All-solid-state battery with anode layer comprising metal-organic framework

Abstract

The present invention relates to an all-solid-state battery having an anode layer comprising a solid electrolyte and a metal organic framework; a solid electrolyte layer disposed on the anode layer; and a cathode layer disposed on the solid electrolyte layer. The all-solid-state battery may also include a lithium layer interposed between the anode layer and the solid electrolyte layer.

Description

Technical Field

[0001] The present invention relates to an all-solid-state battery having an anode layer comprising a metal organic framework. Background Art

[0002] Nowadays, secondary batteries are widely used in large devices such as automobiles and power storage systems, as well as small devices such as mobile phones, cameras, and notebook computers.

[0003] As the application areas of secondary batteries continue to expand, the demand for improved battery safety and higher performance continues to increase.

[0004] Lithium secondary batteries are a type of secondary batteries and have the advantages of high energy density and large capacity per unit area compared to nickel-manganese batteries or nickel-cadmium batteries.

[0005] However, most electrolytes used in conventional lithium secondary batteries are liquid electrolytes, such as organic solvents, etc. Therefore, safety issues such as electrolyte leakage and the risk of fire caused thereby are constantly raised.

[0006] Therefore, there has been recent interest in using solid electrolytes as electrolytes rather than liquid electrolytes in all-solid-state batteries to improve the safety of lithium secondary batteries. Summary of the invention

[0007] The present invention provides an all-solid-state battery comprising an electrode layer, wherein the electrode layer comprises a metal-organic framework (MOF).

[0008] In a particular embodiment, an all-solid-state battery comprising an anode layer is provided, wherein the anode layer comprises a metal organic framework (MOF). Suitably, the anode layer comprises a solid electrolyte and a metal organic framework (MOF).

[0009] On the one hand, an all-solid-state battery may include: 1) an anode current collector; 2) an anode layer disposed on the anode current collector; 3) a solid electrolyte layer disposed on the anode layer; 4) optionally, a cathode layer disposed on the solid electrolyte layer; 5) optionally, a cathode current collector disposed on the cathode layer, wherein the anode layer may include a solid electrolyte and a metal organic framework (MOF).

[0010] The solid electrolyte layer may include a sulfide-based solid electrolyte.

[0011] In certain embodiments, the solid electrolyte of the battery may include a sulfide-based solid electrolyte. The solid electrolyte layer may include a sulfide-based solid electrolyte. The solid electrolyte may be the same as the solid electrolyte of the solid electrolyte layer.

[0012] The terms "metal organic framework" and "MOF" are used herein according to their ordinary meaning and refer to a composition comprising metal atoms coordinated with organic ligands (e.g., metal organic framework linkers). In one aspect, a metal organic framework can be referred to as a periodic coordination network of metal nodes connected by ligands. The organic ligands (e.g., metal organic framework linkers), metal ion nodes, and optional additional ions (e.g., O 2- ) may be collectively referred to as a secondary building unit (SBU). In an embodiment, the SBU comprises a metal and a metal organic framework linker. In an embodiment, the SBU comprises a metal ion node. In an embodiment, the metal organic framework comprises one or more metal organic framework linkers, which may be the same or different.

[0013] The term "metal organic framework linker" or "ligand" is used according to its usual meaning in chemistry and MOF chemistry, and refers to an organic ligand capable of connecting a metal (e.g., a metal atom, a metal ion node within an SBU, a metal ion node) in a MOF by means of a metal binding ligand portion or a metal binding atom. In an embodiment, the metal organic framework linker is covalently linked (e.g., directly or indirectly) to a different metal organic framework linker. In an embodiment, a first metal organic framework linker is covalently linked to a second metal organic framework linker via a covalent linker portion (e.g., a polymer). In an embodiment, a first metal organic framework linker is covalently linked to an identical second metal organic framework linker. In an embodiment, the metal organic framework linker is divalent. In an embodiment, the metal organic framework linker is a substituted terephthalic acid. In an embodiment, the metal organic framework linker includes a di- or poly-metal binding ligand portion. Metal organic framework linkers have been reported in U.S. Patent No. 7,196,210.

