positive electrode active material layer from being peeled from the positive electrode current collector due to stress concentration.
In addition, after the drying, the current collector may be pressed to increase the density of the positive electrode active material in the positive electrode. The pressing may include mold pressing and roll pressing.
The positive electrode manufactured by the above-described composition and manufacturing method, specifically the positive electrode active material layer may have the porosity of 50 to 80 volume %, specifically 60 to 75 volume %. When the porosity of the positive electrode is less than 50 volume %, due to high filling of the positive electrode slurry composition comprising the positive electrode active material, the conductive material and the binder, it fails to maintain a sufficient quantity of electrolyte for ionic conductivity and/or electrical conductivity in the positive electrode active material, resulting in degradation of the output characteristics or cycling characteristics of the battery, and the problem with overvoltage and discharge capacity reduction of the battery gets worse. On the contrary, when the porosity of the positive electrode is higher than 80 volume %, too high porosity reduces the physical and electrical connection with the current collector, resulting in low adhesion strength and poor reaction, and high electrolyte filling reduces the energy density of the battery, and accordingly the porosity of the positive electrode is appropriately adjusted in the above-described range.
In an embodiment of the present disclosure, the loading amount of sulfur in the positive electrode may be less than 3 mAh/cm2, but above 0 mAh/cm2, preferably in a range of from 0.1 to 2.9 mAh/cm2, more preferably from 0.5 to 2.8 mAh/cm2, even more preferably from 1 to 2.7 mAh/cm2, especially more preferably from 1.5 to 2.6 mAh/cm2, or especially even more preferably from 2.0 to 2.5 mAh/cm2. The loading amount of sulfur may be a value calculated from the total weight of sulfur (S) contained as a positive electrode active material in the positive electrode and the capacity of the electrode calculated from this. In another embodiment, the weight of sulfur in the positive electrode may be measured from the positive electrode active material used during the manufacturing step, or may be measured through thermogravimetric analysis (TGA) on the positive electrode after manufacturing. In other embodiment, the fully charged lithium-sulfur battery is disassembled under an inert atmosphere to obtain a positive electrode, and then the positive electrode is washed and dried using an appropriate washing solvent, and then the positive electrode active material layer is scraped off. The content of sulfur (S) derived from the active material can be measured and calculated through thermogravimetric analysis (TGA) of the obtained result, but the measurement method is not limited to this.
The separator may comprise a porous non-conductive or insulating material that separates or insulates the positive electrode from the negative electrode, and allows lithium ion transport between the positive electrode and the negative electrode, and may include any separator commonly used in lithium secondary batteries without limitation. The separator may be a stand-alone member such as a film, and may be a coating layer added to the positive electrode and/or the negative electrode.
Preferably, the separator may have low resistance to electrolyte ion transport and high electrolyte wettability.
In an embodiment of the present disclosure, the separator may comprise a porous substrate, and the porous substrate may include any type of porous substrate commonly used in secondary batteries. The separator may include a porous polymer film either used alone or in stack, and for example, may include a nonwoven fabric made of high melting point glass fibers, polyethylene terephthalate fibers or a polyolefin-based porous membrane, but is not limited thereto.
The porous substrate is not limited to a particular material in the present disclosure, and may include any porous substrate commonly used in electrochemical devices. For example, the porous substrate may comprise at least one material selected from the group consisting of polyolefin such as polyethylene, polypropylene, polyester such as polyethylene terephthalate, polybutylene terephthalate, polyamide, polyacetal, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylene sulfide, polyethylene naphthalene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, cellulose, nylon, poly(p-phenylene benzobisoxazole) and polyarylate.
In an embodiment of the present disclosure, the thickness of the porous substrate is not limited to a particular range, but may be 1 to 100 μm, preferably 5 to 50 μm. The thickness range of the porous substrate is not limited to the above-described range, but when the thickness is too small below the above-described lower limit, the mechanical properties may degrade, causing damage to the separator during the use of the battery.
In an embodiment of the present disclosure, the average diameter and porosity of the pores present in the porous substrate are also not limited to a particular range, may be 0.001 to 50 μm and 10 to 95 volume %, respectively.
