KR20200078198A - A solid electrolyte layer and an all-solid-state battery comprising the same - Google Patents

Abstract

The present invention relates to a solid electrolyte membrane for an all-solid battery and a battery including the same. In the present invention, the battery can include lithium metal as a negative active material. The solid electrolyte membrane for an all-solid battery according to the present invention has an effect of inhibiting the growth of lithium dendrite by ionizing lithium deposited as a metal. Accordingly, when lithium metal is used as a negative electrode in the all-solid battery including the solid electrolyte membrane, the growth of lithium dendrites is delayed and/or suppressed, thereby effectively preventing an electrical short due to the growth of the dendrites.

Description

A solid electrolyte layer and an all-solid-state battery comprising the same}

The present invention relates to a solid electrolyte membrane for an all-solid-state battery and a battery comprising the same. In addition, the present invention relates to an all-solid-state battery comprising lithium metal as a negative electrode active material.

A lithium ion battery using a liquid electrolyte has a structure in which a negative electrode and a positive electrode are partitioned by a separator, and thus a short circuit may occur when the separator is damaged due to deformation or external shock, which may lead to danger of overheating or explosion. Therefore, it can be said that the development of a solid electrolyte capable of securing safety in the field of lithium ion secondary batteries is a very important task.

Lithium secondary batteries using solid electrolytes have the advantages of increasing the safety of the battery, preventing leakage of the electrolyte, improving the reliability of the battery, and making the thin battery easy. In addition, since lithium metal can be used as a negative electrode, energy density can be improved, and accordingly, it is expected to be applied to a high-capacity secondary battery for electric vehicles as well as a small secondary battery, and is attracting attention as a next-generation battery.

As the solid electrolyte, a polymer material of an ion-conducting material may be used, or an inorganic material of an oxide or sulfide having ion-conducting properties may be used, and a hybrid type material in which a polymer material and an inorganic material are mixed is also proposed.

On the other hand, when lithium metal is used as the negative electrode active material, there is a problem that lithium dendrites grow from the surface of the negative electrode, and when the grown lithium dendrites contact the positive electrode, a short circuit of the battery is caused. 1 is a schematic view showing such a conventional all-solid-state battery. In an all-solid-state battery, a solid electrolyte membrane instead of a separator serves as a positive/negative electrical insulator. However, when a polymer material is used as the solid electrolyte, the solid electrolyte membrane may be damaged by the growth of lithium dendrites. 1 is a schematic view showing a mechanism for generating a short circuit according to lithium dendrite growth in an all-solid-state battery using a conventional solid electrolyte. In addition, the inorganic solid electrolyte is usually formed as a layered structure by integrating particulate ion-conducting inorganic materials, and contains a large number of pores due to interstitial volumes between particles. Accordingly, lithium dendrites may grow into the space provided by the pores, and a short circuit may occur when the lithium dendrites grown through the pores contact the anode. Accordingly, development of an electrolyte membrane for an all-solid-state battery capable of suppressing lithium dendrite growth is required.

The present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a solid electrolyte membrane for an all-solid-state battery in which lithium dendrite growth is suppressed. In addition, another object of the present invention is to provide an all-solid-state battery containing lithium metal as a negative electrode active material. Other objects and advantages of the present invention will be understood by the following description. On the other hand, it will be readily appreciated that the objects and advantages of the present invention can be realized by means or methods described in the claims, and combinations thereof.

The first aspect of the present invention relates to a solid electrolyte membrane for an all-solid-state battery, wherein the solid electrolyte membrane has an ion conductivity of 1x10 ^-7 S/cm or more, and the solid electrolyte membrane is a suppression layer comprising a dendrite growth inhibitory substance (a) And one or more, wherein the dendrite growth inhibitory material (a) is derived from any one of (a1) metal(s) having a lower ionization tendency than lithium and (a2) two or more of the metal(s). It is included in the suppression layer in the form of at least one of their salts and their ions, and the suppression layer is patterned by including a plurality of pattern units containing the suppression material, and the pattern units are within the suppression layer. They are distributed regularly or irregularly.

In a second aspect of the present invention, in the first aspect, the inhibitory layer includes a dendrite growth inhibitory substance and a polymer copolymer in which the inhibitory substance is chemically bonded, and self-assembly of the polymer copolymer. ), the polymer copolymer includes a functional group capable of chemically bonding with the inhibitor, and the inhibitor is combined with the polymer copolymer through the functional group.

In a third aspect of the present invention, in at least one of the first to second aspects, the inhibitory layer has a shape in which micelles are aligned according to a hexagonal compact structure by self-assembly of the polymer copolymer.

In the fourth aspect of the present invention, in at least one of the first to third aspects, the functional group is one or more of ether and amine.

The fifth aspect of the present invention, in at least one of the first to fourth aspects, the polymer copolymer is polystyrene-blockpooly (2-vinylpyridine) copolymer, polystyrene-block-poly (4-vinylpyridine) copolymer, poly It contains at least one selected from (1,4-isoprene)-blockpolystyrene-block-poly(2-vinylpyridine) copolymer and polystyrene-block-poly(ethylene oxide) copolymer.

The sixth aspect of the present invention, in at least one of the first to fifth aspects, the metal is K, Sr, Ca, Na, Mg, Be, Al, Mn, Zn, Cr (+3), Fe , Cd, Co, Ni, Sn, Pb, Cu, Hg, Ag, Pd, Ir, Pt(+2), Au and Pt(+4).

In the seventh aspect of the present invention, in at least one of the first to sixth aspects, the inhibitory substance includes one or more selected from the group consisting of Au and Pt.

In the eighth aspect of the present invention, in at least one of the first to seventh aspects, the metal salt is chloride (chloride), iodide (iodide), cyanide (cyanide), boride (bromide), sulfide ( It is one or more of sulfide, hydrate, phosphite, and chloride hydrate.

In the ninth aspect of the present invention, in at least one of the first to eighth aspects, the solid electrolyte membrane includes two or more solid electrolyte layers and one or more suppression layers, and the suppression layer is disposed between the solid electrolyte layers. .

In the tenth aspect of the present invention, in at least one of the first to ninth aspects, the solid electrolyte membrane is a first solid electrolyte layer, a suppression layer, and a second solid electrolyte layer sequentially stacked.

