Positive electrode lithium supplement, and positive electrode and lithium secondary battery comprising same

Abstract

Provided are a positive electrode lithium supplement, and a positive electrode and a lithium secondary battery comprising same. The positive electrode lithium supplement includes an inorganic lithium-supplemented solid electrolyte material and a two-dimensional MXene material. The inorganic lithium-supplemented solid electrolyte material includes a sulfide-based lithium-supplemented solid electrolyte and / or a halide-based lithium-supplemented solid electrolyte. The two-dimensional MXene material is used as a conductive agent for constructing a three-dimensional conductive network and also as a catalyst for effectively reducing the decomposition voltage of an inorganic lithium-supplemented solid electrolyte material. The positive electrode lithium supplement supplies additional lithium ions to the battery through an electrochemical decomposition reaction at a low voltage during first charging / discharging in a battery formation process, thereby improving the initial efficiency, energy density, and cycle stability of the battery. In addition, elements such as P, S, and halogen are introduced as effective components of a negative electrode SEI film, further enhancing the cycle stability of the battery.

Description

Anode lithium supplements and anodes and lithium secondary batteries containing the same

[0001] The present disclosure relates to the field of lithium secondary batteries, and specifically, to a positive lithium supplement and a positive and lithium secondary battery containing the same.

[0002] Lithium-ion batteries are widely applied due to their advantages, such as high capacity, high energy density, high operating voltage, and long service life.

[0003] Generally, in lithium secondary batteries, the negative electrode and the electrolyte react at the interface during the charging and discharging process to form a solid electrolyte interface film (i.e., SEI film) that covers the surface of the negative electrode. The formation of the SEI film consumes some lithium, resulting in irreversible lithium loss and reducing the initial Coulomb efficiency of the negative electrode, which further reduces the energy density and capacity of the lithium secondary battery. Therefore, lithium replenishment must be performed on the lithium secondary battery.

[0004] Currently, lithium replenishment methods can be classified into positive electrode lithium replenishment, negative electrode lithium replenishment, and separator lithium replenishment. Among these, the positive electrode lithium replenishment method can be completed by introducing the original lithium secondary battery production process, and this method can be well integrated with existing lithium secondary battery manufacturing processes without the need for new equipment. Compared to negative electrode lithium replenishment and separator lithium replenishment, positive electrode lithium replenishment offers advantages such as high safety, low process costs, and high process compatibility.

[0005] Conventional cathode lithium replenishment technologies are broadly classified into inorganic oxide lithium replenishment materials (e.g., Li₅FeO₄, Li₂NiO₂, Li₆CoO₄Li₄SiO₄, lithium oxide (Li₂O), etc.), organic lithium replenishment materials (e.g., lithium oxalate (Li₂C₂O₄), lithium citrate (Li₃C₆H₅O₇), etc.), and lithium nitride (Li₃N). Inorganic oxide lithium materials possess high capacity, but they present problems such as high decomposition voltage during the lithium replenishment process, oxygen release during decomposition, and the influx of foreign metal ions into the battery system. Furthermore, since iron-based or cobalt-based lithium replenishers release large amounts of oxygen during the replenishment process, the amount added to the cathode must not be excessive; otherwise, severe oxygen release from the cathode during the battery cycle can cause adverse effects with the electrolyte, leading to battery swelling and severely affecting the battery's cycle performance. Lithium niobate replenishers have low lithium replenishment capacity and are expensive, resulting in poor lithium replenishment efficacy when applied to lithium secondary batteries. Lithium silicate lithium supplements have a high intrinsic decomposition voltage, requiring the addition of two separate catalysts (e.g., elemental sulfur) and conductive agents. However, the introduction of elemental sulfur has an adverse effect on the late-stage cycle of the battery. The decomposition voltage of organic lithium supplement materials is too high, making it difficult to decompose within the charge / discharge cutoff voltage range of typical lithium secondary battery systems, and the actual lithium supplement capacity during normal use is much lower than the theoretical capacity. Furthermore, organic lithium supplement materials currently present relatively significant technical challenges in terms of both synthesis and application. Conventional lithium oxide and lithium nitride materials have even higher intrinsic decomposition voltages and unstable compounds, making them unsuitable for addition to lithium secondary batteries as lithium supplements.

[0006] Therefore, there is a demand for a cathode lithium supplement to provide lithium secondary batteries that improve the long-cycle performance of lithium secondary batteries and satisfy growing application requirements in different fields such as energy storage and power.

[0007] According to one embodiment, an anode lithium supplement is provided comprising a mixture of an inorganic solid electrolyte having a low intrinsic decomposition potential and an MXene material as a lithium supplement material.

[0008] According to another embodiment, a positive electrode comprising the above-mentioned positive electrode lithium supplement is provided.

[0009] According to another embodiment, a lithium secondary battery including the anode is provided.

[0010] Other embodiments will be described in part in the following description, and may become partially apparent from the above description or obtainable by practicing the embodiments of the present disclosure.

[0011] According to one embodiment, the positive lithium supplement may include an inorganic lithium supplement solid electrolyte material and a two-dimensional MXene material, and the intrinsic decomposition voltage of the inorganic lithium supplement solid electrolyte material is 4V or less.

[0012] In one embodiment, the inorganic lithium-replenished solid electrolyte material may include a sulfide-based lithium-replenished solid electrolyte and / or a halide-based lithium-replenished solid electrolyte.

[0013] In one embodiment, the sulfide-based lithium supplemented solid electrolyte may include a lithium sulfide-based lithium supplemented solid electrolyte, a lithium argyrodite-type solid electrolyte, a lithium-germanium-phosphorus-sulfur-type solid electrolyte, and / or other sulfide-based lithium supplemented solid electrolytes.

[0014] In one embodiment, the lithium sulfide-based lithium supplemental solid electrolyte is Li3PS4 and / or Li7P3S 11It may include; and the lithium azyrodite-type solid electrolyte is Li7PS6 and / or Li 7-x PS 6-x A x It may include, where A is Cl, Br and / or I, and x is 0 to 2; the lithium-germanium-phosphorus-sulfur type solid electrolyte is Li 10 Ge(Sn)P2S 12 It may include; additionally, other sulfide-based lithium supplemented solid electrolytes may include Li4SnS4 and / or Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 It may include.

[0015] In one embodiment, the halide-based lithium supplemented solid electrolyte may include an anti-perovskite type solid electrolyte.

[0016] In one embodiment, the antiperovskite-type solid electrolyte may include Li3OCl or Li3YBr6.

[0017] In one embodiment, the two-dimensional MXene material is of the formula M n+1 X n T x It is represented as, where M is a transition element; A is an element of Group 13 or 14 of the periodic table; X is C or N; and T x is a surface functional group; n is 1 to 4.

[0018] In one embodiment, M may include Ti, V, Mo, W, Nb, Zr, Hf, or Ta; A may include B, Al, Ga, In, Si, Ge, or Sn; and T x It may include a hydrogen functional group, an oxygen functional group, a hydroxy functional group, or a halogen functional group.

[0019] In one embodiment, the two-dimensional MXene material is Ti2CT x and / or Mo2CT x It could be.

[0020] In one embodiment, the weight ratio of the inorganic lithium-replenished solid electrolyte material to the two-dimensional MXene material may be 1:0.2 to 1:2.

[0021] According to one or more embodiments, the anode may include an anode lithium supplement.

[0022] According to one or more embodiments, the lithium secondary battery may include the positive electrode comprising the positive electrode lithium supplement.

[0023] In the present disclosure, the anode lithium supplement comprises a sulfide-based lithium supplement solid electrolyte or a halide-based lithium supplement solid electrolyte material and a two-dimensional MXene material. Here, the two-dimensional MXene material is used not only as a conductor to build a three-dimensional conductive network but also as a catalyst to effectively reduce the decomposition voltage of the inorganic lithium supplement solid electrolyte material. The anode lithium supplement additionally supplies lithium ions to the battery through an electrochemical decomposition reaction at a low voltage during the first charge / discharge in the battery formation process, thereby improving the initial efficiency, energy density, and cycle stability of the battery. At the same time, P, S, and halogen elements introduced by the sulfide-based lithium supplement solid electrolyte material act as effective components of the cathode SEI film, further improving the cycle stability of the battery.

[0024] To provide a further understanding of the present disclosure, drawings are included, which are incorporated into this specification and constitute a part of the specification. The drawings illustrate embodiments of the present disclosure and, together with the description, explain the principles of the present disclosure. By following the description of the combined drawings, the above-described contents and other aspects, features, and advantages of the embodiments of the present disclosure will become more apparent.

[0025] FIGS. 1 to 4 are schematic drawings illustrating a liquid-type lithium secondary battery according to one embodiment.

[0026] FIG. 5 is a schematic diagram of an all-solid-state lithium secondary battery according to one embodiment.

[0027] Figure 6 is an image of the positive lithium supplement prepared in Example 1, magnified 9000 times using a scanning electron microscope (SEM).

[0028] Refer to the embodiments below in more detail. An example of an embodiment is shown in the drawings, and the same reference numerals denote the same components, and redundant descriptions thereof are omitted. In this regard, the described embodiments may have different forms and should not be interpreted as being limited to the presented description. Accordingly, embodiments are described with reference to the drawings to explain aspects of the present disclosure.