In an embodiment of the present disclosure, the separator may further comprise a porous coating layer on at least one surface of the porous substrate, comprising inorganic particles and a binder.
In an embodiment of the present disclosure, the inorganic particles and the binder included in the porous coating layer are not limited to a particular type and may include those commonly used in the porous coating layer of the separator, and its manufacturing method is not limited to a particular method.
The electrolyte solution comprises a nonaqueous solvent as a medium for the movement of ions involved in the electrochemical reaction of the lithium-sulfur battery and a lithium salt as an electrolyte.
The electrolyte solution may include, without limitation, any composition used in the lithium secondary battery, specifically the lithium-sulfur battery.
In an embodiment of the present disclosure, the electrolyte solution may comprise the nonaqueous solvent, the lithium salt and the additive.
In an embodiment of the present disclosure, the nonaqueous solvent is not limited to a particular type and may include any type of solvent used in the lithium-sulfur battery, and may include, for example, an ether-based solvent, ester, amide, linear carbonate and cyclic carbonate.
In an embodiment of the present disclosure, the ester may include, for example, at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone and ε-caprolactone, but is not limited thereto.
In an embodiment of the present disclosure, the linear carbonate may typically include, for example, at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate, methylpropyl carbonate and ethylpropyl carbonate, but is not limited thereto.
In an embodiment of the present disclosure, the cyclic carbonate may include, for example, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate and their halides. The halides may include, for example, fluoroethylene carbonate, but is not limited thereto.
In an embodiment of the present disclosure, the nonaqueous solvent may comprise an ether-based solvent.
In an embodiment of the present disclosure, the ether-based solvent may be included in an amount of 60 volume % or more, for example, 60 volume % to 100 volume %, 70 volume % to 100 volume %, 80 volume % to 100 volume %, 85 volume % to 100 volume %, 90 volume % to 100 volume %, 95 volume % to 100 volume %, 98 volume % to 100 volume %, 90 volume % to 98 volume %, or 90 volume % to 95 volume % based on the total volume of the nonaqueous solvent. When the amount of the ether-based solvent is in the above-described range based on the total volume of the nonaqueous solvent, it may be possible to improve the solubility of the constituents of the electrolyte solution such as the lithium salt, but the present disclosure is not limited thereto.
In an embodiment of the present disclosure, the ether-based solvent may comprise noncyclic ether, cyclic ether or a mixture thereof.
In an embodiment of the present disclosure, the noncyclic ether may comprise, for example, at least one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diisobutyl ether, ethylmethyl ether, ethylpropyl ether, ethylterbutyl ether, dimethoxymethane, trimethoxymethane, dimethoxyethane, diethoxyethane, dimethoxypropane, diethyleneglycol dimethylether, diethyleneglycol diethylether, triethyleneglycol dimethylether, tetraethyleneglycol dimethylether, ethyleneglycol divinylether, diethyleneglycol divinylether, triethyleneglycol divinylether, dipropylene glycol dimethylene ether, butylene glycol ether, diethyleneglycol ethylmethylether, diethyleneglycol isopropylmethylether, diethyleneglycol butylmethylether, diethyleneglycol terbutylethylether and ethyleneglycol ethylmethylether. Preferably, the noncyclic ether may comprise at least one selected from the group consisting of dimethylether, dimethoxyethane, diethoxyethane, diethyleneglycol dimethylether, triethyleneglycol dimethylether and tetraethyleneglycol dimethylether, and more preferably dimethoxyethane.
In an embodiment of the present disclosure, the cyclic ether may comprise, for example, at least one selected from the group consisting of 2-methylfuran, 1,3-dioxolane, 4,5-dimethyl-dioxolane, 4,5-diethyl-dioxolane, 4-methyl-1,3-dioxolane, 4-ethyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, 2-methyl-1,3-dioxolane, 2-vinyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 2-ethyl-2-methyl-1,3-dioxolane, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxy benzene, 1,3-dimethoxy benzene, 1,4-dimethoxy benzene and isosorbide dimethyl ether. Preferably, the cyclic ether may comprise at least one selected from the group consisting of 2-methylfuran, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran and 2,5-dimethyltetrahydrofuran, and more preferably 2-methylfuran.