In the eleventh aspect of the present invention, in at least one of the first to tenth aspects, at least one of the two or more solid electrolyte layers includes an inhibitory substance, and the content (% by weight) of the inhibitory substance in each solid electrolyte layer is It is lower than the content of the inhibitory substance contained in the inhibitory layer (% by weight).

The twelfth aspect of the present invention according to at least one of the first to eleventh aspects, the solid electrolyte membrane comprises an ion conductive solid electrolyte material, the ion conductive solid electrolyte material is a polymer solid electrolyte, an inorganic solid electrolyte or It includes both mixtures.

The thirteenth aspect of the present invention is at least one of the first to twelfth aspects, wherein the polymer solid electrolyte comprises a polymer resin and a solvated lithium salt.

The fourteenth aspect of the present invention relates to an electrochemical device, wherein the electrochemical device is an all-solid-state battery comprising a negative electrode, a positive electrode, and a solid electrolyte membrane interposed between the negative electrode and the positive electrode, wherein the negative electrode contains lithium metal. , The solid electrolyte membrane is according to at least one of the first to thirteenth aspect.

The fifteenth aspect of the present invention according to at least one of the first to fourteenth aspect, wherein the solid electrolyte membrane is a first solid electrolyte layer, a suppression layer and a second solid electrolyte layer sequentially laminated, the first solid The electrolyte layer includes an inhibitory substance (a), and the inhibitory substance is derived from any one of (a1) metal(s) having a lower ionization tendency than lithium and (a2) alloys(s) of two or more of the metals. will be.

The solid electrolyte membrane for an all-solid-state battery according to the present invention includes a suppression layer formed by self-assembly of a polymer material, and the suppression layer has an effect of inhibiting lithium dendrite growth by ionizing lithium precipitated with metal. Therefore, in the all-solid-state battery including the solid electrolyte membrane, when lithium metal is used as a negative electrode, lithium dendrite growth is delayed and/or suppressed, so that an electrical short circuit caused by dendrite growth can be effectively prevented. In addition, the suppression layer is formed of a fine pattern formed by self-assembly of the polymer material, and thus performs the growth suppression function of lithium dendrites and does not lower the ion conductivity.

The drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to better understand the technical spirit of the present invention together with the contents of the above-described invention, and thus the present invention is limited only to those described in those drawings. Is not interpreted. Meanwhile, the shape, size, scale, or ratio of elements in the drawings included in the present specification may be exaggerated to emphasize a clearer description.
1 schematically illustrates a problem in which a short circuit is caused due to growth of lithium dendrites from a negative electrode in a conventional all-solid-state battery.
2 schematically illustrates a solid electrolyte membrane according to an embodiment of the present invention.
3 schematically illustrates an all-solid-state battery according to an embodiment of the present invention and schematically illustrates a reaction in which lithium dendrite growth is inhibited by a growth-inhibiting material included in the all-solid electrolyte membrane.
Figure 4 shows the AFM image of the suppression layer prepared in Example 1.
5 and 6 schematically show a cross section of a solid electrolyte membrane according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor appropriately explains the concept of terms in order to explain his or her invention in the best way. Based on the principle that it can be defined, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention. Therefore, the configuration described in the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent all of the technical spirit of the present invention, and various equivalents that can replace them at the time of this application It should be understood that there may be variations.

Throughout this specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In addition, the terms "about", "substantially" and the like used throughout the present specification are used as meanings in or close to the numerical values when manufacturing and substance tolerances unique to the stated meanings are used, and to help understand the present application. Hazards are used to prevent unreasonable abuse by unconscionable infringers of the disclosures that are accurate or absolute.

Throughout this specification, the description of "A and/or B" means "A or B or both".

Certain terms used in the detailed description that follows are for convenience only and are not limiting. The words'right','left','upper' and'lower' indicate the direction in the drawings to which reference is made. The words'inward' and'outward' respectively indicate the direction toward or away from the geometric center of the designated device, system and its members. 'Forward','Rear','Upward','Downward' and related words and phrases represent positions and orientations in the referenced drawings and should not be limiting. These terms include the words listed above, derivatives thereof, and words of similar meaning.

The present invention relates to an electrolyte membrane for a secondary battery and a secondary battery comprising the electrolyte membrane. In the present invention, the secondary battery may be a lithium ion secondary battery. In one embodiment of the present invention, the secondary battery is an all-solid-state battery using a solid electrolyte as the electrolyte, and the battery may include lithium metal as a negative electrode active material.

2 schematically shows a secondary battery according to an embodiment of the present invention, and includes a solid electrolyte membrane between the positive electrode and the negative electrode. The configuration of the present invention will be described in more detail with reference to FIG. 2 above.

(1) Solid electrolyte membrane

In the present invention, the solid electrolyte membrane includes two or more solid electrolyte layers. The solid electrolyte layer includes an ion conductive solid electrolyte material, and the solid electrolyte membrane may be applied as an ion conductive electrolyte to an all-solid-state battery that does not use a liquid electrolyte, for example. In addition, in the present invention, the solid electrolyte membrane includes at least one suppressing layer, and the suppressing layer is disposed between the two or more solid electrolyte layers. The suppressing layer includes a dendrite growth inhibiting material.

In the present invention, the solid electrolyte membrane includes an inhibitory layer and has an ion conductivity of 1x10 ^-5 S/cm or more.

In one embodiment of the present invention, the solid electrolyte membrane may have a thickness in the range of 5 μm to 500 μm. The solid electrolyte membrane may be, for example, 10 μm or more, 20 μm or more, 30 μm or more, 50 μm or more, 100 μm or more, 200 μm or more, or 300 μm or more in terms of physical strength and shape stability. Meanwhile, in terms of ion conductivity, it may be 400 μm or less, 300 μm or less, 200 μm or less, 100 μm or less, 70 μm or less, or 50 μm or less. For a specific example, the thickness of the solid electrolyte membrane may be 30 μm to 100 μm or 30 μm to 50 μm.

The ion conductive solid electrolyte material may include at least one of a polymer solid electrolyte and an inorganic solid electrolyte.

In one embodiment of the present invention, the polymer solid electrolyte comprises a polymer resin and a lithium salt, and is a solid polymer electrolyte having a form of a mixture of a solvated lithium salt and a polymer resin, or containing an organic solvent and a lithium salt It may be a polymer gel electrolyte containing an organic electrolyte solution in a polymer resin.

