All-solid-state battery comprising porous composite anode current collector

Abstract

The present invention relates to an all-solid-state battery comprising: a cathode; an anode including a porous composite anode current collector; and a solid electrolyte or separator positioned between the cathode and the anode, wherein the porous composite anode current collector includes a metal foam and a plated layer formed on the metal foam. The all-solid-state battery according to one aspect ensures excellent battery performance in terms of high energy density and lifespan characteristics while simultaneously achieving outstanding safety.

Description

All-solid-state battery comprising a porous composite cathode collector

[0001] The present invention relates to an all-solid-state battery comprising a porous composite negative electrode collector.

[0002] Recently, as the energy density required for batteries has rapidly increased, research is being conducted on replacing conventional anode materials, such as graphite or silicon, with lithium metal, or on anode-free batteries. Lithium metal possesses a high specific capacity and low reduction potential, and anode-free batteries offer significant potential for reducing cell volume and weight, thereby increasing gravimetric energy density. However, commercial application remains limited.

[0003] For example, stability issues include dendrite accumulation during charge / discharge processes, electrode volume expansion and reduced reversible capacity due to the formation of dead lithium, and the high reactivity of lithium metal with existing electrolytes. Furthermore, for the commercialization of high-energy-density batteries, ensuring safety, such as excellent heat resistance, without compromising battery performance is essential.

[0004] One aspect of the present invention aims to provide an all-solid-state battery having excellent battery performance such as high energy density and lifespan characteristics, as well as excellent safety.

[0005] One aspect of the present invention provides an all-solid-state battery comprising: a positive electrode; a negative electrode including a porous composite negative electrode collector; and a solid electrolyte or separator positioned between the positive electrode and the negative electrode; wherein the porous negative electrode collector includes a metal foam and a plating layer formed on the metal foam.

[0006] The above negative electrode may be composed of the above porous composite negative electrode collector, or may further include a lithium metal layer on the above porous composite negative electrode collector.

[0007] The metal foam may comprise copper, nickel or a combination thereof.

[0008] The above plating layer may include tin (Sn), tin oxide (SnO), cerium (Ce), cerium oxide (CeO), silver (Ag), gold (Au), silicon (Si), silicon oxide (SiO2), or a combination thereof.

[0009] The above solid electrolyte may be a composite solid electrolyte including a crystalline organic electrolyte, a fluorine-based polymer binder, and inorganic particles.

[0010] The above crystalline organic electrolyte may include a sulfone solvent represented by the following chemical formula 1 and a bis(fluorosulfonyl)imide alkali metal salt (MFSI).

[0011] [Chemical Formula 1]

[0012] R 1 R 2 SO2

[0013] (In the above chemical formula 1, the R 1 and R 2 are each independently an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms, or a combination thereof, and R 1 and R 2 ) wherein alkyl, alkoxy and aryl are each independently substituted or unsubstituted with halogen, amino or nitro.

[0014] The above crystalline organic electrolyte may have a cocrystal structure.

[0015] The above solid electrolyte may include a crystalline organic electrolyte and a fluorine-based polymer binder in a weight ratio of 1:0.15 to 0.3.

[0016] The above solid electrolyte may contain a fluorine-based polymer binder and inorganic particles in a weight ratio of 1:7 to 15.

[0017] The above separation membrane may include a porous substrate; and an inorganic particle layer formed on one or both sides of the porous substrate and including inorganic particles and a binder.

[0018] An all-solid-state battery according to one embodiment of the present invention can secure high energy density while simultaneously implementing excellent lifespan characteristics and safety. Specifically, the all-solid-state battery according to one embodiment can improve the reversibility of lithium deposition and desorption reactions during charge / discharge, and can effectively suppress problems such as dendrite growth and reversible capacity decline, thereby implementing excellent lifespan characteristics. At the same time, it has excellent thermal stability without a separate physical separator, excellent interfacial stability between the electrolyte and electrode, and a simple manufacturing process, which may be advantageous for commercialization.

[0019] Figure 1 illustrates the results of interface resistance analysis of Example 1 and Comparative Example 1.