[0029] The term “and / or” as used in the specification includes any combination of one or more of the related listed items and all combinations thereof. Herein, “combination thereof” means a mixture of components, laminates, composites, copolymers, alloys, blends, reaction products, etc.

[0030] When expressions such as “at least one of …” and “selected from ……” used in the specification are placed before or after a series of elements, they modify the entire list of elements rather than the individual elements enumerated. For example, “at least one of a, b, and c”, “selected from at least one of a, b, and c,” etc., may mean only a, only b, c, both a and b (e.g., both), both a and c (e.g., both), all of a, b, and c, or variations thereof.

[0031] Unless otherwise defined, all terms used in this disclosure (including technical and scientific terms) have the same meaning as generally understood by a person skilled in the art to which the present invention pertains. Additionally, terms (e.g., terms generally defined in dictionaries) should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology and may be explicitly defined herein unless interpreted in an ideal or overly formal sense.

[0032] Embodiments are described below with reference to cross-sectional views, which are schematic drawings of ideal embodiments. As such, the depicted shapes may change, for example, due to manufacturing techniques and / or tolerances. Accordingly, the embodiments described in this disclosure should not be interpreted as being limited to the specific shape regions exemplified in this disclosure, and should include shape variations, for example, due to manufacturing. For example, regions depicted or described as flat may generally have rough and / or non-linear features. Additionally, depicted sharp angles may be circular. Accordingly, regions depicted in the drawings are essentially schematic, and the shapes are not intended to describe the exact shape of the regions or to limit the claims.

[0033] The present disclosure may be implemented in various different forms and should not be interpreted as being limited to the embodiments described herein. Embodiments are provided to make the present disclosure thorough and complete and to sufficiently convey the scope of the present disclosure to a person skilled in the art. Identical reference numerals indicate identical elements.

[0034] “Group” refers to a group of the periodic table of elements according to the classification system of Groups I through XVIII of the International Union of Pure and Applied Chemistry (“IUPAC”).

[0035] In the present disclosure, the “particle diameter” of a granule refers to the average particle diameter when the granule is spherical, or the average major axis length when the granule is non-spherical. The particle diameter can be measured using a particle size analyzer (PSA). The “particle diameter” is, for example, the average particle diameter. The “average particle diameter” is, for example, D, which is an intermediate particle diameter. 50 am.

[0036] The term “metal” as used in the specification includes metals and metalloids in an elemental or ionic state (e.g., silicon and germanium).

[0037] The term “alloy” as used in the specification means a mixture of two or more types of metals.

[0038] The term “electrode active material” as used in the specification refers to an electrode material capable of lithiation and delithiation.

[0039] The term “anode active material” as used in the specification refers to an anode material capable of lithiation and delithiation.

[0040] The term “cathode active material” as used in the specification refers to a cathode material capable of lithiation and delithiation.

[0041] The terms “substantially” and similar terms used in the specification are used as terms of approximation rather than terms of degree, and are intended to account for the inherent deviation of a measured or calculated value that is recognizable by a person skilled in the art. Additionally, when used in combination with a number or a range of numbers, the terms “approximately” and similar terms include values ​​within an acceptable range of deviation from the specified value and the specific value determined by a person skilled in the art, taking into account errors related to the measurement in question and the measurement of a specific quantity (e.g., limitations of the measurement system). For example, “approximately” may mean within one or more standard deviations, or within ±30%, ±20%, ±10%, or ±5% of the specified value.

[0042] Hereinafter, a positive lithium supplement according to an embodiment and a positive and lithium secondary battery containing the same will be described in more detail.

[0043] lithium secondary battery

[0044] Lithium secondary batteries can be classified into all-solid-state lithium secondary batteries, semi-solid-state lithium secondary batteries, and liquid-state lithium secondary batteries depending on the electrolyte, but are not limited thereto. In the following description, all-solid-state lithium secondary batteries and liquid-state lithium secondary batteries will be primarily described.

[0045] In addition, lithium secondary batteries can be classified according to their shape into cylindrical batteries, prismatic batteries, pouch batteries, coin batteries, etc., but are not limited thereto.

[0046] Liquid lithium secondary battery

[0047] FIGS. 1 to 4 are schematic drawings illustrating liquid-type lithium secondary batteries according to one embodiment. FIG. 1 is a cylindrical battery, FIG. 2 is a prismatic battery, and FIGS. 3 and 4 are pouch batteries.

[0048] Referring to FIGS. 1 to 4, a lithium secondary battery (100) may include an electrode assembly (140) including a separator (130) installed between a positive electrode (110) and a negative electrode (120); and a housing (150) that accommodates the electrode assembly (140). The positive electrode (110), the negative electrode (120), and the separator (130) may be impregnated with an electrolyte (not shown). As shown in FIG. 1, the lithium secondary battery (100) may further include a sealing member (160) that seals the housing (150). Additionally, as shown in FIG. 2, the lithium secondary battery (100) may further include a positive lead tab (111), a positive terminal (112), a negative lead tab (121), and a negative terminal (122). As illustrated in FIGS. 3 and 4, the lithium secondary battery (100) may further include an electrode tab (170) illustrated in FIG. 4, a positive electrode tab (171) illustrated in FIG. 3, and a negative electrode tab (171) that form an electrical path for guiding the current formed in the electrode assembly (140) to the outside.

[0049] All-solid-state lithium secondary battery

[0050] FIG. 5 is a schematic diagram of an all-solid-state lithium secondary battery according to one embodiment of the present disclosure. Referring to FIG. 5, the all-solid-state lithium secondary battery (200) may include a positive electrode (210), a negative electrode (220), and a solid electrolyte layer (230) between the positive electrode (210) and the negative electrode (220).

[0051] anode

[0052] In one embodiment, the positive electrode may include a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, and the positive electrode active material layer may include a positive electrode active material and a positive electrode lithium supplement. Additionally, the positive electrode active material layer may further include a binder and / or a conductive material.

[0053] In the positive active material layer, the weight ratio of the positive lithium supplement, positive active material, conductive material and binder can be x:y:z:w, and 2≤x≤30, 50≤y≤96, 0≤z≤10, 2≤w≤10, x+y+z+w=100.

[0054] positive electrode active material

[0055] The positive electrode active material may include a compound capable of inserting and deinserting lithium (lithiation absorption compound). The positive electrode active material may include, for example, an oxide-based positive electrode active material, a sulfide-based positive electrode active material, or a combination thereof.

[0056] The oxide-based cathode active material may include a lithium transition metal oxide. The lithium transition metal oxide may include a lithium nickel-based oxide, a lithium cobalt-based oxide, a lithium manganese-based oxide, a lithium iron phosphate compound, and / or a cobalt-free lithium nickel manganese-based oxide.

[0057] For example, as an oxide-based cathode active material, a compound represented by one of the following chemical formulas may be used: Li a A 1-b X b D 1 2(0.90≤a≤1.8,0≤b≤0.5);Li a A 1-b X b O 2-c1 D 1 c1 (0.90≤a≤1.8,0≤b≤0.5,0≤c1≤0.05);Li a E 1-b X b O 2-c1 D 1 c1 (0.90≤a≤1.8,0≤b≤0.5,0≤c1≤0.05);Li a E 2-b X b O 4-c1 D 1 c1 (0.90≤a≤1.8,0≤b≤0.5,0≤c1≤0.05);Li a Ni 1-b-c Co b Xc D 1 α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α≤2);Li a Ni 1-b-c Co b X c O 2-α T α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α<2);Li a Ni 1-b-c Co b X c O 2-α T2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α<2);Li a Ni 1-b-c Mr b X c D 1 α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α≤2);Li a Ni 1-b-c Mr b X c O 2-α T α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α<2);Li a Ni 1-b-c Mr b X c O 2-α T2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α<2);Li a Ni b HAVE BEEN c G d O2(0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0.001≤d≤0.1;Li a Ni b Co c L 1 d G e O2(0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5,0≤e≤0.1);Li a NiG b O2(0.90≤a≤1.8,0.001≤b≤0.1);Li a CoG bO2(0.90≤a≤1.8,0.001≤b≤0.1);Li a Mn 1-b G b O2(0.90≤a≤1.8,0.001≤b≤0.1);Li a Mn2G b O4(0.90≤a≤1.8, 0.001≤b≤0.1);Li a Mn 1-g G g PO4(0.90≤a≤1.8, 0≤g≤0.5);QO2;QS2;LiQS2;V2O5;LiV2O5;LiZO2;LiNiVO4;Li (3-f) J2(PO4)3(0≤f≤2);Li (3-f) Fe2(PO4)3(0≤f≤2); and Li a FePO4(0.90≤a≤1.8).

[0058] In the above chemical formula, A may be Ni, Co, Mn, or any combination thereof; X may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, or any combination thereof; and D 1 may be O, F, S, P, or any combination thereof; E may be Co, Mn, or any combination thereof; T may be F, S, P, or any combination thereof; G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or any combination thereof; Q may be Ti, Mo, Mn, or any combination thereof; Z may be Cr, V, Fe, Sc, Y, or any combination thereof; J may be V, Cr, Mn, Co, Ni, Cu, or any combination thereof; L 1 can be Mn, Al, or any combination thereof.