In one embodiment of the present invention, the solid polymer electrolyte is, for example, a polyether polymer, polycarbonate polymer, acrylate polymer, polysiloxane polymer, phosphazene polymer, polyethylene derivative, alkylene as a polymer resin. One or two or more mixtures selected from the group consisting of oxide derivatives, phosphate ester polymers, poly agitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride and polymers comprising ionic dissociative groups It may include, but is not limited to.

In one specific embodiment of the present invention, the solid polymer electrolyte is a polymer resin, copolymerized with an amorphous polymer such as PMMA, polycarbonate, polysiloxane (pdms) and/or phosphazene in a polyethylene oxide (PEO) backbone. It may include a mixture of one or two or more selected from the group consisting of branched copolymers, comb-like polymers and cross-linked polymer resins.

In addition, in a specific embodiment of the present invention, the polymer gel electrolyte comprises an organic electrolyte solution containing a lithium salt and a polymer resin, and the organic electrolyte solution may include 60 to 400 parts by weight based on the weight of the polymer resin. The polymer resin applied to the gel electrolyte is not limited to a specific component, for example, PVC (Polyvinyl chloride) based, PMMA (Poly (methyl methacrylate) based), polyacrylonitrile (Polyacrylonitrile, PAN), polyvinyl fluoride Liden (PVdF) and polyvinylidene fluoride-poly(vinylidene fluoride-hexafluoropropylene:PVdF-HFP) may be selected from the group consisting of one or two or more mixtures, but is not limited thereto.

In the electrolyte of the present invention, the lithium salt described above can be expressed as Li ⁺ X ^- as an ionizable lithium salt. In this lithium salt anion (X) is not particularly ^{limited, F -, Cl -, Br} -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, ( ^{_{CF 3) 2 PF 4 -,}} (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 ^{_{CF 2 SO 3 -, (CF}} 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) _{^{3 C -, (CF 3 SO}} 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN -, (CF 3 CF 2 SO 2) 2 N ^- and the like can be given.

Meanwhile, in one specific embodiment of the present invention, the polymer solid electrolyte may further include an additional polymer gel electrolyte. The polymer gel electrolyte has excellent ionic conductivity (or 10 ^-4 s/m or more), and has a binding property, which not only provides a function as an electrolyte, but also a binding force between electrode active materials and a binding force between an electrode layer and a current collector. The function of the provided electrode binder resin can be provided.

On the other hand, in the present invention, the solid electrolyte membrane may further include a crosslinking agent and/or an initiator when preparing a solid electrolyte layer when a polymer material is used as the electrolyte material of the solid electrolyte layer. The crosslinking agent and/or initiator may be initiated by a crosslinking reaction or a polymerization reaction depending on heat, light, and/or temperature conditions, and is not limited to a special component as long as it can induce crosslinking and/or polymerization of a polymer material. In one embodiment of the present invention, as the crosslinking agent and/or the initiator, an organic peroxide, an organometallic reagent such as silver alkylation, an azo-based compound, or the like may be used, but is not limited thereto.

Meanwhile, in the present invention, the inorganic solid electrolyte may be a sulfide-based solid electrolyte, an oxide-based solid electrolyte, or both.

In one specific embodiment of the present invention, the sulfide-based solid electrolyte is one that contains a sulfur atom in the electrolyte component, and is not limited to a specific component, crystalline solid electrolyte, amorphous solid electrolyte (glassy solid electrolyte), glass ceramic It may include one or more of the solid electrolyte. Specific examples of the sulfide-based solid electrolyte, LPS-type sulfide containing sulfur and phosphorus, Li _4-x Ge _1-x P _x S ₄ (x is 0.1 to 2, specifically x is 3/4, 2/3 ), Li _10±1 MP ₂ X ₁₂ (M=Ge, Si, Sn, Al, X=S, Se), Li _3.833 Sn _0.833 As _0.166 S ₄ , Li ₄ SnS ₄ , Li _3.25 Ge _0.25 P _0.75 S ₄ , Li ₂ SP ₂ S ₅ , B ₂ S ₃ -Li ₂ S, xLi ₂ S-(100-x)P ₂ S ₅ (x is 70 to 80), Li ₂ S-SiS ₂ -Li ₃ N, Li ₂ SP ₂ S ₅ -LiI, Li ₂ S-SiS ₂ -LiI, Li ₂ SB ₂ S ₃ -LiI, and the like, but are not limited thereto.

In one specific embodiment of the present invention, the oxide-based solid electrolyte is, for example, LLT-based perovskite structure such as Li _3x La _2/3-x TiO ₃ , Li ₁₄ Zn(GeO ₄ ) ₄ LISICON, LATP system such as Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , LAGP system such as (Li _1+x Ge _2-x Al _x (PO ₄ ) ₃ ), and phosphate system such as LiPON are appropriately selected. It can be used, and is not particularly limited thereto.

(2) suppression layer

The suppressing layer may have the suppressing material dispersed in an even distribution or a non-uniform distribution over the entire inhibitory layer. In one embodiment of the present invention, the suppression layer may be patterned in such a way that pattern units containing the suppression material are regularly or irregularly arranged in the suppression layer. The pattern unit is a high concentration of the inhibitory substance contained in the suppression layer, for example, means a portion contained in a concentration of 50% by weight or more in one pattern unit. The pattern unit may include only the inhibitor material or, if necessary, a mixture of the inhibitor material and the solid electrolyte material. Meanwhile, the non-coated portion that may exist between the pattern units may be embedded with a solid electrolyte layer stacked on the upper and lower portions of the suppression layer or filled with a separate solid electrolyte material. 5 is a schematic diagram of a cross-section of a solid electrolyte membrane including such a suppression layer. The pattern units are not limited to a special shape, and may have, for example, a stripe or dot plane shape.

In one embodiment of the present invention, the inhibitory layer may be formed by introducing an inhibitory substance into an appropriate solvent to prepare a solution of the inhibitory substance and coating it on the surface of the solid electrolyte layer. When the suppression layer is introduced in this manner, the thickness of the suppression layer can be made very thin. In addition, the solution can be coated so that the suppression layer has the shape of a stripe or a dot. In this case, since the thickness of the non-patterned portion where the pattern unit is not formed is very thin, it is buried by the solid electrolyte layer stacked on the upper and lower layers. It is possible to minimize the occurrence of separation or an increase in interfacial resistance.