[0014] In an embodiment, the metal organic framework may include: a metal ion; and an organic ligand bonded to the metal ion.

[0015] In an embodiment, the metal ions may include ions of at least one metal selected from lithium (Li), manganese (Mn), nickel (Ni), cobalt (Co), and combinations thereof.

[0016] In an embodiment, the organic ligand may include at least one selected from 1,4-benzenedicarboxylic acid (1,4-BDCA), 2,6-naphthalenedicarboxylic acid (2,6-NDCA), ellagic acid (EA), 1,4,5,8-naphthalenetetracarboxylic acid (1,4,5,8-naphthalenetetracarboxylic acid, 1,4,5,8-NTCA), 3,4,9,10-pyrenetetracarboxylic acid (3,4,9,10-perylenetetracarboxylic acid, 3,4,9,10-PTCA), biphenyltetracarboxylic acid (BPTC), 2,5-thiophenedicarboxylic acid (2,5-TPDC), and combinations thereof.

[0017] In certain aspects, the organic ligand may comprise 2,5-thiophenedicarboxylic acid (2,5-TPDC), which has been shown to provide significant results. See Examples below.

[0018] In certain embodiments, the anode layer may comprise about 30 wt % to about 55 wt % of a solid electrolyte and about 45 wt % to about 70 wt % of a metal organic framework. The anode layer may comprise greater than about 55 wt % of a solid electrolyte and less than about 45 wt % of a MOF.

[0019] In some systems, all-solid-state batteries may also contain a lithium layer inserted between the anode layer and the solid electrolyte layer.

[0020] In some systems, the lithium layer may comprise lithium powder.

[0021] According to the present invention, an all-solid-state battery having an anode layer comprising a metal organic framework can be obtained.

[0022] According to the present invention, an all-solid-state battery with improved initial coulombic efficiency can be obtained.

[0023] According to the present invention, an all-solid-state battery with improved capacity retention can be obtained.

[0024] In some embodiments, the all-solid-state battery comprises an anode layer comprising a solid electrolyte and a metal organic framework (MOF); a lithium layer disposed on the anode layer; a solid electrolyte layer disposed on the lithium layer; and a cathode layer disposed on the solid electrolyte layer.

[0025] In some embodiments, the all-solid-state battery comprises an anode layer, the anode layer comprising a solid electrolyte and a metal organic framework MOF, the metal organic framework MOF comprising cobalt as a metal ion and 2,5-thiophenedicarboxylic acid (2,5-TPDC) as an organic ligand bonded to the metal ion; a lithium layer disposed on the anode layer; a solid electrolyte layer disposed on the lithium layer; and a cathode layer disposed on the solid electrolyte layer.

[0026] The present invention also provides a vehicle comprising the all-solid-state battery described herein.

[0027] As used herein, the term "all-solid-state battery" includes or refers to a rechargeable battery (including a secondary battery) that includes a solid state, such as a gel or polymer (cured) electrolyte, which may include ionomers and other electrolytic components that enable ion migration between the electrodes of the battery.

[0028] Other embodiments of the present invention are disclosed below.

[0029] The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 A first embodiment of the all-solid-state battery according to the present invention is shown.

[0031] Figure 2 A second embodiment of the all-solid-state battery according to the present invention is shown.

[0032] Figure 3 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 1 are shown.

[0033] Figure 4 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 2 are shown.

[0034] Figure 5 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 3 are shown.

[0035] Figure 6 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 4 are shown.

[0036] Figure 7 The specific capacity according to charge and discharge of the all-solid-state battery according to Example 1 is shown.

[0037] Figure 8 The specific capacity according to charge and discharge of the all-solid-state battery according to Example 2 is shown.

[0038] Fig. 9The specific capacity according to charge and discharge of the all-solid-state battery according to Example 3 is shown.

[0039] Fig.10 The specific capacity according to charge and discharge of the all-solid-state battery according to Example 4 is shown.

[0040] Fig.11 The capacity retention rate of the all-solid-state battery according to Example 1 is shown.

[0041] Fig.12 The capacity retention rate of the all-solid-state battery according to Example 2 is shown.

[0042] Fig.13 The capacity retention rate of the all-solid-state battery according to Example 3 is shown.