[0020] Figure 2 illustrates the results of high-temperature life characteristics analysis of Example 1 and Comparative Example 1.

[0021] Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0022] As used herein, the singular forms may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0023] Throughout this specification, the terms "comprises," "includes," "contains," or "has" a component, unless specifically stated to the contrary, do not exclude other components, but rather may include other components, and do not exclude additional unrecited elements, materials, or processes.

[0024] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0025] Unless otherwise specified herein, “about” may be considered a value within 30%, 25%, 20%, 15%, 10% or 5% of the stated value.

[0026] Below, the present disclosure will be described in detail. However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0027] One aspect of the present invention provides an all-solid-state battery that has excellent battery performance such as high energy density and lifespan characteristics, while also having excellent safety.

[0028] Specifically, an all-solid-state battery according to one aspect includes: a positive electrode; a negative electrode including a porous composite negative electrode collector; and a solid electrolyte or separator positioned between the positive electrode and the negative electrode; wherein the porous negative electrode collector may include a metal foam and a plating layer formed on the metal foam.

[0029] The all-solid-state battery according to one aspect may be an anode-less battery in which the negative electrode is composed of the porous composite negative electrode collector, or may be a lithium metal battery further including a lithium metal layer on the porous composite negative electrode collector.

[0030] The above metal foam is not particularly limited as long as it is a conductive material with a porous structure, but may be selected from, for example, copper, nickel, or a combination thereof.

[0031] The metal foam may have a porosity of 60% to 95%, or 70% to 95%, or 80% to 95%, or 85% to 95%, and the metal foam may have a thickness of 10 μm to 200 μm, or 10 to 150 μm, or 15 to 150 μm, or 20 to 150 μm, or 25 to 150 μm, or 25 to 100 μm, or 25 to 80 μm, or 25 to 50 μm, and may include all possible combinations of the upper and lower limits of the above numerical ranges, but is not necessarily limited thereto.

[0032] The above-mentioned plating layer may be a porous plating layer formed by plating only on the metal surface of the metal foam. The type of the plating layer is not particularly limited as long as it is a metal having lithium ion conductivity, but may include, for example, tin (Sn), tin oxide (SnO), cerium (Ce), cerium oxide (CeO), silver (Ag), gold (Au), silicon (Si), silicon oxide (SiO2), or a combination thereof.

[0033] An all-solid-state battery according to one aspect can improve the reversibility of lithium deposition and desorption reactions during charge / discharge by including a porous negative electrode collector as described above, and can effectively suppress problems such as dendrite growth and reversible capacity decline, thereby realizing excellent life characteristics.

[0034] The first aspect of the above all-solid-state battery includes a positive electrode; a negative electrode including a porous composite negative electrode collector; and a solid electrolyte positioned between the positive electrode and the negative electrode; wherein the porous negative electrode collector may include a metal foam and a plating layer formed on the metal foam.

[0035] The above solid electrolyte may be a composite solid electrolyte including a crystalline organic electrolyte, a fluorine-based polymer binder, and inorganic particles, and can simultaneously satisfy high ionic conductivity and thermal stability, and in combination with the above-described porous negative electrode collector, can realize excellent battery performance such as low interfacial resistance and high life characteristics.

[0036] The above crystalline organic electrolyte may include a sulfone solvent represented by the following chemical formula 1 and a bis(fluorosulfonyl)imide alkali metal salt (MFSI).

[0037] [Chemical Formula 1]

[0038] R 1 R 2 SO2

[0039] (In the above chemical formula 1, the R 1 and R 2 are each independently an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms, or a combination thereof, and R 1 and R 2 ) wherein alkyl, alkoxy and aryl are each independently substituted or unsubstituted with halogen, amino or nitro.