In an embodiment of the present disclosure, the nonaqueous solvent may comprise a mixture of the noncyclic ether and the cyclic ether.
In an embodiment of the present disclosure, the nonaqueous solvent may comprise dimethoxyethane (DME) and 2-methylfuran (2-MeF).
In an embodiment of the present disclosure, a volume ratio (v/v) of the noncyclic ether and the cyclic ether may be 5:95 to 95:5 (v/v), specifically 95:5 to 50:50, and more specifically 90:10 to 70:30, 85:15 to 75:25 or 80:20. In the present disclosure, the volume ratio corresponds to a ratio of “volume % of the noncyclic ether”:“volume % of the cyclic ether” in the ether-based solvent.
In an embodiment of the present disclosure, the nonaqueous solvent may not comprise the carbonate-based solvent in terms of the solubility of the electrolyte. Alternatively, the nonaqueous solvent may comprise the carbonate-based solvent in such a very small amount that the carbonate-based solvent does not affect the solubility of the lithium salt, and for example, when the nonaqueous solvent comprises the carbonate-based solvent, the amount of the carbonate-based solvent may be 3 weight % or less, 2 weight % or less, 1 weight % or less, 0.5 weight % or less or 0 weight % (i.e., none) based on the total weight of the electrolyte solution for the lithium secondary battery.
In an embodiment of the present disclosure, the lithium salt is not limited to a particular type and may include those used as electrolytes of lithium secondary batteries. The lithium salt may comprise, for example, at least one of LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiC4BO8, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2Nli, (C2F5SO2)2Nli, (SO2F)2Nli, (CF3SO2)3Cli, lithium chloroborane, lower aliphatic lithium carboxylate, lithium tetraphenylborate or lithium imide.
In an embodiment of the present disclosure, the one lithium salt selected from the group consisting of LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiC4BO8, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2Nli, (C2F5SO2)2Nli, (SO2F)2Nli, (CF3SO2)3Cli, lithium chloroborane, lower aliphatic lithium carboxylate, lithium tetraphenylborate, and lithium imide, preferably (CF3SO2)2Nli, may not contain nitrate.
In an embodiment of the present disclosure, the electrolyte solution comprises a nonaqueous solvent, lithium nitrate (LiNO3), a lithium salt and optionally an additive.
In an embodiment of the present disclosure, one lithium salt does not contain nitrate.
In a specific embodiment of the present disclosure, the electrolyte solution comprises a nonaqueous solution, lithium nitrate (LiNO3) and (CF3SO2)2NLi.
In an embodiment of the present disclosure, the concentration of the lithium salt may be properly determined in view of ionic conductivity and solubility, and may be, for example, 0.1 to 4M, preferably 0.25 to 2M, more preferably 0.5 to 1.5M, even more preferably 0.5 to 1.0M. When the concentration of the lithium salt is in the above-described range, it may be possible to ensure suitable ionic conductivity for the operation of the battery or appropriate viscosity of the electrolyte solution, thereby improving mobility of lithium ions and suppressing decomposition reaction of the lithium salt itself, but the present disclosure is not limited thereto.
In an embodiment of the present disclosure, the additive may comprise a nitrogen compound to improve the electrical conductivity of the electrolyte solution comprising the lithium salt and increase the lifespan of the lithium-sulfur battery.
Specifically, the efficacy of the nitrogen compound is not limited thereto, but for example, the nitrogen compound may suppress the reduction reaction of polysulfide produced during charging/discharge of the lithium-sulfur battery, thereby preventing irreversible consumption of polysulfide, leading to improved performance of the lithium-sulfur battery.
In an embodiment of the present disclosure, the nitrogen compound is not limited to a particular type and may include those which stably form the SEI layer of the negative electrode and improve the charge⋅discharge efficiency, and may include, for example, a nitric acid compound, a nitrous acid-based compound or a mixture thereof.
