Electrolyte and battery containing the electrolyte

Abstract

An electrolyte comprising a porous insulator having pores, and a metal salt and a medium disposed in the pores, wherein the metal salt is at least one kind selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio (medium / metal salt) of the medium to the metal salt is 0.1-2.0.

Description

[Technical Field]

[0001] The present disclosure relates to electrolytes and batteries comprising the electrolytes. [Background technology]

[0002] Batteries include air batteries, fuel cells, secondary batteries, etc., and are used for a variety of purposes. Batteries include a positive electrode and a negative electrode, and an electrolyte that transports ions between the positive electrode and the negative electrode.

[0003] For example, Patent Document 1 discloses an insulating structure made of a porous coordination polymer having metal salt coordinated unsaturated sites and a [R-SO2-N-SO2-R'] - (R and R' represent fluorine atoms or fluoroalkyl groups) and a metal cation (e.g., Li + , Na + , or Mg 2+ ) and an ion-conductive composite (electrolyte) comprising the same is disclosed.

[0004] Furthermore, Patent Document 2 discloses an electrolyte regulator that can be used in metal batteries, the electrolyte regulator comprising a liquid electrolyte and a metal-organic framework (MOF) material that is incorporated into the liquid electrolyte to form a MOF slurry electrolyte, where MOFs are a class of crystalline porous solids constructed from metal cluster nodes and organic linkers, and that are capable of binding anions, removing ion pairs, and enhancing cation transport upon activation and impregnation with the liquid electrolyte. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6222635 [Patent Document 2] Special Publication No. 2020-508542 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have realized that there are still problems to be overcome with the above electrolytes and have found the need to take measures to solve these problems. Specifically, the present inventors have found that there is room for improvement in the ionic conductivity of the electrolytes.

[0007] The present disclosure has been made in view of the above-mentioned problems. That is, a main object of the present disclosure is to provide an electrolyte having superior ionic conductivity compared to conventional electrolytes. [Means for solving the problem]

[0008] The present inventors attempted to solve the above problems by taking a new approach rather than simply extending the conventional technology, and as a result, they have invented an electrolyte that achieves the above-mentioned main object.

[0009] The electrolyte according to one embodiment of the present disclosure comprises: A porous insulator having pores, and a medium and a metal salt disposed in the pores, the metal salt is at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, The molar ratio of the medium to the metal salt (medium / metal salt) is 0.1 or more and 2.0 or less.

[0010] Moreover, the battery according to an embodiment of the present disclosure comprises: The electrolyte is as described above. [Effects of the Invention]

[0011] The present disclosure can provide an electrolyte with superior ionic conductivity. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a conceptual diagram showing an example of a battery according to a second embodiment of the present disclosure. [Figure 2]FIG. 2 shows Raman spectra in the range of 550 to 600 cm −1 of the electrolytes of Examples 1 to 8 and Comparative Examples 1 and 2. [Figure 3] FIG. 3 shows Raman spectra in the range of 680 to 780 cm −1 of the electrolytes of Examples 1 to 8 and Comparative Examples 1 and 2. [Figure 4] FIG. 4 is a graph showing the relationship between the molar ratio (SL / LiFSI) and the ionic conductivity at room temperature. [Figure 5] FIG. 5 is a graph showing the relationship between the molar ratio (EC / LiFSI) and the ionic conductivity at room temperature. [Figure 6] FIG. 6 shows Raman spectra of the electrolytes of Examples 23, 25 and 26 and Comparative Example 1 in the range of 870 to 930 cm −1 . [Figure 7] FIG. 7 shows Raman spectra in the range of 680 to 800 cm −1 of the electrolytes of Examples 23, 25 to 26 and Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0013] The "electrolyte" and the "battery" including the electrolyte of the present disclosure will be described in detail below with reference to the following embodiments. While the description will be made with reference to the drawings as needed, the contents shown in the drawings are merely shown as a schematic example for the purpose of understanding the present disclosure, and the appearance and dimensional ratios may differ from the actual products.

[0014] Numerical ranges mentioned in this specification are intended to include the lower and upper limit values ​​themselves, unless otherwise specified, such as "less than," "smaller," or "greater than." That is, for example, a numerical range such as 1 to 10 is interpreted as including the lower limit of 1 and the upper limit of 10.

[0015] In this specification, "a target component is substantially composed of a specific material" or "a target component consists of a specific material" means that the target component contains the specific material at a ratio of 95% by mass or more, 97% by mass or more, 99% by mass or more, or 100% by mass. For example, "mesoporous silica is substantially composed of silica (SiO2)" means that the mesoporous silica contains silica (SiO2) at a ratio of 95% by mass or more, 97% by mass or more, 99% by mass or more, or 100% by mass.

[0016] In this disclosure, the term "battery" broadly refers to a device equivalent to 1 or 2 that can extract energy using an electrochemical reaction. In a narrower sense, the term "battery" refers to a device that includes a pair of electrodes and an electrolyte, and that is charged and discharged particularly through the movement of ions. By way of example only, examples of batteries include primary batteries and secondary batteries, and more specifically, lithium batteries, magnesium batteries, sodium batteries, and potassium batteries.