[0040] For example, the above R 1 and R 2 Each independently may be an alkyl having 1 to 7 carbon atoms, preferably an alkyl having 1 to 3 carbon atoms, and the R 1 and R 2may be identical to each other. In this case, due to the symmetrical structure of the solvent compound molecules, a solid electrolyte having the melting point range desired by the present invention can be easily implemented compared to solvent compound molecules having an asymmetrical structure. Specifically, the sulfone-based solvent may include at least one selected from the group consisting of dimethyl sulfone and diethyl sulfone, and most preferably, dimethyl sulfone. Dimethyl sulfone has the advantage of having a high dielectric constant and excellent electrochemical stability, being inexpensive, and being harmless to the human body.

[0041] The above bis(fluorosulfonyl)imide alkali metal salt (MFSI) is dissolved in the above-described sulfone solvent, and acts as a source of alkali metal ions in the battery, enabling the basic operation of the secondary battery and promoting the movement of alkali metal ions between the positive and negative electrodes. The alkali metal (M) in the above bis(fluorosulfonyl)imide alkali metal salt (MFSI) can be adjusted depending on the type of battery, and as a non-limiting example, in the case of a sodium secondary battery, the alkali metal (M) can be sodium (Na), and in the case of a lithium secondary battery, it can be lithium (Li).

[0042] The above crystalline organic electrolyte is a solid at room temperature, and may be manufactured by eutecticizing a sulfone-based solvent represented by the above chemical formula 1 and a bis(fluorosulfonyl)imide alkali metal salt (MFSI) and then cooling the same, and may form a eutectic system. The above crystalline organic electrolyte may have a cocrystal structure, and the melting point of the above crystalline organic electrolyte may be determined depending on the melting point and mixing ratio of the sulfone-based solvent and the metal salt itself.

[0043] The above crystalline organic electrolyte may contain the bis(fluorosulfonyl)imide alkali metal salt (MFSI) and the sulfone solvent represented by the chemical formula 1 in a molar ratio of 1:9 to 4:6, and specifically, in a molar ratio of 1:9 to 3:7.

[0044] The above crystalline organic electrolyte may have a melting point of 50 to 170°C, and specifically, may have a melting point of 60 to 170°C.

[0045] The above composite solid electrolyte may contain 60 to 90 wt%, or 70 to 90 wt%, of the crystalline organic electrolyte based on the total weight.

[0046] The above composite solid electrolyte may include a crystalline organic electrolyte and a fluorine-based polymer binder in a weight ratio of 1:0.15 to 0.3.

[0047] The above composite solid electrolyte may contain a fluorine-based polymer binder and inorganic particles in a weight ratio of 1:7 to 15.

[0048] The above fluorine-based polymer binder may be selected from the group consisting of a homopolymer, a copolymer, and a ternary copolymer containing vinylidene fluoride (VDF). Specifically, the fluorine-based polymer is polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-trifluoroethylene, polyvinylidene fluoride-co-trifluoroethylene-co-chlorofluoroethylene, polyvinylidene fluoride-co-hexafluoroethyelene, polyvinylidene fluoride-co-hexafluoroethyelene, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), and polyvinylidene fluoride-co-chlorotrifluoroethylene (Poly(vinylidene It may be at least one selected from the group consisting of fluoride-co-chlorotrifluoroethylene (PVDF-CTFE).

[0049] A second aspect of the above all-solid-state battery includes: a positive electrode; a negative electrode including a porous composite negative electrode collector; and a separator positioned between the positive electrode and the negative electrode; wherein the porous negative electrode collector may include a metal foam and a plating layer formed on the metal foam.

[0050] The above separator is not particularly limited as long as it is commonly used in the relevant technical field, but as an example, the separator may be a composite separator including a porous substrate; and an inorganic particle layer formed on one or both sides of the porous substrate and including inorganic particles and a binder.

[0051] The porous substrate is not limited to those commonly used in the relevant field, and may be, for example, a woven fabric, a non-woven fabric, or a porous film. Specifically, the porous substrate may be a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate or polybutylene terephthalate, a polyacetal, a polyamide, a polyimide, a polycarbonate, a polyetheretherketone, a polyaryletherketone, a polyetherimide, a polyamideimide, a polybenzimidazole, a polyethersulfone, a polyphenylene oxide, a cyclic olefin copolymer, a polyphenylene sulfide, a polyethylene naphthalate, glass fiber, Teflon, and / or a polytetrafluoroethylene, and any two or more thereof may be used. Among the porous substrates, the porous film is manufactured by a dry method and a wet method, and is well known in the art, so it will not be described further.