In a specific embodiment of the present invention, the patterning of the suppression layer is a method of patterning and applying the mixture or solution, patterning the suppression layer on a separate release sheet, and then forming the patterned suppression layer as a solid electrolyte A method of transferring to a layer or a patterning method using lithography on a solid electrolyte layer can be applied. Meanwhile, when a pattern is applied to the suppression layer, the suppression material may be further exposed through O ₂ plasma, UV-ozone, etching, etc. after performing a patterning process.

In addition, in a specific embodiment of the present invention, it can be achieved by applying a method of self-assembly (self-assembly) of the polymer copolymer, through which the nanometer-level very fine pattern units in a uniform distribution to the suppression layer Can be aligned. The inhibitor layer formed by self-assembly of the polymer copolymer includes an inhibitor material and a polymer copolymer, and the inhibitor material is chemically bound to the polymer copolymer. In the present specification, the term “chemically bound” means that the inhibitory substance is bound to the polymer copolymer in a chemical manner such as ionic bond, covalent bond, and coordinate bond. Meanwhile, in the present specification, the dendrite growth inhibitory substance may be abbreviated and referred to as an inhibitory substance.

In the present invention, the inhibitory substance has a lower ionization tendency than lithium. The inhibitor material is less reactive than lithium, that is, it has a low ionization tendency. For this reason, it is possible to prevent lithium ions from being reduced and precipitated as a lithium metal by the inhibitory substance, and there is an effect of reducing the amount of dendrites by oxidizing the precipitated lithium back to lithium ions.

In the present invention, the inhibitory substance (a) is a1) a metal(s) having a lower ionization tendency than lithium; And a2) two or more alloy(s) among metals having a lower ionization tendency than lithium; It is derived from at least any one of these, and is a mixture containing at least one of their salts and their ions, and the mixture is distributed in the suppression layer. That is, the suppression layer includes at least one of a salt of the metal, a salt of the alloy, an ion of the metal, and an ion of the alloy.

In one embodiment of the present invention, the metal a1) is K, Sr, Ca, Na, Mg, Be, Al, Mn, Zn, Cr(+3), Fe, Cd, Co, Ni, Sn, Pb, Cu, Hg, Ag, Pd, Ir, Pt(+2), Au and Pt(+4). In addition, in the a2) alloy, two or more selected from the metal components are alloyed. In one embodiment of the present invention, the metal salt is, for example, chloride (chloride), iodide (iodide), cyanide (cyanide), boride (bromide), sulfide (hydride), phosphide (phosphite) ), one or more of chloride hydrate. However, if it is a form capable of reacting with the lithium metal and oxidizing the lithium metal in the form of ions, it is not limited and is not limited to the form. On the other hand, in one embodiment of the present invention, the inhibitory material has a lower ionization tendency, the higher the lithium dendrite growth inhibitory effect. Accordingly, the inhibitory material may include one or more of Au and Pt. In one embodiment of the present invention, when Au is used as the inhibitory substance, HAuCl ₄ ·3H ₂ O, which is a salt form thereof, may be introduced in the production of the inhibitory layer, and when Pt is used as the inhibitory substance, In the form of a salt, H ₂ PtCl ₆ ·H ₂ O can be added when preparing the inhibitory layer.

On the other hand, in the patterning of the inhibitory substance according to the self-assembly according to an embodiment of the present invention, the polymer copolymer is to include a functional group (functional group) capable of chemical bonding with the inhibitory substance, that is, the inhibitory substance It is combined with the polymer copolymer via the functional group. In one embodiment of the present invention, the functional group includes oxygen or nitrogen, and may include at least one selected from a functional group capable of binding to a metal salt, such as, for example, ether and amine. Can. In this functional group, an attraction force acts between the (-) charge of oxygen or nitrogen and the (+) charge of metal ions in the metal salt.

Such polymer copolymers include polystyrene-blockpooly (2-vinylpyridine) copolymer, polystyrene-block-poly(4-vinylpyridine) copolymer, poly(1,4-isoprene)-blockpolystyrene-block-poly(2-vinylpyridine) copolymer and polystyrene- There is a block-poly(ethylene oxide) copolymer, but it is not limited to a special type as long as it includes the above-described functional groups and can form a nano-scale fine pattern by self-assembly.

In one specific embodiment of the present invention, the suppression layer may exhibit a shape in which micelles formed by a self-assembled block copolymer are aligned according to a hexagonal dense structure. For example, when polystyrene-block-poly4vinyl pyridine is used as the block copolymer, micelles mainly containing polyvinylpyridine block (PVP) are arranged in a matrix mainly containing polystyrene block (PS) by self-assembly. The inhibitory material bound to the PVP block can ensure a high level of uniform dispersion across the entire inhibitory layer according to the arrangement of these micelles. The micelle may be composed of a core portion and a shell portion surrounding the surface of the core, and the inhibitory material is combined with the core portion and/or the shell portion. Figure 4 shows the AFM image of the suppression layer prepared in Example 1, it can be seen that the micelles are arranged in a hexagonal dense structure on the surface of the solid electrolyte layer.

In one specific embodiment of the present invention, the thickness of the suppression layer may be formed very thinly at a nanometer scale of less than 1 μm, preferably 100 nm or less, for example 80 nm or less, 70 nm or less, or 60 nm or less.

6 schematically shows a cross-section of the suppression layer. According to this, micelles, among them, the core portion is relatively thick, but the micelle and the micelle are relatively thin. Alternatively, a matrix may not be formed between micelles and micelles according to process conditions, for example, the speed of spin coating, the concentration of micelle solutions, and the like. Therefore, even if the suppression layer is disposed in a form that is coated on most of the surface of the solid electrolyte layer, lithium ions can be transmitted through the matrix, so that the ionic conductivity of the solid electrolyte layer can be properly maintained, and although somewhat reduced, it is a problem to use it as a solid electrolyte membrane There is no In one embodiment of the present invention, the thickness of the suppression layer may be controlled through O ₂ plasma or UV-ozone treatment. In this way, ion conduction is possible, and at the same time, lithium dendrite growth is suppressed by an inhibitory substance bound to the core of the micelle.

In one specific embodiment of the present invention, the size of the micelles may be 20 nm to 300 nm, and the spacing between micelles may be 10 nm to 500 nm.

As described above, the electrolyte membrane according to the present invention includes an inhibitory material that inhibits lithium growth, and thus, when applied to an all-solid battery containing lithium metal as a negative electrode active material, it is possible to effectively suppress a short circuit caused by lithium dendrite growth.