[0059] In one embodiment, the oxide-based cathode active material is, for example, LiCoO2, LiFePO4, LiMn2O4, LiNi x Co y Mn z O2(x+y+z=1), LiNi x Co yAl z O2(x+y+z=1), LiNiO2, LiVO2, LiCrO2, LiCoMnO4, Li2NiMn3O8, LiNi 0.5 Mn 1.5 It may include one or more types such as O4.

[0060] Particle size (D) of oxide-based positive electrode active material 50 ) may be, for example, about 0.1 μm to about 30 μm, about 0.5 μm to about 20 μm, or about 1 μm to about 15 μm. The oxide-based cathode active material may be in the form of a single crystal or a polycrystalline form.

[0061] Sulfide-based cathode active materials may include, for example, Li2S, Li2S-containing complexes, or a combination thereof.

[0062] The Li2S-containing composite may include, for example, a composite of Li2S and carbon, a composite of Li2S, carbon and a solid electrolyte, a composite of Li2S and a solid electrolyte, a composite of Li2S and a lithium salt, a composite of Li2S, a lithium salt and carbon, a composite of Li2S and a metal carbide, a composite of Li2S, carbon and a metal carbide, a composite of Li2S and a metal nitride, or a combination thereof. The carbon may be, for example, crystalline carbon, amorphous carbon, or a combination thereof. The solid electrolyte may be, for example, a crystalline solid electrolyte, an amorphous solid electrolyte, or a combination thereof used as an ion-conducting material in the field (e.g., Li3PO4-Li2SO4, Li2S-P2S5, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, etc.). The lithium salt may be, for example, a binary compound, a ternary compound, or a combination thereof containing lithium and one type (or kind) of element selected from Groups XIII to XVII of the periodic table (e.g., LiF, LiCl, LiBr, LiI, LiH, Li2S, Li2O, Li2Se, Li2Te, Li3N, Li3P, Li3As, Li3Sb, LiI3LiB3, etc.). The metal carbide may be, for example, a two-dimensional metal carbide. The metal nitride may be, for example, a two-dimensional metal nitride.

[0063] In one embodiment, the positive electrode active material may include, for example, a high-nickel positive electrode active material, and based on 100 mol% of metal other than lithium in the lithium transition metal composite oxide, the high-nickel positive electrode active material may have a nickel content of about 80 mol% or more, about 85 mol% or more, about 90 mol% or more, about 91 mol% or more, or about 94 mol% or more, or about 99 mol% or less. The high-nickel positive electrode active material can realize high capacity and can also be applied to high-capacity, high-density lithium secondary batteries.

[0064] Anode Lithium Supplement

[0065] The positive lithium supplement may be a composite lithium supplement comprising an inorganic lithium supplement solid electrolyte material and a two-dimensional MXene material.

[0066] In one embodiment, the inorganic lithium-replenished solid electrolyte material has a low intrinsic decomposition voltage and may include a sulfide-based lithium-replenished solid electrolyte and / or a halide-based lithium-replenished solid electrolyte.

[0067] Sulfide-based lithium supplemented solid electrolytes are lithium sulfide-based lithium supplemented solid electrolytes (e.g., Li3PS4 or Li7P3S 11 ), lithium azyrodite-type solid electrolyte (e.g., Li7PS6 and / or Li 7-x PS 6-x A x and, where A is Cl, Br and / or I, and x is 0 to 2), lithium-germanium-phosphorus-sulfur type solid electrolyte (e.g., Li 10 Ge(Sn)P2S 12 ) and other sulfide-based lithium-supplemented solid electrolytes (e.g., Li4SnS4 or Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 It may include one or more of the following. The lithium azyrodite-type solid electrolyte may be, for example, Li6PS5Cl, but is not limited thereto. The halide-based lithium supplemental solid electrolyte may include an antiperovskite-type solid electrolyte, for example, Li3OCl or Li3YBr6.

[0068] The intrinsic electrochemical stability of sulfide-based lithium-replenished solid electrolytes is poor, and the electrochemical stability window is narrow, ranging from 1.7V to 3.2V. At voltages higher than 3.2V, the sulfide-based lithium-replenished solid electrolyte can easily undergo a decomposition reaction as shown in the following reaction equation.

[0069] [Reaction Equation]

[0070] Li6PS5Cl → Li2S+Li3P+LiCl

[0071] 2D MXene materials are precursor M n+1 AX n It is a two-dimensional layered material obtained through chemical etching. The two-dimensional MXene material has the chemical formula M n+1 X n T x It may be represented as follows. M is a transition element and may include, but is not limited to, Ti, V, Mo, W, Nb, Zr, Hf, Ta, or combinations thereof; A is a Group 13 or Group 14 element of the periodic table and may include, but is not limited to, B, Al, Ga, In, Si, Ge, Sn, or combinations thereof; X may include, but is not limited to, C, N, or combinations thereof; and T x may be a surface functional group that is a hydrogen functional group (-H), an oxygen functional group (=O), a hydroxyl functional group (-OH), a halogen functional group (-F, -Cl, etc.), or a combination thereof, and n may be in the range of 1 to 4.

[0072] In one embodiment, it may be a two-dimensional MXene material with a halogen surface functional group or a two-dimensional MXene material with an oxygen functional group. In one embodiment, the two-dimensional MXene material has a particle size (D 50 It may be a small particle powder with a size of 5μm or less.

[0073] Two-dimensional MXene materials are conductive materials with high conductivity that can enhance electrical conductivity and, for example, accelerate the decomposition of sulfide-based lithium-replenished solid electrolytes under high voltage to release lithium. At the same time, transition metal atoms in the two-dimensional MXene materials (e.g., Ti2CT x Ti and Mo2CT in xMo) can serve as an effective catalyst center or active site, and, for example, can further improve lithium replenishment efficiency by accelerating the catalytic decomposition of sulfide-based lithium-replenished solid electrolytes. For example, MoS2 produced by decomposition can lower the decomposition voltage of the cathode lithium replenishment. That is, the two-dimensional MXene material can release lithium by accelerating the decomposition of lithium-replenished solid electrolytes, such as sulfide-based ones, as a conductive agent and also as a catalyst.

[0074] In one embodiment, the weight ratio of the inorganic lithium-replenishing solid electrolyte material to the two-dimensional MXene material may be 1:0.2 to 1:2, for example, 1:0.5 to 1:1 or 1:1. If the proportion of the two-dimensional MXene material increases, the content of the inorganic lithium-replenishing solid electrolyte material decreases, and thus the lithium replenishment capacity of the anode lithium supplement decreases, which may reduce the lithium replenishment effect. If the proportion of the two-dimensional MXene material is less than 25%, the dispersion of the inorganic lithium-replenishing solid electrolyte material and the two-dimensional MXene material is non-uniform, so the inorganic lithium-replenishing solid electrolyte material cannot completely decompose and release lithium, which may reduce the effective lithium replenishment capacity of the anode lithium supplement, i.e., reduce the lithium replenishment effect.

[0075] The anode lithium supplement according to an embodiment of the present disclosure is applied to a lithium secondary battery system as a lithium supplement on the anode side and does not introduce unnecessary metal ions (impurities). At the same time, since elements such as P, S, and halogens in the inorganic lithium supplement solid electrolyte material are all effective components of the negative electrode SEI film, in addition to replenishing the lithium consumed in the SEI film after the decomposition of the anode lithium supplement, elements such as P, S, and halogens that help in the effective formation of the SEI film can also be introduced into the system.

[0076] When manufacturing a positive lithium supplement according to one embodiment, the positive lithium supplement can be formed by mixing an inorganic lithium supplement solid electrolyte and a two-dimensional MXene material in a weight ratio of 1:0.2 to 1:2 in an inert gas protective atmosphere.

[0077] A positive lithium supplement can be formed by dry mixing or wet mixing an inorganic lithium-supplemented solid electrolyte material and a two-dimensional MXene material. In one embodiment, the inorganic lithium-supplemented solid electrolyte material and the two-dimensional MXene material can be ball-milled with high energy. When the inorganic lithium-supplemented solid electrolyte material and the two-dimensional MXene material are formed through wet mixing, the inorganic lithium-supplemented solid electrolyte material and the two-dimensional MXene material are sufficiently stirred and mixed in a non-polar solvent (e.g., anhydrous acetonitrile, toluene, etc.), and then the non-polar solvent is evaporated to obtain the positive lithium supplement. In addition to magnetic stirring, the material can be prepared using a spray drying method for wet mixing. In wet mixing, impurities may be introduced due to the incomplete evaporation of the non-polar solvent. Furthermore, trace amounts of water contained in the non-polar solvent may cause decomposition of the sulfide-based lithium-supplemented solid electrolyte, which can affect the purity of the material. In addition, simple dry mixing of pistil and mortar can also be used to manufacture anode lithium supplements, but the disadvantage is that the mixing effect and the uniformity of the powder after mixing do not match that of ball milling.