[0043] Fig.14 The capacity retention rate of the all-solid-state battery according to Example 4 is shown. DETAILED DESCRIPTION

[0044] Through the following preferred embodiments and in conjunction with the accompanying drawings, the above-mentioned purpose, other purposes, features and advantages of the present invention will be more easily understood. However, the present invention is not limited to the embodiments described herein and can be implemented in other forms. On the contrary, the embodiments introduced herein are provided so that the disclosed content can be thorough and complete, and the spirit of the present invention can be fully conveyed to those skilled in the art.

[0045] When explaining each figure, the same reference numerals refer to the same elements. In the accompanying drawings, for the sake of clarity of the present invention, the size of the structure is exaggerated than the actual size. Although terms such as "first", "second", etc. can be used to describe various elements, these elements should not be limited by these terms. The above terms are only used to distinguish one component from another component. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component. Singular expressions also include plural expressions unless the context clearly indicates otherwise.

[0046] In this specification, terms such as "comprising", "having", etc. should be understood as the presence of the features, numbers, steps, operations, components, parts, or combinations thereof in the specification, but these terms do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof. In addition, when a part of a layer, film, region, plate, etc. is referred to as being "on" another part, this includes not only the case where it is directly "on" another part, but also the case where another part is interposed. Conversely, when a part of a layer, film, region, plate, etc. is referred to as being "under" another part, this includes not only the case where it is directly "under" another part, but also the case where another part is interposed.

[0047] Unless otherwise stated, since all the numbers, values ​​and / or expressions used in this specification that represent the amount of components, reaction conditions, polymer compositions and formulations are approximate values ​​reflecting the various uncertainties in the measurements generated when these values ​​are obtained from these substantially different numbers, they should be understood to be modified by the term "about" in all cases. In addition, when the present invention discloses a numerical range, unless otherwise stated, the range is continuous and includes all numerical values ​​from the minimum to the maximum, and the maximum is included in the range. In addition, when the range refers to an integer, unless otherwise stated, it includes all integers from the minimum to the maximum, and the maximum is included in the range. Unless specifically stated or clearly visible from the context, the term "about" used herein should be understood to be within the normal tolerance range of this field, such as within 2 standard deviations of the mean value. "About" can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05% or 0.01% of the value. Unless otherwise stated in the context, all numerical values ​​provided herein are modified by the term "about".

[0048] In addition, unless otherwise stated, when the specification discloses a numerical range, the range is continuous and includes all values ​​from the minimum value of the range to its maximum value. Moreover, unless otherwise stated, when such a range involves an integer value, all integers from the minimum value to the maximum value are included. For example, a range of "5 to 10" will be understood to include any subranges, such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., as well as individual values ​​5, 6, 7, 8, 9 and 10, and should also be understood to include any value between the valid integers within the range, such as 5.5, 6.5, 7.5, 5.5 to 8.5, 6.5 to 9, etc. In addition, for example, a range of "10% to 30%" will be understood to include sub-ranges such as 10% to 15%, 12% to 18%, 20% to 30%, etc., and all integers including values ​​of 10%, 11%, 12%, 13%, etc. up to 30%, and should also be understood to include any values ​​between the valid integers in the stated range, such as 10.5%, 15.5%, 25.5%, etc.

[0049] It should be understood that the term "vehicle" or "transportation means" or other similar terms used herein include general motor vehicles, such as passenger cars, including sports utility vehicles (SUVs), buses, trucks, various commercial vehicles, ships including various boats, large ships, aircraft, etc., and include hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (such as fuels derived from resources other than petroleum). As mentioned herein, a hybrid vehicle is a vehicle with two or more power sources, such as gasoline-powered and electric-powered vehicles. In certain preferred embodiments, the vehicle can be electric, including a hybrid vehicle, a plug-in hybrid vehicle, or a vehicle with electricity as the main or sole power source.

[0050] Figure 1 The first embodiment of the all-solid-state battery according to the present invention is shown. The all-solid-state battery may include an anode current collector 10, an anode layer 20 disposed on the anode current collector 10, a solid electrolyte layer 30 disposed on the anode layer 20, a cathode layer 40 disposed on the solid electrolyte layer 30, and a cathode current collector 50 disposed on the cathode layer 40.