(3) Structure of solid electrolyte membrane

In one embodiment of the present invention, the solid electrolyte membrane includes a suppression layer including an inhibitory substance, and may include two or more solid electrolyte layers and one or more suppression layers, and the suppression layer is between the solid electrolyte layers. Is placed. For example, the solid electrolyte membrane may exhibit a layered structure in which the first solid electrolyte layer, the suppression layer, and the second solid electrolyte layer are sequentially stacked. Alternatively, the solid electrolyte membrane may include first, second, and third solid electrolyte layers, and a first suppression layer between the first and second solid electrolyte layers and a second suppression layer between the second and third solid electrolyte layers. 2 A suppression layer may be disposed. Each of the suppression layers is independent of each other in terms of shape or material, and any one suppression layer may be the same as or different from the other. In addition, each of the solid electrolyte layers is independent of each other in terms of shape or material, and any one solid electrolyte layer may be the same or different from the other.

In the present invention, the solid electrolyte membrane has a ionic conductivity of 1x10 ^-5 S/cm or more in a state in which an inhibitory layer is included.

The inhibitory layer is one in which the inhibitory substance is contained in a higher concentration than other layers (for example, a solid electrolyte layer). For example, the inhibitory layer may contain 10% by weight to 90% by weight of the inhibitory material relative to 100% by weight of the inhibitory layer. The content of the inhibitory substance may be 30% by weight or more, 50% by weight or more, 70% by weight or more, 80% by weight or more within the above range, and together or independently, the content is 80% by weight or less, 70% by weight or less, or 60 It may be less than or equal to weight percent. The concentration of the inhibitory substance can be appropriately adjusted in consideration of the dendrite inhibitory effect, the ionic conductivity of the solid electrolyte membrane, and the manufacturing cost of the battery due to the use of the noble metal as the inhibitory substance. Meanwhile, in one embodiment of the present invention, at least 50% by weight of 100% by weight of the total inhibitory substances included in the solid electrolyte membrane may be included in the suppression layer.

In one embodiment of the invention, it is preferred that the solid electrolyte layer has less than 80%, less than 70%, less than 60% or less than 50% of the area covered by the inhibitory layer relative to 100% of its surface area. When the suppression layer is formed in such a way that the surface of the solid electrolyte layer is excessively covered, the ion conduction path may be blocked by the suppression layer, thereby deteriorating the ion conductivity characteristics of the solid electrolyte membrane. When the coverage area of the suppression layer satisfies the above range, the lithium dendrite growth suppression effect is high, and a decrease in lithium ion conductivity due to formation of the suppression layer can be prevented. However, the shapes of the above-described suppression layer and the solid electrolyte membrane are exemplary and can be applied without particular limitations as long as the shapes of the structural features of the present invention can be implemented.

In one specific embodiment of the present invention, the suppression layer may have a thickness greater than 0 and 1 μm, and may be 700 nm or less, 500 or less, 300 nm or less, 100 nm or less, or 50 nm or less within the above range.

In the present invention, the thickness of the suppression layer, the concentration of the suppression layer increase inhibitor material, the area where the suppression layer covers the solid electrolyte layer, etc. can be appropriately adjusted in consideration of the ion conductivity of the solid electrolyte membrane. That is, the suppression layer included in the solid electrolyte membrane has a suitable range of the thickness of the suppression layer, the concentration of the suppression material, and the covering area of the solid electrolyte layer by the suppression layer so that the solid electrolyte membrane can exhibit an ion conductivity of 1x10 ^-5 S/cm or more. It can be adjusted to have.

In one embodiment of the present invention, the suppressing layer may be formed by the following method. However, the present invention is not limited thereto, and any structure may be applied as long as the micelles are aligned by self-assembly. For example, an appropriate polymer copolymer capable of self-assembly is introduced into a solvent to prepare a polymer solution, and an inhibitor is introduced into the polymer solution to prepare a mixture for forming an inhibitor. The polymer solution and the mixture may be subjected to a stirring process for uniform dispersion of the components added in the solvent. In particular, chemical bonding between the inhibitor and the polymer copolymer may be promoted by stirring the mixture. Next, the thus prepared mixture is applied to the surface of the prepared solid electrolyte layer and dried to induce self-assembly. The coating may be, for example, a spin coating method. At this time, the coating speed may be controlled in a range of about 1,000 rpm to 5,000 rpm. On the other hand, in the present invention, the solvent may include one or more selected from toluene, tetrahydrofuran, ethylene, acetone, chloroform, and dimethylformamide (DMF), for example, the side of arrangement of micelles of hexagonal dense structure In the solvent, toluene may be included.

In addition, the first and second solid electrolyte layers include an ion conductive solid electrolyte material, and may further include an inhibitory material, a binder resin, or both, if necessary. In the first and second solid electrolyte layers, the inhibitory material may be dispersed in a uniform distribution. In addition, the inhibitory substance in 100% by weight of the solid electrolyte layer may be included in a proportion of 0% to 50% by weight. The content of the inhibitory substance in the solid electrolyte layer may be 40% by weight or less, 30% by weight or less, 20% by weight or 10% by weight or less within the above range.

The suppression material and the ion conductive solid electrolyte material included in the suppression layer and the first and second solid electrolyte layers may refer to the foregoing.

Meanwhile, in one specific embodiment of the present invention, the compositions of the ion conductive solid electrolytes included in the first and second solid electrolyte layers may be the same or different. For example, the first layer may include an oxide-based solid electrolyte material, and the second layer may include a sulfide-based solid electrolyte material.

In one embodiment, the solid electrolyte membrane may be made by forming a first solid electrolyte layer and then forming a suppression layer on its surface and forming a second solid electrolyte layer on the surface of the suppression layer. If two or more suppression layers are included, a method of forming a suppression layer on the surface of the second solid electrolyte layer and then forming a third solid electrolyte layer thereon may be prepared. In one embodiment of the present invention, when manufacturing a solid electrolyte membrane including more than one suppression layer or solid electrolyte layer, the method of forming the suppression layer and the solid electrolyte layer may be repeatedly performed.

(3) All-solid battery

The present invention provides an all-solid-state battery comprising the solid electrolyte membrane. In one embodiment of the present invention, the all-solid-state battery includes a negative electrode, a positive electrode, and a solid electrolyte membrane interposed between the negative electrode and the positive electrode, wherein the solid electrolyte membrane has the aforementioned characteristics.