[0078] bookbinder

[0079] The binder can be configured so that the positive active material particles are sufficiently attached to each other and the positive active material is sufficiently attached to the positive current collector. As a non-limiting example, examples of binders include at least one of polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyamideimide, polyimide (PI), polyethylene, polypropylene, styrene butadiene rubber, nitrile rubber (NBR), (meth)acrylated styrene-butadiene rubber, epoxy resin, (meth)acrylic resin, polyester resin, and nylon.

[0080] Challenge materials

[0081] A conductive material can impart electrode conductivity. Any conductive material that conducts electrons without causing unwanted chemical changes in a lithium secondary battery may be used. The conductive material may include a carbon material which is at least one of natural graphite, artificial graphite, carbon black, acetylene black, graphene, Super P, Ketjenblack, carbon fiber, carbon nanofiber, and carbon nanotube; a metal-based material which includes at least one of copper, nickel, aluminum, and silver in the form of metal powder or metal fibers; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.

[0082] positive current collector

[0083] The positive current collector according to the embodiment has no particular limitations and must be conductive without causing chemical changes in the lithium secondary battery. The positive current collector may include aluminum (Al), stainless steel (SUS), indium (In), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), germanium (Ge), lithium (Li), or a combination thereof, and may be in the form of a foil, sheet, or foam.

[0084] The thickness of the positive current collector according to the embodiment may be about 1 μm to about 50 μm, for example, about 2 μm to about 40 μm, about 5 μm to about 30 μm, or about 10 μm to about 20 μm. In addition, the tensile strength of the positive current collector is about 200 N / mm 2 Up to about 1000 N / mm 2 It could be, for example, about 200 N / mm 2 Up to about 800 N / mm 2 , approximately 200 N / mm 2 Up to about 600 N / mm 2 , or about 200 N / mm 2 Up to about 300 N / mm 2 When the thickness and tensile strength of the anode current collector are within the above range, the strength of the anode current collector is improved, and by manufacturing a high-density anode, the capacity of the anode can be increased.

[0085] An anode according to an embodiment of the present disclosure may be manufactured through a wet electrode method: under an inert gas atmosphere, an anode lithium supplement, an anode active material, a conductive material, and a binder are mixed in a solvent (e.g., NMP) according to a weight ratio of x:y:z:w, and stirred and dispersed at a constant temperature (e.g., 60°C) for a certain period of time (e.g., 24 hours) to prepare an anode slurry; the dispersed anode slurry is applied to an anode current collector (e.g., copper foil), and then dried and roll-pressed thereon. However, the method of manufacturing the anode is not limited thereto.

[0086] For example, an anode according to an embodiment of the present disclosure can be manufactured through a dry electrode method: a composite anode powder (anode active material, anode lithium supplement, and conductive material) and a binder (e.g., PTFE) are uniformly mixed in a weight ratio of (90:10) to (99.5:0.5), the mixture is placed on an anode current collector (e.g., aluminum foil) and roll-press molded.

[0087] Here, the thickness of the anode may be 2 μm to 50 μm, but is not limited thereto.

[0088] cathode

[0089] The cathode may further include a cathode current collector and a cathode active material layer on the cathode current collector, and the cathode active material layer may include a cathode active material. Additionally, the cathode active material layer may further include a binder and / or a conductive material.

[0090] In the cathode active material layer, the weight ratio of the cathode active material and the binder may be m:n, and m:n may be (80:20) to (98:2).

[0091] cathode active material

[0092] The negative electrode active material may include a material capable of reversibly inserting / deinserting lithium ions, lithium ions, lithium metal alloys, a material capable of doping / dedoping lithium, or a transition metal oxide.

[0093] A material capable of reversibly inserting / extending lithium ions may include a carbon-based negative electrode active material, for example, crystalline carbon, amorphous carbon, or a combination thereof. Crystalline carbon may be graphite such as natural graphite or artificial graphite in amorphous, plate-like, flake-like, spherical, or fibrous forms. Amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, etc.

[0094] The lithium metal alloy may include an alloy of lithium and at least one of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.

[0095] Materials capable of doping and dedoping lithium may include Si-based negative electrode active materials or Sn-based negative electrode active materials. Si-based negative electrode active materials include silicon, silicon-carbon composites, and SiO₂. x (0 <x≤2), Si-Q 합금(Q는 알칼리 금속, 알칼리 토금속, 13족 원소, 1족 원소(Si를 포함하지 않음), 15족 원소, 16족 원소, 전이금속, 희토류 원소 및 이들의 조합중 적어도 1종의 원소를 포함할 수 있고, 예를 들면 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po 및 이들의 조합) 또는 이들의 조합을 포함할 수 있다. Sn계 음극 활물질은 Sn, SnO2, Sn합금 또는 이들의 조합을 포함할 수 있다.

[0096] The silicon-carbon composite may comprise a silicon and an amorphous carbon composite. According to an embodiment, the silicon-carbon composite may be in the form of silicon particles; and amorphous carbon, which is applied to the surface of the silicon particles. For example, the silicon-carbon composite may comprise secondary particles (nuclei) formed by the aggregation of primary particles and an amorphous carbon coating layer (case) on the surface of the secondary particles. Amorphous carbon may also exist between the silicon primary particles, for example, the silicon primary particles are coated with amorphous carbon. The secondary particles may be dispersed in the amorphous carbon matrix.

[0097] The silicon-carbon composite may further include crystalline carbon. For example, the silicon-carbon composite may include a core comprising crystalline carbon and silicon particles, and an amorphous carbon coating layer on the surface of the core. The crystalline carbon may include artificial graphite, natural graphite, or a combination thereof. The amorphous carbon may include soft carbon or hard carbon, mesophase pitch carbide, and calcined coke.

[0098] When the silicon-carbon composite comprises silicon and amorphous carbon, based on 100 weight% of the silicon-carbon composite, the silicon content may be about 10 weight% to about 50 weight%, and the amorphous carbon content may be about 50 weight% to about 90 weight%. Additionally, when the composite comprises silicon, amorphous carbon, and crystalline carbon, based on 100 weight% of the silicon-carbon composite, the silicon content may be 10 weight% to about 50 weight%, the crystalline carbon content may be about 10 weight% to about 70 weight%, and the amorphous carbon content may be about 20 weight% to about 40 weight%.

[0099] In addition, the thickness of the amorphous carbon coating layer may be about 5 nm to about 100 nm. The average particle size (D) of the silicon particles (silicon primary particles) 50 ) can be about 10 nm to about 1 μm, or about 10 nm to about 200 nm. Silicon particles may exist in the form of silicon alone, a silicon alloy, or an oxidized form. The oxidized form of silicon is SiO x (0 <x≤2)로 표시될 수 있다. 이때, 산화정도를 나타내는 Si:O의 원자 함량비는 약 99:1 내지 33:67일 수 있다. 본문에서 사용되는 경우, 달리 정의가 없는 한, 평균 입경(D 50 ) represents the diameter of the particle at which the cumulative volume in the particle distribution is about 50 volume%.

[0100] Si-based negative electrode active material or Sn-based negative electrode active material can be mixed with carbon-based negative electrode active material. When using a mixture of Si-based negative electrode active material or Sn-based negative electrode active material and carbon-based negative electrode active material, the mixing weight ratio may be about 1:99 to about 90:10.

[0101] bookbinder

[0102] The binder can be configured to sufficiently adhere the negative electrode active material particles to each other and also sufficiently adhere the negative electrode active material to the negative electrode current collector. The binder may include a water-insoluble binder, a water-soluble binder, a dry binder, or a combination thereof.

[0103] The water-insoluble binder may include at least one of polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene propylene copolymer, polystyrene, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide (PI), and combinations thereof.

[0104] The water-soluble binder may be one or more of styrene-butadiene rubber (SBR), (meth)acrylated styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, (meth)acrylic rubber, butyl rubber, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, poly(meth)acrylonitrile, polyacrylic acid (PAA), polymethacrylic acid, ethylene propylene diene copolymer, polyvinyl pyridine, chlorosulfonated polyethylene, latex, polyester resin, (meth)acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

[0105] When a water-soluble binder is used as a cathode binder, it may further include a cellulose-based compound capable of imparting viscosity. The cellulose-based compound may include one or more of carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, or alkali metal salts thereof. The alkali metal may include Na, K, or Li.

[0106] The dry binder may be a fiberizable polymer material. For example, the dry binder may include polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, or a combination thereof.

[0107] Challenge materials

[0108] A conductive material can impart electrode conductivity. Any conductive material that conducts electrons without causing unwanted chemical changes in a lithium secondary battery may be used. The conductive material may include a carbon material which is at least one of natural graphite, artificial graphite, carbon black, acetylene black, graphene, SuperP, Ketjenblack, carbon fiber, carbon nanofiber, and carbon nanotube; a metallic material which includes at least one of copper, nickel, aluminum, and silver in the form of metal powder or metal fibers; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.

[0109] cathode current collector

[0110] The negative electrode current collector according to the embodiment is not subject to any particular limitations, but must not cause chemical changes in the lithium secondary battery. In one embodiment, the negative electrode current collector may include, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof, and may be in the form of a foil, sheet, or foam.