[0052] In one embodiment, the porous substrate may have a porosity of, but is not limited to, 20 to 60%, or 30 to 60%, or 30 to 50%, or 35 to 45%.

[0053] The thickness of the porous substrate is not particularly limited and may be, for example, 1 μm to 100 μm, 1 μm to 50 μm, 1 μm to 30 μm, 5 μm to 20 μm, or any value between the above values.

[0054] The above inorganic particles may be used without limitation as long as they are commonly used in the relevant technical field, and as non-limiting examples, they may be one or more selected from metal oxides, metal hydrates, metal carbides, metal nitrides, and metal carbonitrides such as boehmite, BaSO4, CeO2, MgO, CaO, ZnO, Al2O3, TiO2, BaTiO3, HfO2, SrTiO3, SnO2, NiO, ZrO2, Y2O3, and SiC.

[0055] The average particle diameter (D50) of the above-mentioned inorganic particles may be, for example, 0.01 ㎛ or more, 0.02 ㎛ or more, 0.05 ㎛ or more, 0.1 ㎛ or more, and may include, but is not limited to, all possible combinations of the upper and lower limits of the above numerical ranges of 0.01 ㎛ to 10 ㎛, or 0.02 ㎛ to 5.0 ㎛, or 0.1 ㎛ to 5.0 ㎛, or 0.1 ㎛ to 3.0 ㎛, or 0.1 ㎛ to 2.0 ㎛, or 0.1 ㎛ to 1.0 ㎛, or the like.

[0056] The above binder is not particularly limited as long as it is a conventional binder used in this technical field, and as a non-limiting example, it may be one or two or more selected from acrylic polymers such as polyacrylate, polymethacrylate, polybutylacrylate, and polyacrylonitrile; fluorine polymers such as polyvinylidene fluoride, hexafluoropropylene, polyvinylidene fluoride-hexafluoropropylene, and polyvinylidene fluoride-trichloroethylene; polyvinylacetate, polyvinylacetate, polyethylene oxide, cellulose, modified cellulose, polyamide, polyacrylamide, rubber, and elastomer, but is not limited thereto.

[0057] When the all-solid-state battery according to one embodiment includes a separator, the all-solid-state battery may further include an electrolyte, and the electrolyte may include an organic solvent and a lithium salt, and any electrolyte commonly used in the relevant technical field may be used without limitation, and thus a detailed description thereof will be omitted. The positive electrode may include a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector, and when the all-solid-state battery according to one embodiment includes the above-described solid electrolyte, the positive electrode active material layer may have a portion of the solid electrolyte according to one embodiment impregnated within pores, and the positive electrode and the solid electrolyte may be integrated with each other, and specifically, the positive electrode may be impregnated with at least a portion of the components of the above-described composite solid electrolyte layer, for example, a crystalline organic electrolyte, a fluorine-based polymer binder, inorganic particles, or a combination thereof.

[0058] In addition, when the all-solid-state battery according to one embodiment includes the above-described solid electrolyte, the negative electrode may include a part of the above-described solid electrolyte, for example, the crystalline organic electrolyte, a fluorine-based polymer binder, inorganic particles, or a combination thereof, within the pores of the porous composite negative electrode body.

[0059] For example, the thickness of the solid electrolyte may be 10 to 100 μm, or 30 to 100 μm, or 30 to 80 μm, wherein the thickness of the solid electrolyte means the thickness of a section where the positive electrode active material layer and the solid electrolyte are not mixed and only the solid electrolyte exists.

[0060] Non-limiting examples of the positive electrode current collector may include a foil made of aluminum, nickel, or a combination thereof, and the positive electrode active material layer may include a positive electrode active material, a binder, a conductive material, a dispersing agent, etc., as needed.