On the other hand, in one embodiment of the present invention, the all-solid-state battery is disposed such that the first solid electrolyte layer of the electrolyte membrane contains a lower concentration of the inhibitory substance than the inhibitory layer, and the first solid electrolyte layer faces the negative electrode. Can be. In the all-solid-state battery of this structure, the first solid electrolyte layer has a higher concentration of the inhibitor compared to the second solid electrolyte layer, or the first solid electrolyte layer has a thicker thickness than the second solid electrolyte layer. Both of these features can be provided.

In addition, in one embodiment of the present invention, an element such as a separate protective layer may be further added to the surface of the solid electrolyte membrane facing the negative electrode. In particular, a passivation film using an inorganic solid electrolyte, an inorganic material such as LiF, Li ₂ O, or an organic material such as PEO may be disposed for the purpose of suppressing the reaction by direct contact with Li metal.

In the present invention, the negative electrode may include a current collector, a negative electrode active material layer formed on the surface of the current collector, and the negative electrode active material layer includes one or more elements belonging to alkali metal, alkaline earth metal, group 3B, and transition metal. can do. In one specific embodiment of the present invention, the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or francium (Fr) as a non-limiting example of the alkali metal And at least one metal selected from, and preferably contains lithium. In one specific embodiment of the present invention, the negative electrode may be a negative electrode current collector and a lithium metal thin film having a predetermined thickness bonded by compression to be stacked.

In the present invention, the positive electrode includes a current collector and a positive electrode active material layer formed on at least one side of the current collector, and the positive electrode active material layer includes a positive electrode active material, a solid electrolyte, and a conductive material. In addition, in one specific embodiment of the present invention, the positive electrode active material layer may further include a binder material. The binding of the positive electrode active material layer to the current collector and/or the solid electrolyte membrane may be increased due to the introduction of the binder material, and it also helps to improve the binding force between the components included in the positive electrode active material independently or simultaneously.

The positive electrode active material may be used without limitation as long as it can be used as a positive electrode active material of a lithium ion secondary battery. For example, the positive electrode active material may include a layered compound such as lithium cobalt oxide (LiCoO ₂ ) and lithium nickel oxide (LiNiO ₂ ), or a compound substituted with one or more transition metals; Lithium manganese oxides such as the formula Li _1+x Mn _2-x O ₄ (where x is 0 to 0.33), LiMnO ₃ ,LiMn ₂ O ₃ ,LiMnO ₂ ; Lithium copper oxide (Li ₂ CuO ₂ ); vanadium oxide such as LiV ₃ O ₈ ,LiFe ₃ O ₄ ,V ₂ O ₅ ,Cu ₂ V ₂ O ₇ ; Represented by the formula LiNi _1-x M _x O ₂ (where M = Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and includes one or more of the above elements, x = 0.01 to 0.3) Lithium nickel oxide, for example LiN _0.8 C _0.1 M _0.1 O ₂ ; Formula LiMn _2-x M _x O ₂ (where M = Co, Ni, Fe, Cr, Zn or Ta, x = 0.01 to 0.1) Or Li ₂ Mn ₃ MO ₈ (where M = Fe, Co, Ni, Cu or Zn); A lithium manganese composite oxide having a spinel structure represented by LiNi _x Mn _2-x O ₄ ; LiMn ₂ O _{4 in} which a part of Li in the formula is substituted with alkaline earth metal ions; a disulfide compound; Fe ₂ (MoO ₄ ) ₃ and the like. However, it is not limited to these.

The conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery. For example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers such as VGCF (Vapor grown carbon fiber); Metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; It may include one or a mixture of two or more selected from conductive materials such as polyphenylene derivatives.

The binder material is not particularly limited as long as it is a component that assists in the bonding of the active material and the conductive material and the like to the current collector, for example, polyvinylidene fluoride polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, and hydroxy Roxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluorine rubber, various aerials Coalescence and the like. The binder resin may be usually included in the range of 1 to 30% by weight, or 1 to 10% by weight relative to 100% by weight of the electrode layer.

In one embodiment of the present invention, the negative electrode and/or positive electrode may further include various additives for the purpose of supplementing or improving physical and chemical properties. The additive is not particularly limited, but may include one or more additives such as an oxidation stabilizer additive, a reducing stable additive, a flame retardant, a heat stabilizer, and an antifogging agent.

In addition, the current collector is generally made to a thickness of 3 to 500 μm. The current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. For example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surfaces made of carbon, nickel, titanium, silver, or the like may be used. Among them, it may be appropriately selected and used according to the polarity of the positive electrode or the negative electrode.

In addition, the present invention provides a battery module including the secondary battery as a unit battery, a battery pack including the battery module, and a device including the battery pack as a power source.

At this time, as a specific example of the device, a power tool (power tool) moving under power by an omniscient motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; And a power storage system, but is not limited thereto.

(4) Manufacturing method of solid electrolyte membrane

Next, a method of manufacturing a solid electrolyte membrane having the above-described characteristics will be described. The manufacturing method described below is one of various methods that can be employed in manufacturing the solid electrolyte membrane according to the present invention, but is not limited thereto. First, a first solid electrolyte layer is prepared. The electrolyte layer may be in accordance with a method for preparing a solid electrolyte layer according to an embodiment of the present invention, and is not limited to a specific method. For example, when the electrolyte layer is a polymer electrolyte, the solid electrolyte layer may be prepared in the following manner. A polymer solution is prepared by dissolving a polymer resin in an appropriate solvent such as acetonitrile, and a lithium salt is added thereto to prepare a slurry for forming an electrolyte layer. The slurry may be heated to an appropriate temperature for dissolving the polymer resin and lithium salt, and may be stirred for several hours to several tens of hours. In addition, the polymer solution may further include an initiator and a curing agent. The initiator and the curing agent may be added to the slurry by separately preparing an additive solution containing the initiator and the curing agent, or added together to the polymer solution. In one specific embodiment of the present invention, the initiator may be included in the range of about 10 to 20 parts by weight relative to the polymer resin used, and the curing agent may be included in the range of about 0.2 to 3 parts by weight compared to the polymer resin used. Then, the prepared slurry is applied to a release film and dried. In this way, the first solid electrolyte layer can be obtained. The release film may be removed in the final step after removing the release film and using a first solid electrolyte layer or forming a solid electrolyte membrane having all the elements.