[0051] The anode current collector 10 may be a plate-shaped substrate having conductivity. Specifically, the anode current collector 10 may have the form of a sheet, a film, or a foil.

[0052] The anode current collector 10 may include a material that does not react with lithium. Specifically, in certain embodiments, the anode current collector 10 may include at least one selected from nickel (Ni), copper (Cu), stainless steel, and a combination thereof.

[0053] The anode layer 20 may suitably include a solid electrolyte and a metal organic framework (MOF).

[0054] The solid electrolyte may suitably conduct lithium ions in the anode layer 20 or other materials.

[0055] In certain preferred embodiments, the solid electrolyte may include at least one selected from oxide-based solid electrolytes, sulfide-based solid electrolytes, polymer electrolytes, and combinations thereof. Preferably, the solid electrolyte may include a sulfide-based solid electrolyte.

[0056] In certain preferred embodiments, the sulfide-based solid electrolyte may include Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiI, Li 2 SP 2 S5 -LiCl, Li 2 SP 2 S 5 -LiBr, Li 2 SP 2 S 5 -Li 2 O. Li 2 SP 2 S 5 -Li 2 O-LiI、Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 SB 2 S 3 , Li 2 SP 2 S 5 -Z m S n (where m and n are positive numbers, and Z is one of Ge, Zn and Ga), Li 2 S-GeS 2 , Li 2 S-SiS 2 -Li 3 PO 4 , Li 2 S-SiS 2 -Li x MO y (where x and y are positive numbers, and M is one of P, Si, Ge, B, Al, Ga and In), Li 10 G 2 S 12 wait.

[0057] In certain preferred embodiments, the oxide-based solid electrolyte may include a perovskite-type Li 3x La 2 / 3-x TiO 3 (LLTO), phosphate-based NASICON-type Li1+x Al x Ti 2-x (PO 4 ) 3 (LATP) etc.

[0058] In certain preferred embodiments, the polymer electrolyte may include a gel polymer electrolyte, a solid polymer electrolyte, and the like.

[0059] As described above, a metal organic framework (MOF) may include a metal ion and an organic ligand bonded to the metal ion. The metal ion and the organic ligand may be coordinately bonded or covalently bonded.

[0060] In a preferred embodiment, the metal organic framework (MOF) may have micropores and mesopores, which can effectively suppress the volume expansion of the anode layer 20 due to the charging product. In addition, since the combination of metal ions and organic ligands in the metal organic framework (MOF) is various, the use of organic ligands containing functional groups having lithium ion conductivity may help to improve the conductivity of lithium ions in the anode layer 20.

[0061] In certain preferred embodiments, the metal ions of the metal organic framework may include ions of at least one metal selected from lithium (Li), manganese (Mn), nickel (Ni), cobalt (Co), and combinations thereof.

[0062] In certain preferred embodiments, the organic ligand of the metal organic framework may include at least one selected from 1,4-benzenedicarboxylic acid (1,4-BDCA), 2,6-naphthalene dicarboxylic acid (2,6-NDCA), ellagic acid (EA), 1,4,5,8-naphthalenetetracarboxylic acid (1,4,5,8-NTCA), 3,4,9,10-pyrenetetracarboxylic acid (3,4,9,10-PTCA), biphenyltetracarboxylic acid (BPTC), 2,5-thiophene dicarboxylic acid (2,5-TPDC), and combinations thereof.

[0063] In certain preferred embodiments, the metal organic framework (MOF) may have an average particle size (D50) of nanometer scale. For example, the metal organic framework (MOF) may have an average particle size (D50) of about 1 nm to 500 nm. Since the size of a general metal organic framework (MOF) is micrometer scale, the conductivity of its electrons is reduced to such an extent that it is difficult to use it for electrochemical purposes. However, the present invention prevents the reduction of the electronic conductivity in the anode layer 20 by using a nanometer-sized metal organic framework (MOF).

[0064] The method for preparing the metal organic framework (MOF) is not particularly limited. For example, the metal organic framework (MOF) can be prepared by hydrothermal synthesis, ultrasonic synthesis, etc., and ultrasonic synthesis is preferred.