[0061] The above cathode active material may be a conventional cathode active material used in this technical field, and non-limiting examples thereof include lithium cobalt oxide composite oxide (LiCoO2), spinel crystal type lithium manganate composite oxide (LiMn2O4), lithium manganate composite oxide (LiMnO2), lithium nickelate composite oxide (LiNiO2), lithium iron phosphate (LiFePO4), lithium manganese phosphate (LiMnPO4), lithium cobalt phosphate (LiCoPO4), lithium iron pyrophosphate (Li2FeP2O7), lithium niobate composite oxide (LiNbO2), lithium ironate composite oxide (LiFeO2), lithium magnesiumate composite oxide (LiMgO2), lithium cuprate composite oxide (LiCuO2), lithium zincate composite oxide (LiZnO2), lithium molybdate composite oxide (LiMoO2), and tantalum acid. Lithium composite oxide (LiTaO2), lithium tungstate composite oxide (LiWO2), lithium permanganate nickel cobalt composite oxide (xLi2MnO3(1-x)LiMn1-y-zNiyCozO2), lithium nickel cobalt aluminum composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O2), lithium nickel cobalt manganese composite oxide (LiNi 0.33 Co 0.33 Mn 0.33 O2, LiNi 0.4 Co 0.2 Mn 0.4 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.7 Co 0.15 Mn 0.15 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2), manganese nickel oxide (LiNi 0.5 Mn 1.5 O4) but are not limited to these.

[0062] The conductive material may include, but is not limited to, carbon black such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, etc.; conductive fibers such as carbon fibers and metal fibers; metal powders such as fluorinated carbon, aluminum, and nickel powders; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives, but is not particularly limited as long as it has conductivity and does not cause chemical changes in the battery.

[0063] The above binder polymer may include one or two or more selected from the group consisting of nitrile butadiene rubber, polybutadiene rubber, polyethylene glycol, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, polypropylene oxide, polydimethylsiloxane, polyvinylidene fluoride, polyvinylidene carbonate, and polyvinylpyrrolidinone.

[0064] Hereinafter, the above-described implementation examples will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0065] [Example 1]

[0066] Solid electrolyte manufacturing

[0067] Lithium bis(fluorosulfonyl)imide (LiFSI) and dimethyl sulfone (DMS) were mixed in a molar ratio of 2.5:7.5, heated to 90°C to eutectic, and then cooled to room temperature to prepare a crystalline organic electrolyte. After the crystalline organic electrolyte was heated to 90°C to eutectic, 15 wt% of polyvinylidene fluoride (PVDF) and 120 wt% of alumina particles (Al2O3) with an average diameter of 0.5 μm were added and mixed based on the total weight of the crystalline organic electrolyte, and then cooled to room temperature to prepare a solid electrolyte.

[0068] All-solid-state battery manufacturing

[0069] A cathode material slurry was prepared by adding N-methylpyrrolidone so that the cathode material content was 40 wt% at a weight ratio of cathode active material (NCM811) / conductive material (carbon black) / binder (PVDF) 94 / 3 / 3. The cathode material slurry was applied to an aluminum (Al) thin film having a thickness of 18 μm using a doctor blade, and then dried with hot air at 80°C and vacuum-dried at 120°C for 24 hours to form a cathode active material layer having a thickness of 20 μm. Thereafter, the solid electrolyte obtained above was melted at 90°C, applied to one surface of the cathode active material layer, rolled using a roll press, and then cooled at room temperature to prepare a 30 μm thick solid electrolyte layer integrated with the cathode active material layer.

[0070] Afterwards, a porous composite negative electrode collector doped with tin was manufactured using an electrolytic plating method on the metal surface of copper foam (Cu foam, thickness 30 ㎛, porosity 85%), and the obtained porous composite negative electrode collector was laminated on the other side of the solid electrolyte on which the positive electrode was formed, thereby manufacturing an all-solid-state battery.

[0071] [Comparative Example 1]

[0072] The same procedure as Example 1 was followed except that a copper film was used instead of copper foam when manufacturing the negative electrode collector.