Next, a suppression layer is formed on the surface of the first solid electrolyte layer. The method of forming the suppression layer may refer to the above.

Then, a second solid electrolyte layer is formed on the surface of the suppression layer. The second solid electrolyte layer prepares a slurry for forming a second solid electrolyte layer like the first solid electrolyte layer, and then applies it to the surface of the suppression layer and dries it to prepare in an integral form with the suppression layer, or a first solid electrolyte. After coating on the surface of a separate release film, such as layer formation, the release film can be removed and bonded to the surface of the suppression layer by calendering or lamination.

Meanwhile, in a specific embodiment of the present invention, a suppression layer is further formed on the surface of the second solid electrolyte layer, and a third solid electrolyte layer is disposed on the surface of the suppression layer to include two or more suppression layers. It can provide a solid electrolyte membrane in the form.

The above manufacturing method has been described in which each solid electrolyte layer includes a polymer solid electrolyte, but the present invention is not limited thereto, and each solid electrolyte layer may include an inorganic solid electrolyte by replacing the polymer solid electrolyte with an electrolyte material or together. Can.

Hereinafter, the present invention is further described through examples, but the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

(1) Preparation of the first solid electrolyte layer

A polymer solution of 4 wt% was prepared by dissolving polyethylene oxide (PEO, Mw=4,000,000 g/mol) in a solvent acetonitrile (AN). At this time, LiTFSI was added as a lithium salt so that [EO]/[Li+]=18/1 (molar ratio). The polymer solution was stirred overnight at 70° C. so that PEO and lithium salt were sufficiently soluble. Next, an additive solution including an initiator and a curing agent was prepared. The curing agent uses PEGDA (Mw=575), and the initiator uses benzoyl peroxide (BPO). Polyethylene glycol diacrylate (PEGDA) is 20 wt% compared to PEO, and BPO has an amount of 1% PEGDA. Acetonitrile was used as a solvent. The additive solution was stirred for about 1 hour so that the added components were well mixed. Thereafter, the additive solution was added to the polymer solution and the two solutions were sufficiently mixed. The mixed solution was applied and coated on a release film using a doctor blade. The coating gap was 800 µm and the coating speed was 20 mm/min. The release film coated with the solution was moved to a glass plate to maintain a good level, dried overnight at room temperature, and vacuum dried at 100° C. for 12 hours. In this way, a first solid electrolyte layer was obtained. The thickness of the obtained first solid electrolyte layer was about 50 μm.

(2) Preparation of suppression layer

Polystyrene-block-poly4vinyl pyridine (S4VP, PS Mn 41.5kg/mol, P4VP Mn 17.5kg/mol) was stirred in toluene at a concentration of 0.5wt% at room temperature for 1 day. In this solution, after adding HAuCl _{4 ·} 3H ₂ O at a concentration of 2 wt% compared to P4VP, the mixture was stirred for 6 hours to allow Au ions to bind in the S4VP micelle. The solution was spin-coated on the obtained first solid electrolyte layer at a speed of 3,000 rpm to pattern a single layer of S4VP micelles through self-assembly. Figure 4 shows the AFM image of the obtained suppression layer. The light portion represents the micelle portion, and the dark portion represents the first solid electrolyte layer portion. At this time, the size of the micelle was 40 nm, and the interval between micelles was about 70 nm.

(3) Preparation of the second solid electrolyte layer

A second solid electrolyte layer was prepared in the same manner as in the preparation of the first solid electrolyte layer.

(4) Preparation of multi-layered solid electrolyte membrane

The first solid electrolyte membrane and the second solid electrolyte membrane coated with the suppression layer were superimposed, and the distance between the rolls was adjusted to 100 μm and calendered at 60°C. At this time, the suppression layer was disposed between the first and second solid electrolyte membranes. In this way, a solid electrolyte membrane in which the first solid electrolyte membrane, the suppression layer, and the second solid electrolyte membrane were sequentially stacked was obtained. The thickness of the obtained solid electrolyte membrane was about 100 μm. It was found that the suppression layer of the solid electrolyte membrane was formed so thin that it did not affect the total thickness of the solid electrolyte membrane.

Example 2

When preparing the solid electrolyte membrane, a solid electrolyte membrane was prepared in the same manner as in Example 1, except that the concentration of HAuCl4 in the suppression layer was 5 wt% compared to S4VP.

Example 3

A solid electrolyte membrane was prepared in the same manner as in Example 1, except that a polystyrene-block-poly2vynil pyridine (S2VP, PS Mn 133kg/mol, P2VP Mn 132kg/mol) was used as the block copolymer of the inhibitory layer when preparing the solid electrolyte membrane. .

Comparative Example 1

A solid electrolyte membrane was prepared in the same manner as in Example 1, except that the suppression layer was not inserted when preparing the solid electrolyte membrane.

Comparative Example 2

HAuCl ₄ ·3H ₂ O was added to toluene and mixed to prepare a solution for forming an inhibitory layer, and this was applied to a first solid electrolyte layer and dried to form an inhibitory layer. A solid electrolyte membrane was prepared in the same manner as in Example 1 except for this. The amount of HAuCl ₄ ·3H ₂ O in the inhibitory layer was the same as in Example 2.

Performance evaluation 1: Ion resistance measurement

The solid solid electrolyte membrane obtained in each of the examples and comparative examples was cut to a size of 1.7671 cm ² . This was placed between two sheets of stainless steel (SUS) to produce a coin cell. This was measured using an analytical device (VMP3, Bio logic science instrument), electrochemical impedance at 60°C under the conditions of amplitude 10mV and scan range 500khz to 0.1mHz.

Performance evaluation 2: discharge capacity

All-solid-state batteries were prepared using the solid electrolyte membranes of Examples 1 to 3 and Comparative Examples 1 and 2.

Preparation of positive electrode: NCM811 (LiNi _0.8 Co _0.1 Mn _0.1 O ₂ ) for electrode active material, VGCF (Vapor grown carbon fiber) and polymer solid solid electrolyte (PEO + LiTFSI, 18:1 mol) B) was mixed in a weight ratio of 80:3:17, added to acetonitrile, and stirred to prepare an electrode slurry. An aluminum current collector having a thickness of 20 μm was prepared. The slurry was applied to the current collector using a doctor blade and the resultant was dried under vacuum at 120° C. for 4 hours. A rolling process was performed using a roll press to obtain an electrode having an electrode loading of ² mAh/cm ^2, an electrode layer thickness of 48 μm, and a porosity of 22%.