In an embodiment of the present disclosure, the nitrogen compound may be, for example, selected from the group consisting of an inorganic nitric acid or nitrous acid compound such as lithium nitrate (LiNO3), potassium nitrate (KNO3), cesium nitrate (CsNO3), barium nitrate (Ba(NO3)2), ammonium nitrate (NH4NO3), lithium nitrite (LiNO2), potassium nitrite (KNO2), cesium nitrite (CsNO2), ammonium nitrite (NH4NO2); an organic nitric acid or nitrous acid compound such as methyl nitrate, dialkyl imidazolium nitrate, guanidine nitrate, imidazolium nitrate, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite; an organic nitro compound such as nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitro pyridine, dinitro pyridine, nitrotoluene, dinitrotoluene and a combination thereof, and preferably, may comprise lithium nitrate.
In an embodiment of the present disclosure, the nitrogen compound may be, for example, included in an amount of 1 weight % to 10 weight %, 2 weight % to 10 weight % or 3 weight % to 10 weight %, specifically 3 weight % to 8 weight %, 3 weight % to 6 weight %, or 3 weight % to 5 weight % based on the total weight of the electrolyte solution, but is not limited thereto. When the nitrogen compound is included in the above-described amount, the nitrogen compound may improve the electrical conductivity of the electrolyte solution and suppress the reduction reaction of polysulfide when used in the lithium-sulfur battery, but the present disclosure is not limited thereto.
In a preferred embodiment of the present disclosure, the concentration of the nitrogen compound in the electrolyte solution is in the range of from 0.15 to 1.5 mol/L, preferably in the range of from 0.20 to 1.0 mol/L, more preferably in the range of from 0.25 to 0.80 mol/L, or even more preferably in the range of from 0.30 to 0.60 mol/L.
When the nitrogen compound is included in the above-described amount, the nitrogen compound may improve the electrical conductivity of the electrolyte solution and suppress the reduction reaction of polysulfide when used in the lithium-sulfur battery, but the present disclosure is not limited thereto. In case the nitrogen compound is also a lithium salt, e.g. LiNO3, it may be also possible to ensure suitable ionic conductivity for the operation of the battery or appropriate viscosity of the electrolyte solution, thereby improving mobility of lithium ions and suppressing decomposition reaction of the lithium salt itself, in parallel to improving the electrical conductivity of the electrolyte solution and suppressing the reduction reaction of polysulfide, when used in the lithium-sulfur battery but the present disclosure is not limited thereto. Thus, a lithium-sulfur battery with long life characteristics, while having high energy density, may be provided.
In an embodiment of the present disclosure, the ratio of the concentration of the lithium salt (mol/L) and the concentration of the nitrogen compound (mol/L) is in the range of from 0.5 to 6, preferably in the range of from 1.0 to 4.0, or more preferably in the range of from 1.3 to 2.5.
When the concentration of the lithium salt (mol/L) and the concentration of the nitrogen compound (mol/L) is in the above-described ratio, it may be possible to ensure suitable ionic conductivity for the operation of the battery or appropriate viscosity of the electrolyte solution, thereby improving mobility of lithium ions and suppressing decomposition reaction of the lithium salt itself, while the electrical conductivity of the electrolyte solution is improved and the reduction reaction of polysulfide is suppressed, when used in the lithium-sulfur battery but the present disclosure is not limited thereto. Thus, a lithium-sulfur battery with long life characteristics, while having high energy density, may be provided.
In an embodiment of the present disclosure, the lithium concentration in the electrolyte solution, preferably obtained from the sum of the concentration of the lithium salt (mol/L) in the electrolyte solution and the concentration of the nitrogen compound (mol/L) in the electrolyte solution, is 1 mol/L or more, like in the range of from 0.4 to 3 mol/L, preferably in the range of from 1 to 2.3 mol/L, more preferably in the range of from 1.0 to 2.0 mol/L, or even more preferably in the range of from 1.05 to 1.5 mol/L. When the lithium concentration in the electrolyte solution, preferably obtained from the sum of the concentration of the lithium salt (mol/L) in the electrolyte solution and the concentration of the nitrogen compound (mol/L) in the electrolyte solution, is in the above-described range, it may be possible to ensure suitable ionic conductivity for the operation of the battery or appropriate viscosity of the electrolyte solution, thereby improving mobility of lithium ions and suppressing decomposition reaction of the lithium salt itself, while the electrical conductivity of the electrolyte solution is improved and the reduction reaction of polysulfide is suppressed, when used in the lithium-sulfur battery, but the present disclosure is not limited thereto. Thus, a lithium-sulfur battery with long life characteristics, while having high energy density, may be provided.