[0111] A cathode according to an embodiment of the present disclosure may be manufactured through a wet electrode method: an active material and a binder are mixed in a solvent (e.g., pure water) in a weight ratio of 80:20 to 98:2, stirred and dispersed at a constant temperature for a certain period of time to prepare a cathode slurry; the dispersed cathode slurry is applied to a cathode current collector (e.g., copper foil), and then dried and roll-pressed. However, the method of manufacturing the cathode is not limited thereto.

[0112] For example, a cathode according to an embodiment of the present disclosure can be manufactured through a dry electrode method: a cathode active material and a binder (e.g., PTFE) are uniformly mixed in a weight ratio of 80:20 to 98:2, the mixture is placed on a cathode current collector (e.g., copper foil) and roll-press molded.

[0113] Here, the thickness of the cathode may be 2 μm to 50 μm, but is not limited thereto.

[0114] separator

[0115] In the case of a liquid lithium secondary battery, a separator may be present between the positive and negative electrodes. The separator may comprise polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof, and may be, for example, a mixed multilayer film of at least one of a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, or a polypropylene / polyethylene / polypropylene three-layer separator.

[0116] The separator may include a porous substrate and a coating layer comprising an organic material, an inorganic material, or a combination thereof on one or two surfaces of the porous substrate.

[0117] The porous substrate may include a polymer film, and the polymer film may include at least one of polyolefin (e.g., polyethylene and polypropylene), polyester (e.g., polyethylene terephthalate and polybutylene terephthalate), polyacetal, polyamide, polyimide, polycarbonate, polyetherketone, polyaryletherketone, polyetherketone, polyetherimide, polyamideimide, polybenzimidazole, polyethersulfone, polyphenylene oxide, cyclic olefin copolymer, polyphenylene sulfide, polyethylene terephthalate, glass fiber, and Teflon (or polytetrafluoroethylene).

[0118] The porous substrate may have a thickness of about 1 μm to about 40 μm (e.g., about 1 μm to about 30 μm, about 1 μm to about 20 μm to about 5 μm to about 15 μm, or about 10 μm to about 15 μm).

[0119] The organic material may include a (meth)acrylic acid copolymer, and the (meth)acrylic acid copolymer includes at least one of a first structural unit derived from (meth)acrylamide; a structural unit derived from (meth)acrylic acid or (meth)acrylate; and a structural unit derived from (meth)acrylamide sulfonic acid or a salt thereof.

[0120] The inorganic material may include inorganic particles, and is, for example, at least one of Al2O3, SiO2, TiO2, SnO2, CeO2, MgO, NiO, CaO, GaO, ZnO, ZrO2, Y2O3, SrTiO3, BaTiO3, Mg(OH)2, serpentinite, and combinations thereof, but is not limited thereto. The average particle size (D) of the inorganic particles 50 ) can be about 1 nm to about 2000 nm, for example, 100 nm to about 1000 nm or about 100 nm to about 700 nm.

[0121] Organic materials and inorganic materials may be mixed in a single coating layer, or a coating layer containing organic materials and a coating layer containing inorganic materials may be laminated.

[0122] The thickness of the coating layer may be about 0.5 μm to about 20 μm, for example, about 1 μm to about 10 μm, or about 1 μm to about 5 μm.

[0123] electrolyte

[0124] For example, the electrolyte used in a liquid lithium secondary battery may include a water-insoluble organic solvent and a lithium salt.

[0125] Aqueous organic solvents serve as a medium capable of transporting ions involved in the electrochemical reaction of a battery. Aqueous organic solvents may include carbonate-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, alcohol-based solvents, aprotic solvents, or combinations thereof.

[0126] The carbonate-based solvent may include at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). The ester-based solvent may include at least one of methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methylpropionate, ethylpropionate, decanolide, mevalnolactone, valerolactone, mevalonolactone, and caprolactone. Ether-based solvents may include at least one of dibutyl ether, tetraglame, diglame, dimethoxyethane, 2-methyltetrahydrofuran, 2,5-methyltetrahydrofuran, and tetrahydrofuran. Ketone-based solvents may include at least cyclohexanone, etc. Alcohol-based solvents may include at least one of ethanol and isopropyl alcohol, and aprotic solvents may include nitriles such as R-CN (which is a C2 to C20 straight-chain, branched, or cyclic hydrocarbon group and may include a double bond, an aromatic ring, or an ether group), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane and 1,4-dioxolane, sulfolane, etc.

[0127] Water-insoluble organic solvents can be used alone or as a mixture of two or more types, and when used as a mixture of two or more types, the mixing ratio can be appropriately adjusted according to the desired battery performance.

[0128] When using a carbonate-based solvent, cyclic carbonates and chain carbonates can be mixed and used, and cyclic carbonates and chain carbonates can be mixed in a volume ratio of about 1:1 to about 1:9.

[0129] The water-insoluble organic solvent may further include an aromatic hydrocarbon-based organic solvent. For example, a carbonate-based solvent and an aromatic hydrocarbon-based organic solvent may be mixed and used in a volume ratio of about 1:1 to about 30:1.

[0130] Lithium salts dissolved in water-insoluble organic solvents supply lithium ions to the battery, enabling the basic operation of the lithium secondary battery and improving the transfer of lithium ions between the anode and cathode. Lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiPO2F2, LiCl, LiI, LiN(SO3C2F5)2, Li(FSO2)2N (lithium bis(fluorosulfonyl)imide; LiFSI), LiC4F9SO3, and LiN(C x F 2x+1 SO2)(C y F 2y+1 It may include at least one of SO2)(where x and y are integers from 1 to 20), lithium trifluoromethanesulfonate, lithium tetrafluoroethanesulfonate, lithium difluorobis(oxalate)phosphate (LiDFBOP), lithium difluorobis(oxalate)borate (LiDFBOB), and lithium bis(oxalate)borate (LiBOB).

[0131] The concentration of the lithium salt may be within the range of about 0.1 M to about 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has suitable ion transportability and viscosity, so desired performance, improved or advantageous performance can be realized, and lithium ions can be effectively transported.

[0132] solid electrolyte layer

[0133] In the case of an all-solid-state lithium secondary battery, a solid electrolyte layer may exist between the positive and negative electrodes. The solid electrolyte layer may include, for example, a solid electrolyte and / or a combination of a solid electrolyte and a gel electrolyte.

[0134] Solid electrolytes may include, for example, sulfide-based solid electrolytes, oxide-based solid electrolytes, halide-based solid electrolytes, polymer-based solid electrolytes, and / or combinations thereof.

[0135] In one embodiment, the solid electrolyte may be, for example, a sulfide-based solid electrolyte. The sulfide-based solid electrolyte is, for example, Li2S-P2S5, Li2S-P2S5-LiX (where X is a halogen element), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m and n are both integers, and Z may be one selected from Ge, Zn, and Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p and q are both integers, and M may be one selected from P, Si, Ge, B, Al, Ga, and In), Li 7-x PS 6-x Cl x (where, 0≤x≤2), Li 7-x PS 6-x Br x (where, 0≤x≤2) and Li 7-x PS 6-x I x It may include one or more selected from (where 0≤x≤2). For example, a sulfide-based solid electrolyte can be manufactured by molten quenching or mechanical polishing of a raw material such as Li2S or P2S5. For example, heat treatment may be performed after such treatment. The solid electrolyte may be amorphous, crystalline, or a mixture.

[0136] Oxide-based solid electrolytes are Li 1+x+y Al x Ti 2-xSi y P 3-y O 12 (here, 0 <x<2,0≤y<3), BaTiO3, Pb(Zr,Ti)O3(PZT), Pb 1-x La x Zr 1-y Ti y O3(PLZT)(where, 0≤x<1, 0≤y<1), Pb(Mg3Nb 2 / 3 )O3-PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, Li3PO4, Li x Ti y (PO4)3(here, 0 <x<2, 0<y<3), Li x Al y Ti z (PO4)3(here, 0 <x<2,0<y<1,0<z<3), Li 1+x+y (Al, Ga) x (Ti, Ge) 2-x Si y P 3-y O 12 (here, 0≤x≤1, 0≤y≤1), Li x La y TiO3(here, 0 <x<2,0<y<3), Li2O, LiOH, Li2CO3, LiAlO2, Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2, Li 3+x La3M2O 12 (Here, M=Te, Nb, or Zr, 0≤x≤10) and / or combinations thereof may be included. Oxide-based solid electrolytes can be manufactured, for example, through sintering.