[0065] A non-limiting method of preparing a metal organic framework (MOF) may include the steps of preparing a starting material including a solvent, a metal ion precursor, and an organic ligand, and irradiating the starting material with ultrasonic waves of a preset intensity for a preset time.

[0066] The solvent is not particularly limited, and may include at least one selected from N,N-dimethylformamide, distilled water, methanol, ethanol, propanol, dimethylacetamide, acetone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and combinations thereof.

[0067] The metal ion precursor may include a hydrate of a metal ion, a nitrate of a metal ion, an acetate of a metal ion, and the like.

[0068] The starting material may further include a catalyst that promotes the reaction between the metal ion precursor and the organic ligand. The catalyst is not particularly limited and may include, for example, triethylamine.

[0069] The ultrasonic intensity and irradiation time are not particularly limited and can be appropriately adjusted to provide energy to a degree that allows the metal ion precursor and the organic ligand to react sufficiently.

[0070] The preparation method may further include the steps of washing and drying the metal organic framework (MOF) synthesized by ultrasonic irradiation.

[0071] In some systems, the anode layer 20 may include about 30 wt % to about 50 wt % of a solid electrolyte and about 50 wt % to about 70 wt % of a metal organic framework (MOF). If the content of the solid electrolyte is less than 30 wt %, the initial coulombic efficiency and capacity of the all-solid-state battery may be reduced. When the content of the solid electrolyte exceeds 50 wt %, the content of the metal organic framework (MOF) is relatively low, so the all-solid-state battery may not be driven normally.

[0072] The solid electrolyte layer 30 may be appropriately interposed between the cathode layer 40 and the anode layer 20 , and may appropriately contain a solid electrolyte having lithium ion conductivity.

[0073] The solid electrolyte may appropriately include at least one selected from an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a polymer electrolyte, and a combination thereof. The solid electrolyte of the solid electrolyte layer 30 may be the same as or different from the solid electrolyte of the anode layer 20 .

[0074] The solid electrolyte layer 30 may further appropriately contain a binder. The binder may include butadiene rubber, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), etc.

[0075] The cathode layer 40 may appropriately contain a cathode active material, a solid electrolyte, a conductive material, a binder, etc.

[0076] In some systems, the cathode active material may appropriately reversibly intercalate and deintercalate lithium ions (Li + ). The cathode active material may include an oxide active material. In some systems, the oxide active material may include a rock salt layer type active material such as LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , Li 1+x Ni 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 , etc., a spinel type active material such as LiMn 2 O 4 , Li(Ni 0.5 Mn 1.5 )O 4 , etc., an inverse spinel type active material such as LiNiVO 4 , LiCoVO 4 , etc., an olivine type active material such as LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 , etc., a silicon-containing active material such as Li 2 FeSiO 4 , Li 2 MnSiO 4 , etc., a rock salt layer type active material in which some transition metals are substituted by hetero-metals such as LiNi 0.8 Co (0.2-x) Al x O 2 (0 < x < 0.2), a spinel type active material in which some transition metals are substituted by hetero-metals such as Li1+x Mn 2-x-y M y O 4 (M is at least one of Al, Mg, Co, Fe, Ni and Zn, and 0<x+y<2), or lithium titanate such as Li 4 Ti 5 O 12 wait.

[0077] The solid electrolyte may suitably include at least one selected from oxide-based solid electrolytes, sulfide-based solid electrolytes, polymer electrolytes, and combinations thereof. The solid electrolyte of cathode layer 40 may be the same as or different from the solid electrolyte of anode layer 20 and / or solid electrolyte layer 30 .

[0078] The conductive material may appropriately include carbon black, conductive graphite, vinyl black, carbon fiber, graphene, and the like.

[0079] The binder may appropriately include butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), etc. The binder of cathode layer 40 may be the same as or different from the binder of solid electrolyte layer 30 .

[0080] The cathode current collector 50 may be a conductive plate-shaped substrate or other structures. Specifically, the cathode current collector 50 may be in the form of a sheet or a film.

[0081] The cathode current collector 50 may suitably include, for example, at least one selected from the group consisting of indium, copper, magnesium, aluminum, stainless steel, iron, and combinations thereof.