[0017] In this disclosure, unless otherwise specified, the term "electrolyte solution" refers to the electrolyte according to the present disclosure excluding the porous insulator, and is composed of a metal salt and a medium.

[0018] <First embodiment: electrolyte> The electrolyte according to the first embodiment of the present disclosure is used in, for example, a battery. That is, the electrolyte described in this specification corresponds to an electrolyte for a device capable of extracting energy by utilizing an electrochemical reaction.

[0019] The electrolyte according to the first embodiment is, as a premise, an electrolyte used in a battery having an electrode composed of lithium, magnesium, sodium, or potassium. In particular, it is an electrolyte for a battery having a lithium electrode as the negative electrode. Therefore, the electrolyte according to the first embodiment can also be said to be an electrolyte for a lithium electrode-based battery (hereinafter, also simply referred to as a "lithium electrode-based electrolyte").

[0020] Here, the term "lithium electrode" as used herein broadly refers to an electrode having lithium (Li) as the active component (i.e., active material). In a narrower sense, "lithium electrode" refers to an electrode comprising lithium, for example, an electrode comprising lithium metal or a lithium alloy, particularly a negative electrode of such lithium. While such a lithium electrode may contain components other than lithium metal or a lithium alloy, in a preferred embodiment it is an electrode made of a lithium metal body (for example, an electrode made of lithium metal with a purity of 90% or more, preferably 95% or more, and more preferably 98% or more).

[0021] The electrolyte according to the first embodiment has Li ion conductivity in the case of a lithium electrode system. The ionic conductivity of the electrolyte according to the first embodiment is, for example, 10 -4 The value is on the order of S / cm or more. The method for measuring ionic conductivity will be described in detail in the Examples.

[0022] The electrolyte according to the first embodiment is A porous insulator having pores, a medium (medium molecules) and a metal salt disposed in the pores, the metal salt is at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts; The molar ratio of the medium to the metal salt (medium / metal salt) is 0.1 or more and 2.0 or less.

[0023] (molar ratio (medium / metal salt)) The molar ratio of the medium to the metal salt (medium / metal salt) is 0.1 or more and 2.0 or less. If the molar ratio is less than 0.1 or more than 2.0, the ionic conductivity decreases. From the viewpoint of further improving the ionic conductivity of the electrolyte, the lower limit of the molar ratio is preferably 0.2, more preferably 0.3, and the upper limit of the molar ratio is preferably 1.9, more preferably 1.5, even more preferably 1.2, particularly preferably 1.0, and very preferably 0.8. By arbitrarily selecting and combining from the above multiple suitable numerical ranges, a suitable numerical range of the molar ratio (a numerical range including the upper and lower limits) can be achieved. For example, the molar ratio is preferably 0.2 or more and 2.0 or less.

[0024] In particular, the molar ratio (sulfolane / LiFSi) is preferably 0.1 to 1.5, more preferably 0.2 to 1.2, even more preferably 0.2 to 1.0, and particularly preferably 0.3 to 0.5. The molar ratio (ethylene carbonate / LiFSi) is preferably 0.2 to 2.0, more preferably 0.3 to 1.0.

[0025] -Method for determining the molar ratio (medium / metal salt)- The molar ratio (medium / metal salt) can be determined by the amounts of the medium and metal salt (molar ratio in the raw material state) that constitute the electrolyte according to this embodiment, or the molar ratio (medium / metal salt) can be determined from the electrolyte (as a finished product).

[0026] [Mechanism of action] The electrolyte according to this embodiment has superior ionic conductivity. Without being bound by any particular theory, the reason for this is presumed to be as follows: In the electrolyte according to this embodiment, a bridge structure can be formed by combining a metal salt and a medium at a specific molar ratio (medium / metal salt = 0.1 to 2.0). Specifically, the electrolyte according to this embodiment can have at least one of a bridge structure (hereinafter also referred to as a "first bridge structure") in which the medium and positive ions (more specifically, metal ions) constituting the metal salt are alternately arranged, and a bridge structure (hereinafter also referred to as a "second bridge structure") in which positive ions constituting the metal salt and negative ions constituting the metal salt are alternately arranged.

[0027] When the first bridge structure and the second bridge structure are disposed in the pores of the porous insulator, they form defects (holes) in which metal ions are partially missing, which can serve as paths for efficient transport of metal ions within the electrolyte. Therefore, in the electrolyte according to this embodiment, the formation of the above bridge structures in the pores of the porous insulator increases the ionic conductivity of metal ions.

[0028] (Motivation behind the invention of this disclosure) When porous insulators are impregnated with the electrolyte used in lithium-ion batteries, the ionic conductivity is still low. The present inventors have intensively investigated the concept of increasing ionic conductivity, and as a result, have found that forming bridge structures within the pores and propagating metal ions through at least one of the first and second bridge structures within the pores increases ionic conductivity compared to the mechanism in which metal ions propagate through the pores in a solvated state. This led the inventors to conceive of the electrolyte according to this embodiment, which enhances ion conductivity through a completely new mechanism that does not exist in conventional concepts, namely, carrier transport through at least one of the first bridge structure and the second bridge structure.