[0137] The polymer solid electrolyte may comprise a mixture of a lithium salt and a polymer, or may comprise a polymer having ion-conducting functional groups. The polymer solid electrolyte may be, for example, a polymer electrolyte in a solid state at a temperature of about 25°C and a pressure of about 1 atm. The polymer solid electrolyte may not contain, for example, a liquid. In one embodiment, the polymer solid electrolyte may comprise a polymer, said polymer being, for example, polyethylene oxide (PEO), PVDF, vinylidene fluoride-hexafluoropropylene (PVDF-HFP), poly(styrene-b-ethylene oxide) (PS-PEO) block copolymer, poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-b-divinylbenzene) block copolymer, poly(styrene-ethylene oxide-styrene) block copolymer, polystyrene sulfonate (PSS), polyvinyl fluoride (PVF), polymethyl methacrylate (PMMA), polyethylene glycol (PEG), PAN, polytetrafluoroethylene (PTFE), polyethylenedioxythiophene (PEDOT), polypyrrole (PPY), polyaniline, polyacetylene, NAFION™, AQUIVION ® , FLEMION ® , GORE™, ACIPLEX™, MORGANE ® -ADP, Sulfonated Polyetherketone (SPEEK), Sulfonated Polyarylene Etherketone Sulfone (SPAEKKS), Sulfonated Polyarylene Etherketone (SPAEK), Poly[Bis(Benzimidazoleobenzisoquinolinone)](SPBIBI), Lithium 9,10-Diphenylanthracene-2-Sulfonate (DPASLi +) and / or combinations thereof may be included, but the present disclosure is not limited thereto. Any material that can be used as a polymer electrolyte in the art may be used. As a lithium salt, any material that can be used as a lithium salt in the art may be used. Examples of lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(C x F 2x+1 SO2)(C y F 2y+1 It may include SO2)(x and y are natural numbers from 1 to 20, respectively), LiCl, LiI and / or mixtures thereof.

[0138] In one embodiment, the gel electrolyte may be, for example, a polymer gel electrolyte. In one embodiment, the gel electrolyte may have a gel state without, for example, containing a polymer.

[0139] The polymer gel electrolyte may comprise, for example, a liquid electrolyte and a polymer, or an organic solvent and a polymer having ion-conducting functional groups. The polymer solid gel electrolyte may be a polymer electrolyte that is in a gel state, for example, at a temperature of about 25°C and a pressure of about 1 atm. In one embodiment, the polymer gel electrolyte may have a gel state that may not contain, for example, a liquid. The liquid electrolyte used in the polymer gel electrolyte may comprise, for example, a mixture of an ionic liquid, a lithium salt, and an organic solvent, a mixture of a lithium salt and an organic solvent, a mixture of an ionic liquid and an organic solvent, and / or a mixture of a lithium salt and an ionic liquid.

[0140] In one embodiment, the solid electrolyte layer may further include a binder. The binder included in the solid electrolyte layer may include, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), etc., but the embodiments of the present disclosure are not limited thereto. Any material may be used as long as it can serve as a binder in the relevant field. The binder of the solid electrolyte layer may be the same as or different from the binder included in the positive electrode active material layer and the negative electrode active material layer. In one embodiment, no binder may be provided.

[0141] A solid electrolyte layer can be manufactured through the following steps. Solid electrolyte (e.g., sulfide-based solid electrolyte (e.g., Li6PS5Cl), oxide-based solid electrolyte (e.g., Li 6.4 La3Zr 1.4 Ta 0.6 O 12 (LLZTO) or a halogen-based solid electrolyte (e.g., Li3InCl6)) and a binder (e.g., PTFE) are uniformly mixed in a weight ratio of 90:10 to 99.5:0.5, and then the mixture is fed into a screw extruder and subjected to heat extrusion and roll press forming. When the binder is PTFE, the heating temperature is set to 60°C to 80°C (e.g., 80°C) to completely fiberize the PTFE. In this case, the PTFE binder can completely encapsulate the solid electrolyte powder, thereby further improving the mechanical performance of the film. During the roller pressing operation, the pressure can be set to 2 to 10 tons (e.g., 5 tons). Specifically, if the pressure is too high, the solid electrolyte layer may rupture easily, and if the pressure is too low, it may affect the rolling efficiency. Here, the thickness of the solid electrolyte layer is controlled by repetitive rolling. For example, the thickness of the solid electrolyte layer may be 10 μm to 100 μm.

[0142] In one embodiment, an all-solid-state lithium secondary battery can be manufactured using general methods in the art based on a positive electrode, a negative electrode, and a solid electrolyte layer. At the same time, a liquid-state lithium secondary battery can be manufactured using general methods in the art based on a positive electrode, a negative electrode, a separator, and an electrolyte. Likewise, a positive electrode comprising a positive electrode lithium supplement according to an embodiment of the present disclosure can be applied to the manufacture of a semi-solid-state lithium secondary battery.

[0143] Examples and comparative examples of the present disclosure are described below. However, the following examples are merely illustrative of the present disclosure, and the present disclosure is not limited to the following examples.

[0144] Manufacturing of positive lithium supplements

[0145] Preparation Example 1

[0146] Under an argon atmosphere, 1 g of Li6PS5Cl powder, 1 g of Ti2CT x Two-dimensional MXene powder was ball-milled at 600 rpm for 10 hours (ball-to-material weight ratio of 10:1) to obtain approximately 2 g of gray Li6PS5Cl-MXene Ti2CT x I obtained complex lithium supplement powder.

[0147] Here, Li6PS5Cl-MXene Ti2CT obtained by imaging with a scanning electron microscope (SEM) at a magnification of ×9000 as shown in Fig. 6 x An image of the lithium supplement powder is taken. In Fig. 6, the layered solid is MXene Ti2CT x Igo, MXene Ti2CT x The substance attached to the surroundings is Li6PS5Cl powder.

[0148] Preparation Example 2

[0149] Li3PS4-MXene Ti2CT in the same manner as Preparation Example 1, except that Li3PS4 was used instead of Li6PS5Cl x A complex lithium supplement was manufactured.

[0150] Preparation Example 3

[0151] Li6PS5Cl instead of Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 Except for using Li in the same manner as in Preparation Example 1, 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 -MXene Ti2CT x A complex lithium supplement was manufactured.

[0152] Preparation Example 4

[0153] Li7P3S instead of Li6PS5Cl 11 Except for using Li7P3S in the same manner as in Preparation Example 1, 11 -MXene Ti2CT x A complex lithium supplement was manufactured.

[0154] Preparation Example 5

[0155] Li4SnS4-MXene Ti2CT in the same manner as Preparation Example 1, except that Li4SnS4 was used instead of Li6PS5Cl x A complex lithium supplement was manufactured.

[0156] Preparation Example 6

[0157] Li6PS5Cl instead of Li 10 SnP2S 12 Except for using Li in the same manner as in Preparation Example 1, 10 SnP2S 12 -MXene Ti2CT x A complex lithium supplement was manufactured.

[0158] Preparation Example 7

[0159] Li6PS5Cl instead of Li 10 GeP2S 12 Except for using Li in the same manner as in Preparation Example 1, 10 GeP2S 12 -MXene Ti2CT x A complex lithium supplement was manufactured.

[0160] Preparation Example 8

[0161] Li3OCl-MXene Ti2CT in the same manner as Preparation Example 1, except that Li3OCl was used instead of Li6PS5Cl x A complex lithium supplement was manufactured.

[0162] Preparation Example 9

[0163] Ti2CT x Mo2CT instead of 2D MXene powder x Li6PS5Cl-MXeneMo2CT in the same manner as Preparation Example 1, except that a two-dimensional MXene was used x A complex lithium supplement was manufactured.

[0164] Preparation Example 10

[0165] Li3PS4-MXene Mo2CT in the same manner as Preparation Example 9, except that Li3PS4 was used instead of Li6PS5Cl x A complex lithium supplement was manufactured.

[0166] Preparation Example 11

[0167] Li6PS5Cl instead of Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 Except for using Li in the same manner as in Preparation Example 9, 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 -MXene Mo2CT x A complex lithium supplement was manufactured.

[0168] Preparation Example 12

[0169] Li7P3S instead of Li6PS5Cl 11 Except for using Li7P3S in the same manner as in Preparation Example 9, 11 -MXene Mo2CT x A complex lithium supplement was manufactured.

[0170] Preparation Example 13

[0171] Li4SnS4-MXene Mo2CT in the same manner as Preparation Example 9, except that Li4SnS4 was used instead of Li6PS5Cl x A complex lithium supplement was manufactured.

[0172] Preparation Example 14

[0173] Li6PS5Cl instead of Li 10 SnP2S 12 Except for using Li in the same manner as in Preparation Example 9, 10 SnP2S 12 -MXene Mo2CT x A complex lithium supplement was manufactured.

[0174] Preparation Example 15

[0175] Li6PS5Cl instead of Li 10 GeP2S 12 Except for using Li in the same manner as in Preparation Example 9, 10 GeP2S 12 -MXene Mo2CT x A complex lithium supplement was manufactured.

[0176] Preparation Example 16

[0177] Li3OCl-MXene Mo2CT in the same manner as Preparation Example 9, except that Li3OCl was used instead of Li6PS5Cl x A complex lithium supplement was manufactured.