In another embodiment of the present disclosure, the electrolyte solution comprises the nonaqueous solvent, and two lithium salts which are different from each other, wherein one among the two lithium salts is a nitrogen containing lithium salt, which is the nitrogen compound as defined above, preferably a lithium nitrate.
In an embodiment of the present disclosure, the lithium-sulfur battery may have varying energy density depending on the ratio of the electrolyte solution and the positive electrode active material. The smaller ratio of the electrolyte solution and the positive electrode active material, the higher energy density of the lithium-sulfur battery, and for example, the weight ratio (El/S weight ratio) of the electrolyte solution and sulfur in the sulfur-carbon composite may be 3.5 or less.
In an embodiment of the present disclosure, the lithium-sulfur battery may be, for example, manufactured with the El/S ratio of 3.0 or less, or 2.9 or less.
It may be possible to achieve long life characteristics by limiting the sulfur (S) content in the negative electrode below 3 weight % at SOC 100 as described above according to an embodiment of the present disclosure.
In the present disclosure, long life characteristics of the lithium-sulfur battery represent high capacity retention after repeated charge/discharge cycles.
In an embodiment of the present disclosure, the lithium-sulfur battery may retain 80% or more of the initial capacity after the repeated 190 charge/discharge cycles. Specifically, the lithium-sulfur battery may have 80% or more of the capacity measured in one charge/discharge cycle after at least 190 repeated charge/discharge cycles at 0.3 to 0.5 C rate in a range of from 1.8 V to 2.5 V at room temperature.
In an embodiment of the present disclosure, the room temperature may be, for example, 23° C. to 25° C., and specifically 23° C.
In an embodiment of the present disclosure, the lithium-sulfur battery may be activated by charging/discharging for a number of cycles at which a retention rate is 95% or more based on specification of the lithium-sulfur battery, for example, 10 cycles.
In an embodiment of the present disclosure, the charge/discharge rate may be 0.1C to 1.0C, specifically, 0.3C rate or 0.5C rate, and may be, for example, the charge rate of 0.3 C and the discharge rate of 0.5C, but the charge/discharge rate is not limited to a particular rate and may include any rate of charge and discharge within the above-described rate range.
In an embodiment of the present disclosure, the energy density of the lithium-sulfur battery may be, for example, 300 Wh/kg or more.
In an embodiment of the present disclosure, the energy density of the lithium-sulfur battery may be measured by known methods, and the measurement method is not limited to a particular method. For example, the energy density of the lithium-sulfur battery may be, for example, measured by discharging at 0.5 C rate and charging at 0.3 C rate in a range of from 1.8 V to 2.5 V at room temperature of 23° C.
In an embodiment of the present disclosure, the lithium-sulfur battery may have various shapes, and for example, coin, pouch type or cylindrical shape, but is not limited thereto.
According to another aspect of the present disclosure, there is provided a method for evaluating the lifespan of the lithium-sulfur battery.
In an embodiment of the present disclosure, the lithium-sulfur battery to be evaluated for lifespan comprises the electrode assembly which includes the positive electrode comprising the sulfur-carbon composite, the negative electrode comprising the lithium-containing layer and the SEI layer on at least one surface of the lithium-containing layer, and the separator between the positive electrode and the negative electrode; and the electrolyte solution.
The evaluation method comprises determining the lithium-sulfur battery having the sulfur (S) content of 3 weight % or less based on the total weight of the negative electrode at SOC 100 as a long life lithium-sulfur battery.