[0082] Figure 2 A second exemplary embodiment of an all-solid-state battery according to the present invention is shown. The all-solid-state battery may be a battery in which a lithium layer 60 is inserted between an anode layer 20 and a solid electrolyte layer 30 .

[0083] The lithium layer 60 can appropriately increase the reversibility of the redox reaction occurring in the all-solid-state battery, thereby improving the initial coulombic efficiency, capacity retention rate, etc. of the all-solid-state battery.

[0084] The lithium layer 60 may suitably contain lithium powder. A method of manufacturing the lithium layer 60 is described below.

[0085] According to this embodiment and other embodiments, the manufacturing method of the all-solid-state battery is not particularly limited. For example, the all-solid-state battery manufacturing method may include the following steps: preparing a slurry containing a solid electrolyte and a metal organic framework (MOF); applying the slurry on a substrate and drying to form an anode layer; and stacking the anode current collector, the anode layer, the solid electrolyte layer, the cathode layer, and the cathode current collector in sequence.

[0086] Furthermore, the production method may suitably further include a step of forming a lithium layer by applying a dispersion containing lithium powder onto the anode layer and drying it.

[0087] In one embodiment, the dispersion can be prepared by injecting lithium powder into a dispersion medium that does not react with the lithium powder. For example, the lithium powder can be injected into the dispersion medium so that the concentration of the lithium powder is about 2 wt % to about 5 wt %.

[0088] The dispersion medium is not particularly limited and may include, for example, toluene, dimethylformamide, hexane, heptane, N-methyl-2-pyrrolidone, dimethylacetamide, and the like.

[0089] In one embodiment, the lithium layer may be prepared by depositing lithium powder without injecting the lithium powder into the dispersion medium.

[0090] Below, other forms of the present invention will be described in more detail by way of examples. The following examples are only examples to help understand the present invention and do not limit the scope of the present invention.

[0091] Preparation Example - Preparation of Metal Organic Framework (MOF)

[0092] A solvent is prepared by mixing about 20 ml of N,N-dimethylformamide, about 20 ml of distilled water and about 20 ml of methanol. The solvent is divided into two parts and placed in a first container and a second container.

[0093] About 4 mmol of the metal ion precursor CoCl 2 6H 2 O is injected into the first container.

[0094] About 4 mmol of an organic ligand 2,5-thiophenedicarboxylic acid (2,5-TPDC) is injected into the second container, and about 8 mmol of sodium hydroxide (NaOH) is injected into the second container.

[0095] After the solution contained in the second container was slowly put into the first container, about 0.8 ml of triethylamine as a catalyst was put into the first container and stirred for about 5 minutes to 10 minutes to prepare a starting material.

[0096] After the starting material thus prepared is placed in a reactor isolated from the outside, it is irradiated with ultrasonic waves of about 30 kHz to 50 kHz for about 6 hours to 8 hours to synthesize a metal organic framework (MOF).

[0097] The metal organic framework (MOF) was separated using a centrifugal separator.The metal organic framework (MOF) was washed with ethanol at least 3 times and vacuum dried at about 100° C. to 120° C. for about 12 hours to 18 hours.

[0098] Example 1

[0099] A slurry containing about 70 wt % of the metal organic framework (MOF) of the above-described Preparation Example and about 30 wt % of a sulfide-based solid electrolyte was applied to an anode current collector and dried to form an anode layer.

[0100] The solid electrolyte layer is prepared by pressurizing the sulfide-based solid electrolyte powder at about 400 MPa to 500 MPa.

[0101] The solid electrolyte layer is placed on the anode layer and pressurized at about 350 MPa to 400 MPa to bond the anode layer and the solid electrolyte layer.

[0102] The half-cell is made by bonding a lithium foil to a solid electrolyte layer.

[0103] A pressed cell kit for battery evaluation was assembled to evaluate the electrochemical properties of the half-cell while applying a pressure of about 30 MPa to 40 MPa to the half-cell.

[0104] Example 2

[0105] A half-cell was fabricated in the same manner as in Example 1 except that a slurry containing about 60 wt % of a metal organic framework (MOF) and about 40 wt % of a sulfide-based solid electrolyte was used, and its electrochemical properties were evaluated.