[0029] (First bridge structure) The electrolyte according to this embodiment preferably has a first bridge structure, from the viewpoint of further improving ionic conductivity. In the first bridge structure, the medium and the positive ions constituting the metal salt are alternately arranged, and some of the positive ions (metal ions) are missing. [Chemical Formula 1] [ka] The first bridge structure will be described in detail with reference to Chemical Formula 1. Chemical Formula 1 shows an example of an electrolyte according to this embodiment, in which sulfolane as a medium and metal ions Li are mixed in the pores of a porous insulator. + and an electrolyte containing a metal salt (sulfolane-Li + The following electrolytes are listed: sulfolane-Li + In the electrolyte of this system, the first bridge structure is formed by the sulfonyl group (oxygen atom) of sulfolane. + coordinates to sulfolane and Li + and are arranged alternately in one dimension, and in some places Li + It has a defect (dashed circle in [Chemical formula 1]) where Li + When the first bridge structure is viewed from the viewpoint of the first bridge structure, the first bridge structure is + is bridged by sulfolane. + Because of the presence of defects, the adjacent Li + can move to the defect. + can move sequentially within the first bridge structure, the first bridge structure contributes to efficient transport of metal ions within the electrolyte, and is thought to achieve better ionic conductivity.

[0030] In the first bridge structure, the one-dimensional arrangement means, for example, a combination of sulfolane and Li + However, sulfolane and Li + The arrangement of sulfolane and Li is not limited to this. + The arrangement may be two-dimensional or three-dimensional, and more specifically, the linear arrangement may be curved or branched.

[0031] (How to check the first bridge structure) The first bridge structure can be confirmed by structural analysis using Raman spectroscopy. As described above, the first bridge structure can be constructed by the coordination of metal ions of a metal salt to a medium. In other words, the first bridge structure can be constructed by the metal ions forming a coordinate bond with a specific functional group of the medium. Therefore, the presence of the first bridge structure can be confirmed by using microscopic Raman spectroscopy to confirm that "the peak derived from the specific vibration of the functional group forming the coordinate bond is shifted to the higher wavenumber side compared to the peak derived from the specific vibration of the functional group in an uncoordinated state."

[0032] For example, the above sulfolane-Li + The presence of the first bridge structure in the electrolyte can be confirmed by using micro-Raman spectroscopy to confirm that "in the Raman spectrum, the peak (Raman scattering peak) originating from the SO2 deformation vibration of the sulfonyl group of the medium shifts to the higher wavenumber side." This can be confirmed by the peak attributable to the O=S=O deformation vibration of the sulfonyl group in the state coordinated to the metal ion shifting to the higher wavenumber side compared to the peak (known peak) attributable to the O=S=O deformation vibration of the sulfonyl group in the state not coordinated to the metal ion.

[0033] Also, ethylene carbonate-Li + The presence of the first bridge structure in the electrolyte of this system can be confirmed by the shift of the peak due to the breathing vibration of the heterocycle of the medium (ethylene carbonate) to the higher wavenumber side. + The presence of the first bridge structure in the electrolyte of the system can be confirmed by the shift of the peak due to the stretching vibration of the hetero ring of the medium (GBL) to the higher wavenumber side. A method for checking the first bridge structure will be described in detail in the Examples.

[0034] (Second bridge structure) The electrolyte according to this embodiment preferably has a second bridge structure, from the viewpoint of further improving ionic conductivity. In the second bridge structure, positive ions constituting the metal salt and negative ions constituting the metal salt are alternately arranged. [Chemical Formula 2] [ka] The second bridge structure will be described in detail with reference to Chemical Formula 2. Chemical Formula 2 shows the metal ion Li in the pores of a porous insulator as an example of an electrolyte according to this embodiment. + and an electrolyte containing a metal salt composed of an anionic bis(fluorosulfonyl)imide ion (FSI ion) (Li + -FSI-based electrolytes). + In the -FSI electrolyte, the second bridge structure is formed by the sulfonyl group (oxygen atom) of the FSI ion being connected to Li + coordinated to FSI ions and Li + and are arranged alternately in one dimension, and in some places Li + It has a defect (dashed circle in [Chemical formula 2]) where Li + When the second bridge structure is viewed from the viewpoint of the + are bridged by FSI ions. + Because of the presence of defects, adjacent Li + can move to the defect. + can move sequentially within the second bridge structure, which is thought to contribute to the efficient transport of metal ions within the electrolyte and achieve better ionic conductivity.

[0035] In the second bridge structure, the one-dimensional arrangement means, for example, FSI ions and Li + However, the FSI ion and Li + The arrangement of the FSI ions and Li ions is not limited to this. + The arrangement may be two-dimensional or three-dimensional, and more specifically, the linear arrangement may be curved or branched.

[0036] (How to check the second bridge structure) The second bridge structure can be confirmed by structural analysis using Raman spectroscopy. As described above, the second bridge structure can be constructed by the coordination of a metal ion of a metal salt with an anion. In other words, the second bridge structure can be constructed by the metal ion forming a coordinate bond with a specific functional group of the anion. Therefore, the presence of the second bridge structure can be confirmed by using microscopic Raman spectroscopy to confirm that "the peak derived from the specific vibration of the functional group that forms the coordinate bond is shifted to the higher wavenumber side compared to the peak derived from the specific vibration of the functional group in an uncoordinated state."