In an embodiment of the present disclosure, the long life lithium-sulfur battery may be, for example, a battery having the lifespan of 190 or more cycles after repeated charge/discharge cycles at 0.3 to 0.5 C rate in a range of from 1.8 V to 2.5 V at room temperature, wherein the room temperature is from 23° C. to 25° C.
According to further another aspect of the present disclosure, there is provided a method for manufacturing a lithium-sulfur battery based on a condition that the negative electrode at SOC 100 includes less than a certain amount of the sulfur element.
In an embodiment of the present disclosure, the method for manufacturing a lithium-sulfur battery comprises preparing a positive electrode comprising a sulfur-carbon composite; preparing a negative electrode including a lithium-containing layer and a SEI layer on at least one surface of the lithium-containing layer; disposing a separator between the positive electrode and the negative electrode to form an electrode assembly; accommodating the electrode assembly in a battery housing; injecting an electrolyte solution in the battery housing; sealing the battery housing to form a lithium-sulfur battery; and determining whether the lithium-sulfur battery has 3 weight % or less of sulfur element (S) based on the total weight of the lithium-containing layer and the SEI layer at SOC 100.
According to yet another aspect of the present disclosure, there is provided a lithium-sulfur battery which is manufactured based on a condition that the negative electrode at SOC 100 includes less than a certain amount of sulfur element.
In an embodiment of the present disclosure, the lithium-sulfur battery comprises an electrode assembly which comprises a positive electrode including a sulfur-carbon composite, a negative electrode including a lithium-containing layer and a SEI layer on at least one surface of the lithium-containing layer, and a separator between the positive electrode and the negative electrode; and an electrolyte solution, and the lithium-sulfur battery is manufactured based on the condition that the negative electrode comprises sulfur element (S) in an amount of 3 weight % or less based on the total weight of the negative electrode at SOC 100.
In an embodiment of the present disclosure, the lithium-sulfur battery at SOC 100 may have a potential of 2.4 V to 2.7 V.
In an embodiment of the present disclosure, the electrolyte solution contains 1 weight % or more of a nitrogen compound based on the total weight of the electrolyte solution.
Hereinafter, examples will be described to help an understanding of the present disclosure, but the following examples are provided by way of illustration and it is obvious to those skilled in the art that various changes and modifications may be made thereto within the technical aspect and scope of the present disclosure and such changes and modifications fall within the scope of the appended claims.
Inorganic sulfur (S8) and carbon nanotubes (CNT) as a positive electrode active material were mixed to prepare a sulfur-carbon composite (S/C weight ratio=2.3), and 96 weight % of the prepared sulfur-carbon composite and 4 weight % of polyacrylate (PAA) as a binder were mixed to prepare a positive electrode slurry composition. The positive electrode slurry composition was coated on an aluminum current collector and dried to manufacture a positive electrode. The loading amount of the manufactured positive electrode was 2.5 mAh/cm2 (2.08 mg(s)/cm2).
For a negative electrode, a 60 μm thick lithium metal was used.
The positive electrode and the negative electrode were placed facing each other with a polyethylene separator having the thickness of 16 μm and porosity of 46 vol % interposed between to prepare an electrode assembly.
The prepared electrode assembly was received in a pouch type housing and an electrolyte solution containing 0.75 M lithium salt (LiTFSI) and 2.1 wt % of lithium nitrate (LiNO3) dissolved in a mixed solvent of dimethoxyethane (DME):2-methyl furan (2-MeF) at a volume ratio of 8:2 was injected at an El/S ratio of 2.9 to manufacture a lithium-sulfur battery.
Thus, the concentration of the nitrogen compound, LiNO3, in the electrolyte solution was 0.33 mol/L.
A lithium-sulfur battery was manufactured by the same method as Example 1 except that 3.5 wt % of lithium nitrate (LiNO3) was dissolved in the electrolyte solution. Thus, the concentration of the nitrogen compound, LiNO3, in the electrolyte solution was 0.56 mol/L.
A lithium-sulfur battery was manufactured by the same method as Example 1 except that 5.0 weight % of lithium nitrate (LiNO3) was dissolved in the electrolyte solution. Thus, the concentration of the nitrogen compound, LiNO3, in the electrolyte solution was 0.8 mol/L.