[0178] Evaluation of the decomposition performance of cathode lithium supplements

[0179] 50 mg of Li3InCl6 powder is placed into a hollow cylindrical mold of a ZrO2 ceramic all-solid-state battery with an inner diameter of 10 mm, stainless steel pillars are inserted on both sides, and the mixture is cold-rolled for 3 minutes using an axial press at a pressure of 2 tons. Next, the pressure is released and one stainless steel pillar is removed. 10 mg of the composite lithium supplement powder obtained in Preparation Examples 1 to 16 is placed on one side of the sheet-shaped Li3InCl6 obtained by cold rolling, a stainless steel pillar is inserted, and the mixture is cold-rolled again for 3 minutes using a pressure of 2 tons. After depressurization, the other stainless steel pillar is removed, In foil is filled, and the solid mold pressure-maintaining screw is tightened to complete the assembly of the all-solid-state lithium secondary battery.

[0180] In the manufactured all-solid-state lithium secondary battery, a composite lithium supplement is used as the positive electrode, an In foil is used as the negative electrode, and Li3InCl6 is used as the intermediate solid electrolyte layer; the battery is completed by assembling the all-solid-state battery hollow cylindrical column through a mold.

[0181] At room temperature, using a charge / discharge tester, the manufactured all-solid-state lithium secondary battery is subjected to 0.066C / 0.066C charge / discharge cycles, and the charge / discharge cutoff voltage is 2.5V to 4.2V. Cathode lithium supplement (inorganic lithium supplement solid electrolyte + Ti2CT x / Mo2CT x The lithium replenishment capacity of the anode lithium replenishment and the decomposition voltage of the lithium replenishment solid electrolyte are as shown in Table 1 below.

[0182] Type of Lithium-Replenished Solid Electrolyte Molecular Weight (g / mol) Theoretical Lithium-Replenishing Capacity of Pure Lithium-Replenished Solid Electrolyte (mAh / g) Lithium-Replenished Solid Electrolyte + Ti2CT x Actual Lithium Replenishment Capacity (mAh / g) Lithium Replenishment Solid Electrolyte +Mo2CT xActual Lithium Refill Capacity (mAh / g) Charge / Discharge Cut-off Voltage / Decomposition Voltage Li5FeO4 (Li5FeO4 + Conductive Carbon) 4.3V / 3.9V Li2NiO2 (Li2NiO2 + Conductive Carbon) 4.75V / 4.2V Li6PS5Cl2 6.8V / 6.65V / 4.2V Li3PS4 1.8V / 4.8V / 5.0V Li2NiO2 + Conductive Carbon 4.2V / 3.8V 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 545.2470.3396.64424.2V / 2.1VLi7P3S 11 494380.85342.3345.64.2V / 2.6VLi4SnS4274.7391.37268.3300.24.2V / 3.0VLi 10 SnP2S 12 634.69423.5325.1351.14.2V / 2.4VLi 10 GeP2S 12 588.64456.6410.44164.2V / 2.3VLi3OCl72.51112.1920.0968.54.2V / 3.8V

[0183] Referring to Table 1, it can be seen that the sulfide-based lithium-replenished solid electrolyte (e.g., Li3PS4) and the halide-based lithium-replenished solid electrolyte (e.g., Li3OCl) according to the embodiments of the present disclosure both have a significant lithium replenishment capacity by decomposing and releasing lithium within a voltage range of 1.7 V to 4.2 V.

[0184] The decomposition voltage of the sulfide-based lithium-replenished solid electrolyte according to the embodiment of the present disclosure is very low compared to conventional oxide-based lithium-replenished solid electrolytes (e.g., Li5FeO4, Li2NiO2), so it is easier to replenish lithium in the system by decomposing and releasing lithium, thereby improving the possibility of actual application.

[0185] The decomposition voltage of the halide-based lithium-replenished solid electrolyte according to an embodiment of the present disclosure is 3.8 to 3.9 V, which is relatively high compared to the oxide-based lithium-replenished solid electrolyte. However, compared to the anode lithium supplement containing the oxide-based lithium-replenished solid electrolyte, the lithium replenishment capacity of the anode lithium supplement containing the halide-based lithium-replenished solid electrolyte is much higher.

[0186] In addition, the lithium-replenished solid electrolyte material according to the embodiment of the present disclosure does not contain transition metal elements, so it does not introduce other impurities into the system. At the same time, since elements such as P, S, and halogens in the lithium-replenished solid electrolyte material according to the embodiment of the present disclosure are effective compositional components in the cathode SEI film, after the lithium-replenished solid electrolyte material is decomposed, in addition to replenishing the Li consumed by the formation of the SEI film, elements such as P, S, and halogens beneficial for SEI film formation can be further introduced. For example, decomposition products such as LiCl and Li3P are beneficial components of the cathode SEI layer.

[0187] Also, Ti2CT x and Mo2CT x When comparing cathode lithium supplements manufactured with two types of MXene, MXene Mo2CT x It can be found that the lithium supplementation capacity of cathode lithium supplements containing materials is much higher. This is MXene Mo2CT x Since the Mo element in the material can provide an effective catalytic site and acts as a reliable catalyst for the decomposition of the cathode lithium supplement, MXene Mo2CT x The decomposition of anode lithium supplements containing materials may occur more easily.

[0188] Manufacturing of liquid lithium secondary batteries

[0189] Example 1

[0190] Under an argon atmosphere, 100 mg of Li6PS5Cl-MXene Ti2CT obtained in Preparation Example 1x A composite lithium supplement powder, 800 mg of LiFePO4 cathode active material powder, 50 mg of SuperP conductive carbon, and 50 mg of PVDF were mixed in an NMP solvent and stirred and dispersed at 60°C for 24 hours to prepare a cathode slurry. The dispersed cathode slurry was coated onto aluminum foil, dried, and roll-pressed to obtain a composite lithium supplement cathode electrode plate.

[0191] A liquid lithium secondary battery is manufactured by placing the obtained composite lithium supplemental positive electrode plate, separator, and lithium sheet in a housing, injecting an electrolyte, and sealing it with a clamp sealer. The electrolyte is a solution in which 1.1M LiPF6 is dissolved in a solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a volume ratio of 3:5.

[0192] Example 2

[0193] Li6PS5Cl-MXene Ti2CT obtained in Preparation Example 1 x Li6PS5Cl-MXene Mo2CT obtained in Preparation Example 9 instead of complex lithium supplement powder x A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 1, except that a composite lithium supplement powder was used.

[0194] Example 3

[0195] LiNi instead of LiFePO4 0.6 Co 0.2 Mn 0.2 A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 1, except that O2 was used.

[0196] Example 4

[0197] LiNi instead of LiFePO4 0.8 Co 0.1 Mn 0.1 A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 1, except that O2 was used.

[0198] Example 5

[0199] A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 1, except that LiCoO2 was used instead of LiFePO4.

[0200] Example 6

[0201] Li6PS5Cl-MXene Ti2CT obtained in Preparation Example 1 x Li obtained in Preparation Example 7 instead of the complex lithium supplement powder 10 GeP2S 12 -MXene Ti2CT x A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 1, except that a composite lithium supplement powder was used.

[0202] Example 7

[0203] LiNi instead of LiFePO4 0.6 Co 0.2 Mn 0.2 A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 6, except that O2 was used.

[0204] Example 8

[0205] LiNi instead of LiFePO4 0.8 Co 0.1 Mn 0.1 A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 6, except that O2 was used.

[0206] Example 9

[0207] A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as in Example 6, except that LiCoO2 was used instead of LiFePO4.

[0208]

[0209] Comparative Example 1

[0210] Under the conditions of a drying chamber (dew point -35℃), 20 mg of Li5FeO4 lithium supplement, 10 g of LiFePO4 cathode active material powder, 200 mg of SuperP conductive carbon, and 200 mg of PVDF were mixed in an NMP solvent and dispersed by high-speed ball milling at 2000 rpm for 3 minutes to prepare a cathode slurry. After coating the dispersed cathode slurry onto aluminum foil, drying and roll pressing were performed to obtain a composite lithium cathode electrode plate.

[0211] A liquid lithium secondary battery was manufactured in the same manner as in Example 1, except that the composite lithium supplementary positive electrode plate obtained above was used.

[0212] Comparative Example 2

[0213] A composite lithium positive electrode plate and a liquid lithium secondary battery were manufactured in the same manner as Comparative Example 1, except that Li2NiO2 was used instead of Li5FeO4.

[0214] Comparative Example 3

[0215] Ti2CT x 2D Maxine Instead, Li6PS5Cl-SuperP composite lithium supplement powder was prepared in the same manner as in Preparation Example 1, except that SuperP conductive carbon was used.

[0216] Li6PS5Cl-MXene Ti2CT x A composite lithium positive electrode plate and a liquid lithium secondary battery were prepared in the same manner as in Example 1, except that Li6PS5Cl-SuperP composite lithium supplement powder was used instead of the composite lithium supplement powder.

[0217] Evaluation of charge / discharge performance of liquid lithium secondary batteries

[0218] After allowing the assembled liquid-type lithium secondary batteries of Examples 1 to 9 and Comparative Examples 1 to 3 to stand for 12 hours, a charge / discharge test was performed on a LAND charge / discharge tester. At room temperature (25°C), the liquid-type lithium secondary batteries were charged and discharged in a voltage range of 2.5V to 4.2V with a charge / discharge ratio of 0.066C / 0.066C. After the first charge / discharge, a battery charge / discharge cycle test was performed in a voltage range of 2.5V to 3.8V with a charge / discharge ratio of 1.0C / 1.0C until the battery capacity became less than 80%. During the charge / discharge cycle test, the number of charge / discharge cycles was greater than 100. To better characterize the charge / discharge performance of the manufactured liquid-type lithium secondary battery, the specific capacity of the battery after the first charge / discharge cycle and the specific capacity of the battery after the 50th charge / discharge cycle are measured.