[0037] For example, in the case of the above metal salt LiFSI, its presence can be confirmed by using micro-Raman spectroscopy to confirm that "in the Raman spectrum, the peak originating from the SNS stretching vibration of the negative ion that constitutes the metal salt is shifted to the higher wavenumber side." For example, when the negative ion that constitutes the metal salt is an FSI ion, this can be confirmed by the peak attributed to the SNS stretching vibration of the sulfonyl group in a state coordinated to the metal ion being shifted to the higher wavenumber side compared to the peak (known peak) attributed to the SNS stretching vibration of the sulfonyl group in a state not coordinated to the metal ion. 2 The method for confirming the bridge structure will be described in detail in the Examples.

[0038] The electrolyte according to this embodiment may be a solid electrolyte.

[0039] The electrolyte according to this embodiment includes a porous insulator, a medium, and a metal salt. The electrolyte according to this embodiment may further include components other than these components (porous insulator, medium, and metal salt) within the scope of the main effects of the present disclosure. These components constituting the electrolyte are described below.

[0040] (porous insulator) The porous insulator has pores in which a medium and a metal salt are disposed. This allows the electrolyte according to the first embodiment to easily form a first bridge structure and a second bridge structure that contribute to superior ion conductivity. The porous insulator has pores. The porous insulator is, for example, at least one selected from the group consisting of a metal organic framework, a zeolite, and a mesoporous silica.

[0041] From the viewpoint of improving the ionic conductivity of the electrolyte, the porous insulator is preferably zeolite or mesoporous silica. Without being bound by a particular theory, the reason is presumed to be as follows: In the electrolyte according to this embodiment, when the electrolyte contains at least one of zeolite and mesoporous silica as the porous insulator (when at least one of them is used), silanol groups (Si-OH) present on the inner walls of the pores of the zeolite and mesoporous silica are ionized as carriers (positive ions of metal salts, more specifically, Li + It is thought that the protons (H + It is believed that the silanol groups function as hopping sites for the carriers due to the exchange of silanol groups with the carriers. Therefore, when the electrolyte contains at least one of zeolite and mesoporous silica as a porous insulator, the ionic conductivity of the electrolyte is further improved.

[0042] In the case of zeolite and mesoporous silica among porous insulators, from the viewpoint of improving the ionic conductivity of the electrolyte, the Si / Al ratio is, for example, 5 or more, preferably 15 or more, more preferably 30 or more, even more preferably 100 or more, particularly preferably 500 or more, and very particularly preferably 770 or more. The Si / Al ratio is, for example, 10,000 or less. These upper and lower limit values ​​can be arbitrarily combined to form a numerical range (for example, 5 or more and 10,000 or less). In this specification, the Si / Al ratio refers to the molar ratio of Si (silicon atoms) to Al (aluminum atoms) constituting the porous insulator.

[0043] When the Si / Al ratio is 5 or more, the zeolite and mesoporous silica can have more silanol groups on the inner walls of their pores, which is thought to result in more carrier hopping sites on the inner walls of the zeolite and mesoporous silica, further improving the ionic conductivity of the electrolyte.

[0044] The Si / Al ratio of zeolite and mesoporous silica is measured as follows: The zeolite or mesoporous silica is crushed to a size that allows measurement, and placed in a nuclear magnetic resonance apparatus ("ECA400 FT-NMR apparatus" manufactured by JEOL Ltd.). The magnetic field strength is 9.2 T and the nuclide is: 29 NMR spectra are obtained under Si measurement conditions, and the Si / Al ratio is obtained by spectral analysis. The zeolite or mesoporous silica used to measure the Si / Al ratio can be measured not only in the raw material state, but also in a state separated from a finished product (for example, an electrolyte or a battery containing an electrolyte (more specifically, a measurement cell battery described later in the Examples)).

[0045] Commercially available metal-organic frameworks include, for example, "UiO-67," "HKUST-1," and "F-free MIL-100(Fe) (KRICT (trademark) F100)" manufactured by Strem Chemicals, and "ZIF-8 (Basolite (registered trademark) (Z1200)" and "MIL-53 (Basolite (registered trademark) (Z1200)" manufactured by MERCK). Commercially available zeolites include "HS-690," "HS-642," and "HS-320" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and "HSZ-360HUA," "HSZ-385HUA," "HSZ-390HUA," "HSZ-660HOA," "HSZ-840HOA," "HSZ-890HOA," and "HSZ-980HOA" manufactured by Tosoh Corporation. Commercially available mesoporous silica products include "MCM-41," "MCM-48," "SBA-15," and "SBA-16" manufactured by Sigma-Aldrich.