Preparation of battery: The electrode prepared above was prepared by punching in a circle of 1.4875 cm ² . A lithium metal thin film cut into a circle of 1.7671 cm ² was prepared as a counter electrode. A solid electrolyte membrane obtained in each of the above Examples and Comparative Examples was placed between the two electrodes to produce a coin-type half-cell.

Each battery prepared above was charged and discharged at about 60° C. to evaluate the initial discharge capacity.

Charging conditions: CC (constant current)/CV (constant voltage), (4.15V, 0.05C, 0.005C current cut-off)

Discharge conditions: CC (constant current) 3V (0.05C)

The evaluation results for the above items are summarized in Table 1 below.

Ionic conductivity
(S/cm, 60℃) Discharge capacity
(mAh/g, 4.15V) When a short circuit occurs
(cycle) Example 1 8E-05 151 17 Example 2 8E-05 150 20 Example 3 8E-05 142 14 Comparative Example 1 1E-04 156 5 Comparative Example 2 1E-04 158 14

As shown in the above experimental results, it can be seen that Li dendrite is converted back to Li ion through chemical reaction with Au metal ions, thereby improving life characteristics. At this time, the amount of metal ions or the uniformity of the coating layer becomes important. In particular, the metal ions arranged at the nano scale through self-assembly of the block copolymer showed more effective life-span improvement. The following picture is an AFM picture of the surface of the suppression layer produced through Example 1, and it can be seen that micelles containing metal ions form a certain pattern on the first solid layer.

[Description of codes]

10 all-solid-state battery, 11 current collector, 12 positive electrode, 13 solid electrolyte membrane, 14 negative electrode (lithium metal), 14a dendrites

130 solid electrolyte membrane, 131 second solid electrolyte layer, 132 suppressing layer, 133 first solid electrolyte layer

200 all-solid-state battery, 210 current collector, 220 anode, 231 second solid electrolyte layer, 232 inhibitory layer, 233 first solid electrolyte layer, 240 cathode (lithium metal), 241 dendrites

330 solid electrolyte membrane, 331 second solid electrolyte layer, 333 first solid electrolyte layer, 332 inhibitory layer

430 solid electrolyte membrane, 431 second solid electrolyte layer, 433 first solid electrolyte layer, 432 inhibitory layer, 432a micelle

Claims (15)

As a solid electrolyte membrane for an all-solid battery,
The solid electrolyte membrane has an ion conductivity of 1x10 ^-7 S/cm or more,
The solid electrolyte membrane includes at least one inhibitor layer including a dendrite growth inhibitory substance (a), and the dendrite growth inhibitory substance (a) is (a1) a metal(s) and (a2) having a lower ionization tendency than lithium. It is derived from any one of two or more alloy(s) of the metals, and is included in the suppression layer in the form of at least one of their salts and ions thereof,
The suppression layer is patterned by including a plurality of pattern units comprising an inhibitory material, and the pattern units are solid electrolyte membranes that are regularly or irregularly distributed in the suppression layer.
According to claim 1,
The inhibitory layer includes a dendrite growth inhibitory substance (a) and a polymer copolymer in which the inhibitory substance is chemically bound, and has a fine pattern derived from self-assembly of the polymer copolymer,
The polymer copolymer comprises a functional group capable of chemically bonding with the inhibitory substance, and the inhibitory substance is a solid electrolyte membrane in which the inhibitory substance is combined with the polymer copolymer via the functional group.
According to claim 2,
The inhibiting layer is a solid electrolyte membrane having a shape in which micelles are aligned according to a hexagonal dense structure by self-assembly of the polymer copolymer.
According to claim 1,
The functional group is a solid electrolyte membrane that is at least one of ether and amine.
According to claim 1,
The polymer copolymers are polystyrene-blockpooly(2-vinylpyridine) copolymer, polystyrene-block-poly(4-vinylpyridine) copolymer, poly(1,4-isoprene)-blockpolystyrene-block-poly(2-vinylpyridine) copolymer and polystyrene- Solid electrolyte membrane containing one or more selected from block-poly(ethylene oxide) copolymer
According to claim 1,
The metal is K, Sr, Ca, Na, Mg, Be, Al, Mn, Zn, Cr(+3), Fe, Cd, Co, Ni, Sn, Pb, Cu, Hg, Ag, Pd, Ir, Pt (+2), Au and Pt (+4), a solid electrolyte membrane comprising at least one selected from the group consisting of.
The method of claim 6,
The inhibitory substance will include one or more selected from the group consisting of Au and Pt, a solid electrolyte membrane.
According to claim 1,
The metal salt is one of chloride, iodide, cyanide, boride, sulfide, hydride, phosphite and chloride hydrate. That is, the solid electrolyte membrane.
According to claim 1,
The solid electrolyte membrane includes two or more solid electrolyte layers and one or more suppression layers, wherein the suppression layer is disposed between the solid electrolyte layers.
The method of claim 9,
The solid electrolyte membrane is a solid electrolyte membrane in which a first solid electrolyte layer, a suppression layer and a second solid electrolyte layer are sequentially stacked.
The method of claim 9,
At least one of the two or more solid electrolyte layers includes an inhibitor material, and the content of the inhibitor material (% by weight) in each solid electrolyte layer is lower than the content of the inhibitor material (% by weight) contained in the inhibitor layer .
According to claim 1,
The solid electrolyte membrane includes an ion conductive solid electrolyte material, and the ion conductive solid electrolyte material comprises a polymer solid electrolyte, an inorganic solid electrolyte, or a mixture of both.
The method of claim 12,
The polymer solid electrolyte comprises a polymer resin and a solvated lithium salt, a solid electrolyte membrane.
An all-solid-state battery comprising a negative electrode, a positive electrode, and a solid electrolyte membrane interposed between the negative electrode and the positive electrode, wherein the negative electrode contains lithium metal, and the solid electrolyte membrane is according to claim 1.
The method of claim 14,
In the solid electrolyte membrane, the first solid electrolyte layer, the suppression layer, and the second solid electrolyte layer are sequentially stacked, and the first solid electrolyte layer includes the suppression material (a), and the suppression material is (a1) than lithium. An electrochemical device that is derived from any one of metal(s) and (a2) two or more of the metal(s) having a low ionization tendency.

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