[0219] Here, for the liquid lithium secondary batteries of Examples 3 and 7, the voltage range of the first charge / discharge cycle test is 3.0V to 4.3V. For the liquid lithium secondary batteries of Examples 4 and 8, the voltage range of the first charge / discharge cycle test is 3.0V to 4.2V. For the liquid lithium secondary batteries of Examples 5 and 9, the voltage range of the first charge / discharge cycle test is 3.0V to 4.45V. For the liquid lithium secondary battery of Comparative Example 1, in the first charge / discharge cycle test, during the charging process, it is first charged to 4.2V at a constant rate with a 0.066C multiplier, and then charged again at 4.2V at a constant voltage for 5 minutes so that the Li5FeO4 lithium supplement is completely decomposed to release lithium.

[0220] The results of the charge / discharge performance test of the liquid lithium secondary battery are shown in Table 2 below.

[0221] Lithium Supplement MXene Material Cathode Active Material Specific Capacity after 1st Charge (mAh / g) Specific Capacity after 1st Discharge (mAh / g) Specific Capacity after 50th Discharge (mAh / g) Example 1 Li6PS5ClTi2CT x LiFePO4186.9163.9160.62 Example 2 Li6PS5ClMo2CT x LiFePO4188.75165.1161.8 Example 3Li6PS5ClTi2CT x LiNi 0.6 Co 0.2 Mn 0.2 O2209.76180.5172.91 Example 4Li6PS5ClTi2CT x LiNi 0.8 Co 0.1 Mn 0.1 O2208.83179.98169.36 Example 5Li6PS5ClTi2CT x LiCoO2 190.3168.8154.49 Example 6 Li 10 GeP2S 12 Ti2CT x LiFePO4184.55161.3156.46 Example 7 Li 10 GeP2S 12 Ti2CT x LiNi 0.6 Co 0.2 Mn 0.2 O2206.5176.83169.75 Example 8Li 10 GeP2S 12 Ti2CT x LiNi 0.8 Co 0.1 Mn 0.1 O2207.65180.13169.65 Example 9Li 10 GeP2S 12 Ti2CT x LiCoO2 191.12 170.9 157.1 Comparative Example 1 Li5FeO4 SuperPLiFePO4 167.92 148.94 145.96 Comparative Example 2 Li2NiO2 SuperPLiFePO4 164.63 149.32 146.13 Comparative Example 3 Li6PS5Cl SuperPLiFePO4 173.5 155.31 49.8

[0222] Referring to Table 2, it can be seen that in the case of a liquid lithium secondary battery, the anode lithium supplement comprising a sulfide-based lithium supplemented solid electrolyte and a two-dimensional MXene material according to an embodiment of the present disclosure can effectively improve battery capacity and long cycle performance compared to conventional oxide-based lithium supplemented solid electrolytes (e.g., Li5FeO4, Li2NiO2) and anode supplement comprising conductive carbon black.

[0223] In Examples 1 to 9 and Comparative Examples 1 to 3, the amount of cathode lithium supplement added differs relative to the total mass of the cathode active material layer (specifically, the amount of inorganic lithium supplement material of the sulfide-based lithium supplement solid electrolyte is 5 wt%, while the amount of cathode lithium supplement including oxide-based lithium supplement solid electrolyte Li5FeO4 and Li2NiO2 is 2 wt%). However, if the amount of cathode lithium supplement added exceeds 2 wt% due to the problem of gas generation in Li5FeO4 and Li2NiO2, there is a risk of expansion of the electrode plate. Compared to Comparative Example 3, which contains a cathode lithium supplement including a sulfide-based lithium supplement solid electrolyte and a general conductive carbon black material, Example 1, which contains a cathode lithium supplement including a sulfide-based lithium supplement solid electrolyte and a two-dimensional MXene material, has better catalytic decomposition performance, so the capacity of the cathode lithium supplement can be fully utilized, thereby further improving battery performance.

[0224] The anode lithium supplement presented in the present disclosure may comprise a mixture of an inorganic solid electrolyte and an MXene material as a lithium supplement material, wherein the intrinsic decomposition voltage of the inorganic solid electrolyte is low (decomposition voltage ≤ 4V) and the electrochemical stability window is narrow. In the first charge / discharge cycle of a lithium secondary battery containing the anode lithium supplement, the anode lithium supplement decomposes to produce lithium and replenishes the active lithium consumed by the formation of an SEI film in the first charge / discharge cycle of the lithium secondary battery. Accordingly, a lithium secondary battery containing the anode lithium supplement can have improved battery capacity and long cycle performance.

[0225] Furthermore, compared to conventional lithium supplements such as Li5FeO4 or Li2NiO2, the cathode lithium supplement of the present disclosure does not introduce any separate components, does not generate gas (e.g., oxygen) during the lithium supplementation process, and has a simple, safe, and non-contaminating manufacturing method. Accordingly, the cathode lithium supplement of the present disclosure can be applied to various lithium secondary batteries (e.g., liquid-type lithium secondary batteries, semi-solid-type lithium secondary batteries, all-solid-type lithium secondary batteries, liquid-type lithium-sulfur secondary batteries, or all-solid-type lithium-sulfur secondary batteries).

[0226] Although exemplary embodiments of the present disclosure have been described above, the scope of the present disclosure is not limited to exemplary embodiments. Various modifications may be made to the exemplary embodiments without departing from the spirit and scope of the disclosure as defined by the appended claims, and such modifications are included within the scope of the present disclosure.

Claims

1. Regarding positive lithium supplements, Inorganic lithium supplement solid electrolyte material; and Includes a two-dimensional MXene material; and A positive lithium supplement having an intrinsic decomposition voltage of 4V or less of an inorganic lithium supplement solid electrolyte material.

2. In Paragraph 1, An inorganic lithium-replenishing solid electrolyte material is a positive lithium supplement comprising a sulfide-based lithium-replenishing solid electrolyte, a halide-based lithium-replenishing solid electrolyte, or a combination thereof.

3. In Paragraph 2, A sulfide-based lithium supplemented solid electrolyte comprises a lithium sulfide-based lithium supplemented solid electrolyte, a lithium azirodite-type solid electrolyte, a lithium-germanium-phosphorus-sulfur-type solid electrolyte, other sulfide-based lithium supplemented solid electrolytes, or a combination thereof, an anode lithium supplement.

4. In Paragraph 3, Lithium sulfide-based lithium supplemental solid electrolytes are Li3PS4 and Li7P3S 11 or including a combination thereof, Lithium azyrodite-type solid electrolytes include Li7PS6, Li 7-x PS 6-x A x or a combination thereof, wherein A comprises Cl, Br, I, or a combination thereof, and x is 0 to 2, and Lithium germanium-phosphorus-sulfur type solid electrolyte is Li 10 Ge(Sn)P2S 12 Includes, Other sulfide-based lithium supplemental solid electrolytes include Li4SnS4, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 A positive lithium supplement comprising or a combination thereof.

5. In Paragraph 2, Halogen-based lithium supplemented solid electrolyte is an anode lithium supplement comprising an antiperovskite-type solid electrolyte.

6. In Paragraph 5, The antiperovskite type solid electrolyte is a positive lithium supplement comprising Li3OCl, Li3YBr6, or a combination thereof.

7. In Paragraph 1, Two-dimensional MXene materials have the chemical formula M n+1 X n T x It is displayed as, M is a transition element; A is an element of Group 13, an element of Group 14 of the periodic table, or a combination thereof, and X is C, N, or a combination thereof; T x is a surface functional group; n is a positive lithium supplement, ranging from 1 to 4.

8. In Paragraph 7, M includes Ti, V, Mo, W, Nb, Zr, Hf, Ta, or a combination thereof, and A includes B, Al, Ga, In, Si, Ge, Sn, or a combination thereof, and T x A positive lithium supplement comprising a hydrogen functional group, an oxygen functional group, a hydroxy functional group, a halogen functional group, or a combination thereof.

9. In Paragraph 8, The two-dimensional MXene material is Ti2CT x , Mo2CT x A positive lithium supplement comprising or a combination thereof.

10. In Paragraph 1, A positive lithium supplement, wherein the weight ratio of the inorganic lithium supplement solid electrolyte material to the two-dimensional MXene material is 1:0.2 to 1:

2.

11. In Paragraph 1, The above-mentioned anode lithium supplement is a composite anode lithium supplement formed by mixing an inorganic lithium supplement solid electrolyte material and a two-dimensional MXene material through ball milling.

12. Regarding the anode, A positive electrode comprising a positive electrode lithium supplement according to any one of paragraphs 1 to 11.

13. A lithium secondary battery comprising a positive electrode according to paragraph 12.

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