[0046] (medium) The medium is an electrically neutral molecule. The medium disperses, dissolves, or forms a solid solution of the metal salt in the electrolyte. The medium is preferably at least one of a sulfonyl-based medium, a carbonate-based medium, an ether-based medium, and a dioxolane-based medium. Among these, the carbonate-based medium is preferred. The sulfonyl medium is a medium having a sulfonyl group, and is selected from the group consisting of, for example, sulfolane, dimethyl sulfone, 3-methyl sulfone, and ethyl methyl sulfone. The carbonate-based medium is a cyclic carbonate ester compound (more specifically, a 5- or 6-membered alkylene carbonate compound having 3 to 6 carbon atoms), and is selected from the group consisting of, for example, ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate (fluoroethylene carbonate). The carbonate-based medium may have a halogen group (more specifically, a fluoro group, etc.) and a C-C double bond. The chain ether medium is a compound containing 2 to 4 ether bonds, and is selected from the group consisting of, for example, 1,2-diethoxyethane and diglyme. The lactone medium is a cyclic ester compound (more specifically, a 5- or 6-membered ring ester compound having 4 to 7 carbon atoms), and is selected from the group consisting of, for example, γ-butyrolactone and δ-valerolactone. The cyclic ether medium is a five- or six-membered oxygen-containing heterocyclic compound containing two oxygen atoms as ring atoms, and is selected from the group consisting of dioxolane (1,3-dioxolane) and dioxane (more specifically, 1,3-dioxane, etc.). When the medium is at least one of these, it is easy to form a first bridge structure with the metal ions that constitute the metal salt in the electrolyte, thereby increasing the ionic conductivity of the electrolyte according to this embodiment.

[0047] (metal salts) The metal salt is at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts. Examples of the metal salt include alkali metal salts (more specifically, lithium metal salts, etc.). Examples of the lithium metal salt include lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium tetrafluoroborate (LiBF4), and lithium perchlorate (LiClO4). Among these, preferred lithium salts are LiFSI and LiTFSI, and more preferred is LiFSI. Examples of alkali metal ions constituting the alkali metal salt include Li + , Na + , and K. + Examples of alkaline earth metal ions constituting the alkaline earth metal salt include Mg 2+ The metal ion (positive ion) constituting the metal salt is preferably Li + , K. + , Na + , or Mg 2+ From the viewpoint of further increasing the ionic conductivity of the electrolyte according to this embodiment, the negative ions constituting the metal salt are preferably coordinated with the positive ions constituting the metal salt to form a second bridge structure with the positive ions (metal ions) constituting the metal salt. Examples of the negative ions constituting such metal salts include at least one selected from the group consisting of bis(fluorosulfonyl)imide ions (FSI ions), bis(trifluoromethanesulfonyl)imide ions (TFSI ions), tetrafluoroborate ions, and perchlorate ions.

[0048] (Electrolyte manufacturing method) An example of a method for producing the electrolyte according to the first embodiment will be described below. The method for producing the electrolyte according to the first embodiment includes a step of preparing an electrolyte solution containing a metal salt and a medium (electrolyte solution preparation step), and a step of impregnating a porous insulator having pores with the electrolyte (impregnation step).

[0049] -Electrolyte preparation process- In the electrolyte solution preparation step, an electrolyte solution containing a metal salt and a medium is prepared. -Impregnation process- In the impregnation process, a porous insulator having pores is impregnated with an electrolyte. This fills the pores of the porous insulator with the electrolyte. If the prepared electrolyte is not a liquid at room temperature (25°C) (for example, a solid or quasi-solid (more specifically, a liquid containing a solid)), the electrolyte can be heated to a liquid state and then impregnated into the porous insulator.

[0050] <Second embodiment: battery> The battery according to the second embodiment includes the electrolyte according to the first embodiment. The battery according to the second embodiment can further include a positive electrode and a negative electrode in addition to the electrolyte.

[0051] In the battery according to this embodiment, the positive electrode contains a material constituting the positive electrode (more specifically, a positive electrode active material, etc.). The negative electrode contains an alkali metal (more specifically, Li, Na, K) or an alkaline earth metal (more specifically, Mg) as a material constituting the negative electrode (more specifically, a negative electrode active material). The negative electrode contains, for example, an alkali metal or alkaline earth metal simple substance (more specifically, a plate, foil, or layer) or a compound thereof.

[0052] The battery according to this embodiment can be configured as a secondary battery. A conceptual diagram of this case is shown in FIG. 1. As shown in the figure, during charging, metal ions (M n+ (M represents a metal element, and n represents a positive integer): More specifically, Li + , Na + , K. + and Mg 2+ The metal ions (e.g., ions) move from the positive electrode 10 through the electrolyte 12 to the negative electrode 11, converting electrical energy into chemical energy and storing the electricity. During discharge, the metal ions return from the negative electrode 11 through the electrolyte 12 to the positive electrode 10, generating electrical energy.

[0053] The battery according to the second embodiment can be used as a driving power source or auxiliary power source for, for example, notebook personal computers, PDAs (personal digital assistants), mobile phones, smartphones, cordless phone base units and handset units, video camcorders, digital still cameras, e-books, electronic dictionaries, portable music players, radios, headphones, game consoles, navigation systems, memory cards, cardiac pacemakers, hearing aids, power tools, electric shavers, refrigerators, air conditioners, television receivers, stereos, hot water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights, railroad cars, golf carts, electric carts, and / or electric vehicles (including hybrid vehicles). The battery can also be installed as a power storage power source for buildings such as homes or power generation facilities, or used to supply power to these. In electric vehicles, the converter that converts supplied power into driving force is generally a motor. A control device (control unit) that processes information related to vehicle control includes a control device that displays the remaining battery power based on information about the remaining battery power. The battery can also be used in a power storage device in a so-called smart grid. Such a power storage device can not only supply power but also store power by receiving power from other power sources. Examples of other power sources that can be used include thermal power generation, nuclear power generation, hydroelectric power generation, solar cells, wind power generation, geothermal power generation, and / or fuel cells (including biofuel cells).