[0106] Example 3

[0107] A half-cell was fabricated in the same manner as in Example 1 except that a slurry containing about 50 wt % of a metal organic framework (MOF) and about 50 wt % of a sulfide-based solid electrolyte was used, and its electrochemical properties were evaluated.

[0108] Example 4

[0109] A slurry containing about 70 wt % of the metal organic framework (MOF) of the above-described Preparation Example and about 30 wt % of a sulfide-based solid electrolyte was applied to an anode current collector and dried to form an anode layer.

[0110] A dispersion was prepared by injecting lithium powder into toluene as a dispersion medium in a glove box so that the concentration of the dispersion was about 3 wt %.

[0111] About 20 ml to 50 ml of the dispersion is dropped onto the anode layer. The resulting product is vacuum dried at about 100° C. to 150° C. to form a lithium layer.

[0112] The solid electrolyte layer is prepared by pressurizing a sulfide-based solid electrolyte powder at about 400 MPa to 500 MPa.

[0113] The solid electrolyte layer is placed on the lithium layer and pressurized at about 350 MPa to 400 MPa to bond the lithium layer and the solid electrolyte layer.

[0114] The half-cell is made by bonding a lithium foil to a solid electrolyte layer.

[0115] A pressed battery tool kit for battery evaluation was assembled to evaluate the electrochemical properties of the half-cell while applying a pressure of about 30 MPa to 40 MPa to the half-cell.

[0116] Example 5

[0117] A half-cell was fabricated in the same manner as in Example 1 except that a slurry containing about 45 wt % of a metal organic framework (MOF) and about 55 wt % of a sulfide-based solid electrolyte was used, and its electrochemical properties were evaluated.

[0118] Figure 3 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 1 are shown. Figure 4 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 2 are shown. Figure 5 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 3 are shown. Figure 6 The charge / discharge capacity and coulombic efficiency of the all-solid-state battery according to Example 4 are shown.

[0119] Figure 7 The specific capacity of charge and discharge of the all-solid-state battery according to Example 1 is shown. Figure 8 The specific capacity of charge and discharge of the all-solid-state battery according to Example 2 is shown. Fig. 9 The specific capacity of charge and discharge of the all-solid-state battery according to Example 3 is shown. Fig.10 The specific capacity of charge and discharge of the all-solid-state battery according to Example 4 is shown.

[0120] The capacity retention rate of each all-solid-state battery can be calculated based on Figures 7 to 10 Determination. Fig.11 The capacity retention rate of the all-solid-state battery according to Example 1 is shown. Fig.12 The capacity retention rate of the all-solid-state battery according to Example 2 is shown. Fig.13 The capacity retention rate of the all-solid-state battery according to Example 3 is shown. Fig.14 The capacity retention rate of the all-solid-state battery according to Example 4 is shown.

[0121] Table 1 below shows the electrochemical properties of the all-solid-state batteries of Examples 1 to 5.

[0122] [Table 1]

[0123]

[0124] With reference to Examples 1 to 3 and 5, it can be seen that the higher the solid electrolyte content, the more the initial coulombic efficiency and capacity retention rate are improved. At the same time, when Example 1 and Example 4 are compared, it can be seen that even if the solid electrolyte content is reduced, as long as there is a lithium layer, the initial coulombic efficiency and capacity retention rate can also be increased. When the content of MOF in the all-solid-state battery is less than about 45 wt % and the content of the solid electrolyte is greater than about 55 wt %, the initial coulombic efficiency and capacity retention rate may increase, although too small a amount of MOF and too high a amount of solid electrolyte are not desirable.

[0125] Metal organic frameworks (MOFs) were prepared in the same manner as in the Preparation Examples by changing metal ions and organic ligands, as shown in Table 2 below.

[0126] After manufacturing a half-cell using a metal organic framework (MOF) in the same manner as in Example 2, the electrochemical properties of the half-cell were evaluated. The results are shown in Table 2.