[0073] [Comparative Example 2]

[0074] The same procedure as Example 1 was followed, except that only copper foam (Cu foam) not doped with tin was used as the cathode current collector.

[0075] Evaluation 1. Interface resistance

[0076] Electrochemical impedance spectroscopy (EIS) was used to analyze the battery reaction interface resistance during the electrochemical reaction of the all-solid-state batteries manufactured in Example 1 and Comparative Example 1. EIS measurements were performed at room temperature (25°C) in the frequency range of 5 kHz to 0.1 Hz with an AC voltage amplitude of 10 mV, and the results are shown in Fig. 1.

[0077] Evaluation 2. High-temperature life characteristics analysis

[0078] The all-solid-state batteries manufactured in Example 1 and Comparative Example 1 were charged and discharged three times at 0.1 C constant current in the range of 3 to 4.3 V at 60°C, and then charged and discharged 150 times under conditions of 0.5 C constant current / constant voltage charging and 0.5 C constant current discharging, and the change in capacity (specific capacity) according to the cycle is shown in Figure 2.

[0079] The all-solid-state battery according to an embodiment of the present invention exhibits remarkably low resistance at the interface between the electrode and the solid electrolyte, and exhibits excellent thermal stability even at a high temperature of 60°C, even without the introduction of a separate separator. In contrast, the all-solid-state battery of Comparative Example 1 exhibits significantly deteriorated interface resistance and lifespan characteristics.

[0080] In addition, it was confirmed that the all-solid-state battery of Comparative Example 2 also showed a decrease in battery performance, including not only life characteristics but also ionic conductivity and initial capacity.

[0081] As described above, the present invention has been described by limited embodiments, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0082] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. A cathode comprising a positive electrode; a porous composite negative electrode collector; and a solid electrolyte or separator positioned between the positive electrode and the negative electrode; An all-solid-state battery, wherein the porous composite negative electrode collector comprises a metal foam and a plating layer formed on the metal foam.

2. In paragraph 1, An all-solid-state battery, wherein the negative electrode is composed of the porous composite negative electrode collector.

3. In paragraph 1, An all-solid-state battery, wherein the negative electrode further comprises a lithium metal layer on the porous composite negative electrode collector.

4. In paragraph 1, An all-solid-state battery, wherein the metal foam comprises copper, nickel or a combination thereof.

5. In paragraph 1, An all-solid-state battery, wherein the plating layer comprises tin (Sn), tin oxide (SnO), cerium (Ce), cerium oxide (CeO), silver (Ag), gold (Au), silicon (Si), silicon oxide (SiO2), or a combination thereof.

6. In paragraph 1, An all-solid-state battery, wherein the solid electrolyte is a composite solid electrolyte comprising a crystalline organic electrolyte, a fluorine-based polymer binder, and inorganic particles.

7. In paragraph 6, An all-solid-state battery, wherein the above-mentioned crystalline organic electrolyte comprises a sulfone-based solvent represented by the following chemical formula 1 and a bis(fluorosulfonyl)imide alkali metal salt (MFSI). [Chemical Formula 1] R 1 R 2 SO2 In the above chemical formula 1, the R 1 and R 2 are each independently an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms, or a combination thereof, and R 1 and R 2 The alkyl, alkoxy and aryl of are each independently substituted or unsubstituted with halogen, amino or nitro.

8. In paragraph 6, An all-solid-state battery in which the above crystalline organic electrolyte has a cocrystal structure.

9. In paragraph 6, An all-solid-state battery, wherein the solid electrolyte comprises a crystalline organic electrolyte and a fluorine-based polymer binder in a ratio of 1:0.15 to 0.

3.

10. In paragraph 9, An all-solid-state battery, wherein the solid electrolyte comprises a fluorine-based polymer binder and inorganic particles in a ratio of 1:7 to 15.

11. In paragraph 1, An all-solid-state battery, wherein the separator comprises a porous substrate; and an inorganic particle layer formed on one or both sides of the porous substrate and including inorganic particles and a binder.

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