A lithium-sulfur battery was manufactured by the same method as Example 1 except that 0.8 wt % of lithium nitrate (LiNO3) was dissolved in the electrolyte solution. Thus, the concentration of the nitrogen compound, LiNO3, in the electrolyte solution was 0.13 mol/L.
A lithium-sulfur battery was manufactured by the same method as Example 1 except that 0.4 wt % of lithium nitrate (LiNO3) was dissolved in the electrolyte solution. Thus, the concentration of the nitrogen compound, LiNO3, in the electrolyte solution was 0.06 mol/L.
The weight % and concentration of lithium nitrate (LiNO3), the concentration of lithium salt (LiTFSI) in the electrolyte solution, and the ratio of LiTFSI [mol/L]/LiNO3 [mol/L] and the lithium concentration of the electrolyte solution are shown in Table 1 below.
The energy density of the lithium-sulfur batteries was measured by discharging at 0.5C rate to 1.8 V and charging at 0.5 C rate to 2.5 V at room temperature (23° C.).
The energy density of the manufactured lithium-sulfur battery of Example 1 and Comparative Example 1 was 320 Wh/kg.
Each of the lithium-sulfur batteries of Examples 1 to 3 and Comparative Examples 1 and 2 manufactured as described above undergone activation by charging/discharging for 10 cycles at 0.5 C discharge rate and 0.3 C charge rate in a range of from 1.8 V to 2.5 V at room temperature (23° C.), and was disassembled at SOC 100 to obtain the negative electrode.
In this instance, the obtained negative electrode comprises the lithium metal used to manufacture the lithium-sulfur battery and the SEI layer formed by a discharge and a recharge.
To obtain the negative electrode, the lithium-sulfur battery to be measured was disassembled to separate the positive electrode/separator/negative electrode, and the separated negative electrode was put into a container containing a set mass of solvent and washed for 5 minutes or more. In this instance, the same solvent as the nonaqueous solvent in the electrolyte solution was used.
Analysis was performed to determine the amount of lithium (Li), sulfur (S), nitrogen (N) and fluorine (F) in the obtained negative electrode, and the analysis results are shown in the following Table 2.
The analysis method for determining the amount of lithium (Li), sulfur (S), nitrogen (N) and fluorine (F) was performed as below.
First, to analyze lithium, sulfur and fluorine, the weight of samples of a predetermined amount was measured in a moisture controllable dry room, and primary oxidation reaction was induced using water. After the primary oxidation reaction, nitric acid was added to ionically dissociate the substances in the samples. Quantitative analysis of the processed solution was performed using ICP-OES (or ICP-MS). To determine the fluorine content, quantitative analysis of the solution subjected to the primary oxidation was immediately performed using IC.
To determine the nitrogen content, a predetermined amount was encapsulated with a paraffin film in the dry room, pyrolysis was performed on the encapsulated samples in an oxygen filled atmosphere using oxygen combustion chamber (bomb), and vaporized nitrogen was dissolved in an inner solvent to saturation. Quantitative analysis of the nitrogen absorbed solution was performed using IC.
The mass of each element analyzed according to the above method was calculated in weight percent based on the total weight of the negative electrode to be analyzed, and is shown in Table 2 below. The total sum of mass of each element analyzed according to the above method represents the total weight of the negative electrode.
Each of the lithium-sulfur batteries of Examples 1 to 3 and Comparative Examples 1 and 2 manufactured as described above undergone activation by discharging at 0.5 C rate and charging at 0.3 C rate in a range of from 1.8 V to 2.5 V at room temperature (23° C.), and repeated the charge and discharge process at 0.5 C rate. At the point in time when the lithium-sulfur battery retains 80% capacity based on the battery capacity measured in the first cycle after the activation, the number of cycles until then was measured, and the results are shown in the following Table 2.
As shown in the above Table 2, it was confirmed that the lithium-sulfur battery having long life characteristics could be implemented when the sulfur (S) content in the negative electrode is controlled below 3 wt % or less at SOC 100.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0058000 | May 2023 | KR | national |