[0054] Although the embodiments of the present disclosure have been described above, they are merely typical examples. Therefore, it will be readily understood by those skilled in the art that the present disclosure is not limited thereto and that various modifications are possible within the scope of the present disclosure.

[0055] For example, the electrolyte composition, raw materials used in the production, production method, production conditions, electrolyte properties, and battery configuration or structure are examples, and are not limited to these and can be changed as appropriate. For example, batteries include lithium batteries, magnesium batteries, sodium batteries, and potassium batteries, as well as air batteries and fuel cells. [Example]

[0056] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples.

[0057] Example 1 [1. Preparation of electrolyte solution] (1-1. Ingredients) The following raw materials were used: -Porous insulator: Metal-organic framework (MOF)- "UiO-67" manufactured by Strem Chemicals: MOF represented by Zr6O4(OH)4(BPDC)6 (BPDC: biphenyldicarboxylate) "HKUST-1" from Strem Chemicals: MOF composed of Cu and 1,3,5-benzenetricarboxylic acid MERCK's "ZIF-8 (Basolite (Z1200 (trademark)")": Zeolite-imidazolate framework (ZIF): MOF consisting of Zn and 2-methylimidazole "F-free MIL-100(Fe) (KRICT™ F100)" manufactured by Strem Chemicals: Fe(O)(OH)(CHO): (MOF consisting of Fe and 1,3,5-benzenetricarboxylic acid) MERCK "MIL-53 (Basolite A100)": Al(OH)C8H4O4 -Porous insulator: Zeolite- Fujifilm Wako Pure Chemical Industries, Ltd. "HS-320" (crystal system: Y-type, Si / Al ratio = 5.5, cation species: H; hereinafter also referred to as "HS-320(H)") Fujifilm Wako Pure Chemical Industries, Ltd. "HS-320" (crystal system: Y-type, Si / Al ratio = 5.5, cation species: Na; hereinafter also referred to as "HS-320(Na)") Fujifilm Wako Pure Chemical Industries, Ltd. "HS-642" (crystal system: mordenite, Si / Al ratio = 18, cation species: Na) Fujifilm Wako Pure Chemical Industries, Ltd. "HS-690" (crystal system: mordenite, Si / Al ratio = 180, cation species: H) Tosoh Corporation's "HSZ-360HUA" (crystal system: Y-type, Si / Al ratio = 15, cation species: H) Tosoh Corporation's "HSZ-385HUA" (crystal system: Y-type, Si / Al ratio = 100, cation species: H) Tosoh Corporation's "HSZ-390HUA" (crystal system: Y-type, Si / Al ratio = 770, cation species: H) Tosoh Corporation's "HSZ-660HOA" (crystal system: mordenite, Si / Al ratio = 30, cation species: H) Tosoh Corporation's "HSZ-840HOA" (crystal system: ZSM-5, Si / Al ratio = 40, cation species: H) Tosoh Corporation's "HSZ-980HOA" (crystal system: beta, Si / Al ratio = 500, cation species: H) -Porous insulator: mesoporous silica- Sigma-Aldrich "MCM-41" Sigma-Aldrich "MCM-48" Sigma-Aldrich "SBA-15" Sigma-Aldrich "SBA-16" These four mesoporous silicas are essentially composed of silica (SiO2) because they do not contain artificially added Al. Therefore, the Si / Al ratio of these mesoporous silicas is thought to be at least greater than 10,000.

[0058] -Metal salts- Lithium bis(fluorosulfonyl)imide (manufactured by Kishida Chemical Co., Ltd. (for LBG); hereinafter also referred to as "LiFSI") Lithium bis(trifluoromethanesulfonyl)imide (manufactured by Kishida Chemical Co., Ltd. (for LBG); hereinafter also referred to as "LiTFSI") Lithium hexafluorophosphate (manufactured by Kishida Chemical Co., Ltd. (for LBG); hereinafter also referred to as "LiPF6" or "LiPF6") Lithium tetrafluoroborate (manufactured by Kishida Chemical Co., Ltd. (for LBG); hereinafter referred to as "LiBF4" or "LiBF4") Lithium perchlorate (manufactured by Kishida Chemical Co., Ltd. (for LBG); hereinafter also referred to as "LiClO4" or "LiClO4")