[0127] [Table 2]

[0128]

[0129] The metal organic framework containing lithium ions has a stable structure because it is charged and discharged by inserting and extracting lithium ions. The metal organic framework containing manganese ions presents a thin plate-like particle shape and has stable charging and discharging characteristics. The advantage of the metal organic framework containing nickel ions is that it has a high average capacity. The metal organic framework containing nickel ions and manganese ions exhibits a low plateau potential of 0.5V. The metal organic framework containing cobalt ions exhibits high capacity, high coulombic efficiency and low plateau potential, among which the metal organic framework containing 2,5-TPDC as an organic ligand exhibits the most excellent electrochemical properties. In some embodiments, heterocyclic organic ligands are preferred. In some embodiments, sulfide solid electrolytes are preferred.

[0130] The exemplary embodiments and examples of the present invention have been described in detail above. The scope of rights of the present invention is not limited to the above exemplary embodiments and examples, and various modifications and improvements made by those skilled in the art using the basic concepts of the present invention defined in the claims are also included in the scope of rights of the present invention.

Claims

1. An all-solid-state battery, comprising: an anode layer comprising a solid electrolyte and a metal-organic framework MOF; a solid electrolyte layer disposed on the anode layer; and The cathode layer is disposed on the solid electrolyte layer. 2 . The all-solid-state battery according to claim 1 , wherein the solid electrolyte comprises a sulfide-based solid electrolyte. 3 . The all-solid-state battery according to claim 1 , wherein the solid electrolyte layer comprises a sulfide-based solid electrolyte. 4 . The all-solid-state battery according to claim 1 , wherein the solid electrolyte is the same as a solid electrolyte of the solid electrolyte layer.

5. The all-solid-state battery according to claim 1, wherein the MOF comprises: Metal ions; and An organic ligand that bonds to a metal ion. 6 . The all-solid-state battery according to claim 5 , wherein the metal ions comprise ions of at least one metal selected from lithium Li, manganese Mn, nickel Ni, cobalt Co, and combinations thereof.

7. The all-solid-state battery according to claim 5, wherein the organic ligand is heterocyclic.

8. The all-solid-state battery according to claim 5, wherein the organic ligand comprises at least one selected from 1,4-phthalic acid, 2,6-naphthalene dicarboxylic acid, ellagic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,4,9,10-pyrene tetracarboxylic acid, biphenyl tetracarboxylic acid, 2,5-thiophene dicarboxylic acid, and combinations thereof. 9 . The all-solid-state battery according to claim 5 , wherein the organic ligand comprises 2,5-thiophenedicarboxylic acid. 10 . The all-solid-state battery according to claim 1 , wherein the anode layer comprises 30 wt % to 55 wt % of the solid electrolyte and 45 wt % to 70 wt % of the MOF.

11. The all-solid-state battery according to claim 1, wherein the anode layer comprises greater than 55 wt% of the solid electrolyte and less than 45 wt% of the MOF. 12 . The all-solid-state battery according to claim 1 , wherein the all-solid-state battery further comprises a lithium layer inserted between the anode layer and the solid electrolyte layer.

13. The all-solid-state battery according to claim 12, wherein the lithium layer comprises lithium powder. The all-solid-state battery according to claim 1 , wherein the anode layer is disposed on an anode current collector.

15. The all-solid-state battery according to claim 1, wherein a cathode current collector is disposed on the cathode layer.

16. An all-solid-state battery, comprising: an anode layer comprising a solid electrolyte and a metal-organic framework MOF; a lithium layer disposed on the anode layer; a solid electrolyte layer disposed on the lithium layer; and The cathode layer is disposed on the solid electrolyte layer.

17. An all-solid-state battery, comprising: an anode layer comprising a solid electrolyte and a metal organic framework MOF, wherein the metal organic framework MOF comprises cobalt as a metal ion and 2,5-thiophenedicarboxylic acid as an organic ligand bonded to the metal ion; a lithium layer disposed on the anode layer; a solid electrolyte layer disposed on the lithium layer; and The cathode layer is disposed on the solid electrolyte layer.

18. A vehicle comprising the all-solid-state battery according to claim 1.

19. A vehicle comprising the all-solid-state battery according to claim 16.

20. A vehicle comprising the all-solid-state battery according to claim 17.

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