[0059] - Medium: sulfonyl-based medium - Sulfolane (Kishida Chemical Co., Ltd. (for LBG); hereinafter also referred to as "SL") Dimethyl sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter also referred to as "DMSO2") 3-Methylsulfolane (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter also referred to as "MSL") Ethyl methyl sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter also referred to as "EMS") - Media: Carbonate-based media - Propylene carbonate (manufactured by Kishida Chemical Co., Ltd.; hereinafter also referred to as "PC") Ethylene carbonate (Kishida Chemical Co., Ltd.; hereinafter referred to as "EC") Vinylene carbonate (manufactured by Kishida Chemical Co., Ltd.; hereinafter also referred to as "VC") Fluoroethylene carbonate (manufactured by Kishida Chemical Co., Ltd.; hereinafter referred to as "FEC") - Medium: Lactone-based medium - γ-Butyrolactone (manufactured by Kishida Chemical Co., Ltd.; hereinafter also referred to as "GBL") - Medium: Chain ether medium - Diglyme (Kishida Chemical Co., Ltd.) 1,2-Dimethoxyethane (Kishida Chemical Co., Ltd.; hereinafter also referred to as "DME")

[0060] (1-2. Preparation of solid electrolyte) An electrolyte solution was prepared by mixing LiFSI as a metal salt and sulfolane SL as a medium at a molar ratio (medium / metal salt) of 2.0.

[0061] The porous insulator UiO-67 was dried under vacuum at 250°C. The dried UiO-67 was impregnated with the prepared electrolyte solution, filling the pores of the UiO-67. This produced a powdered solid electrolyte. This impregnation process was performed by manually mixing the electrolyte solution and the porous insulator using a mortar and pestle. The amount (volume) of the impregnated electrolyte was adjusted to 100% of the micropore volume of the porous insulator (UiO-67), which had been measured in advance. The preparation of the solid electrolyte was carried out in a glove box in an argon atmosphere.

[0062] (1-3. Preparation of the measurement cell battery) The prepared powdered solid electrolyte was pressed at 200 MPa using a uniaxial press (Riken Kiki Co., Ltd., "CDM-20PA"). A PET resin mortar with upper and lower punches was used as the press mold. Specifically, the PET resin mortar had a cylindrical shape and a cylindrical through-hole along the central axis. The punch had a cylindrical shape and was inserted and removed from the through-hole of the mortar, with the tip faces (surfaces perpendicular to the insertion direction) of the upper and lower punches facing each other. The powdered solid electrolyte was placed in the through-hole of the mortar so as to be sandwiched between the tip faces of the upper and lower punches. The upper and lower punches were pressed with the uniaxial press to form a solid electrolyte. Furthermore, the upper and lower punches of the PET resin mortar were used as blocking electrodes to form a measurement cell (a cell for measurement). The process of preparing the measurement cell was carried out in a glove box in an argon atmosphere.

[0063] [2. Measurement and evaluation methods] (2-1. Form of electrolyte) The appearance of the electrolyte solution (electrolyte solution consisting of metal salt and medium) obtained in the solid electrolyte preparation process was visually observed. Furthermore, the container containing the electrolyte solution was tilted, and the behavior of the liquid surface changing to become parallel to the horizontal plane was visually observed. Based on these observation results, the evaluation was made according to the following criteria. (Evaluation criteria) Liquid: The electrolyte has a liquid appearance, with no solids mixed in. When a cylindrical container containing the electrolyte is tilted so that the bottom of the container is at an angle of 30° to the horizontal, the liquid surface of the electrolyte becomes parallel to the horizontal within one second of tilting. Sherbet-like: The appearance is a mixture of liquid and solid states, and when a cylindrical container containing the electrolyte is tilted so that the bottom of the container forms an angle of 30° with the horizontal, the shape of the electrolyte surface changes between 1 and 60 seconds after tilting. Solid: The appearance is solid, and when a cylindrical container containing electrolyte is tilted so that the bottom of the container is at an angle of 30° to the horizontal, the liquid level of the electrolyte remains unchanged for 10 minutes or more after tilting.

[0064] (2-2. Measurement of ionic conductivity) -Preparation of measurement samples- The measurement cell battery prepared in (1-3. Preparation of measurement cell) was enclosed in a laminate with a tab electrode to prepare a cell for measuring ionic conductivity as a measurement sample.

[0065] -Measurement of ionic conductivity- The ionic conductivity of the measurement sample was measured using an impedance meter (VMP3 manufactured by Biologic). The ionic conductivity was measured at room temperature (25°C) by an AC impedance method. The solid electrolyte of Example 1 had a molar ratio (SL / LiFSI) of 2.0 and an ionic conductivity of 1.9 × 10 -4 (S / cm). The results are shown in Table 1, along with the results of the appearance observation of the electrolyte solution described above. Table 1 shows the molar ratio (SL / LiFSI), the state of the electrolyte solution at room temperature, and the ionic conductivity at room temperature.

[0066] (2-3. Structural analysis of electrolytes by Raman spectroscopy) The electrolytes of Example 1, and Examples 2 to 8 and Comparative Examples 1 and 2 described below were subjected to structural analysis using Raman spectroscopy. The solid electrolyte formed in (1-3. Preparation of measurement cell) was used as a measurement sample for structural analysis. The obtained measurement sample was placed in a microscopic laser Raman spectrometer ("LabRam HR Evolution" manufactured by Horiba, Ltd.). The surface of the measurement sample was irradiated with infrared laser light (wavelength 1064 nm), and the Raman spectrum was measured using an objective lens with a spot diameter of 7 μm. The Raman spectrum may also be measured by irradiating the infrared laser light onto a cut surface formed by cutting the measurement sample (solid electrolyte) for structural analysis.

[0067] 2 shows the results of the 550 to 600 cm -1 In the Raman spectrum shown in Figure 2, the vertical axis represents the Raman intensity (unit: arbitrary intensity), and the horizontal axis represents the Raman shift (unit: cm -1 The Raman spectrum shown in Figure 2 shows the peak at 580-590 cm -1 This peak is due to the SO scissor vibration (OSO bending vibration) of the sulfonyl group of sulfolane. -1 The peak located nearby was attributed to the peak shifted to the higher wavenumber side.

[0068] 3 shows the results of the electrolytes in Examples 1 to 8 and Comparative Examples 1 and 2 at 680 to 780 cm -1 In the Raman spectrum shown in Figure 3, the vertical axis represents the Raman intensity (unit: arbitrary intensity), and the horizontal axis represents the Raman shift (unit: cm -1 The Raman spectrum shown in Figure 3 shows the peak at 740-750 cm -1 Nearby peaks and 680-690cm -1 It had a peak around 740-750 cm -1 The peak around 720–740 cm is due to the SNS stretching vibration of the FSI anion. -1 The peak located nearby was attributed to a shift to the higher wavenumber side.

[0069] (2-4. Determination of Si / Al ratio by nuclear magnetic resonance) In some of the systems (Examples 41 to 46) in which zeolite or mesoporous silica was used as the porous insulator, the Si / Al ratio of the zeolite or mesoporous silica was determined. Specifically, zeolite or mesoporous silica was crushed to a degree that allowed for measurement. The crushed zeolite or mesoporous silica was placed in a nuclear magnetic resonance apparatus (JEOL "ECA400 type FT-NMR apparatus"). The magnetic field strength was 9.2 T and the nuclide was: 29 Measured under Si measurement conditions 29 Si NMR spectra were obtained. 29 The Si / Al ratio was obtained from the peak area intensity ratio of the Si NMR spectrum.

[0070] <Examples 2 to 8 and Comparative Examples 1 and 2: Molar Ratio> The electrolytes were prepared and the ionic conductivity was measured in the same manner as in Example 1, except that the molar ratio (SL / LiFSI) was changed from 2.0 to the molar ratios shown in Table 1. The appearance of the electrolyte solution obtained in the electrolyte preparation process was also observed. The results are shown in Table 1. When the concentration of the metal salt in the electrolytic solution composed of the metal salt and the medium is relatively high (i.e., when the concentration of the medium is relatively low), the electrolytic solution may become a solid or a liquid with a solid precipitated at room temperature (25° C.). In such cases, the electrolytic solution is heated (for example, to 100° C.) until the solid in the prepared electrolytic solution is completely dissolved, and the solution is then liquid, and the impregnation treatment is carried out. In Example 6, the electrolyte of Example 6 and Li4Ti5O as the negative electrode were used. 12 A lithium ion secondary battery was fabricated using the cathode and LiFePO4. Charging and discharging were carried out at a current of 0.2 C (coulomb). The charging and discharging potential was approximately 1.8 V.

[0071] [Results: Examples 1 to 8 and Comparative Examples 1 and 2: Molar Ratio] (ionic conductivity) Table 1 shows the molar ratio (SL / LiFSI) and the ionic conductivity at room temperature. Figure 4 was created based on Table 1. Figure 4 shows the relationship between the molar ratio (SL / LiFSI) and the ionic conductivity at room temperature. The horizontal axis in Figure 4 shows the molar ratio, and the vertical axis shows the ionic conductivity (unit: S / cm) at room temperature. Note that, for example, 1.0E-03 in the scale of the vertical axis in Figure 4 corresponds to 1.0 x 10 -3 Shows.

[0072] [Table 1]

[0073] As shown in Figure 4, in the SL-LiFSI electrolyte, the ionic conductivity at room temperature simply increased as the molar ratio (SL / LiFSI) increased from 0.1 to 0.3, the ionic conductivity at room temperature simply decreased as the molar ratio (SL / LiFSI) increased from 0.3 to 2.6, and the ionic conductivity at room temperature remained almost the same as the molar ratio (SL / LiFSI) increased from 2.6 to 9.6. Furthermore, when the ionic conductivity of the electrolyte solution composed of SL and LiFSI in Example 4 was measured, it was found to be below the lower limit of measurement (or below the measurement limit; more specifically, about 10 -7 This corresponds to the ionic conductivity of an insulator.

[0074] (First bridge structure) In the SL-LiFSI electrolyte, as shown in Figure 2, the peak (Raman scattering peak) due to the OSO bending vibration appears at 560–570 cm when the molar ratio (SL / LiFSI) is 2.6–9.6. -1 When the molar ratio (SL / LiFSI) decreases from 0.5 to 2.0, the temperature rises from 580 to 590 cm -1 In the electrolytes of Examples 1 to 5, the peaks derived from OSO bending vibrations were shifted to the higher wavenumber side compared to the electrolytes of Comparative Examples 1 and 2. From these results, it can be seen that in the electrolytes of Examples 1 to 8, the Li constituting the metal salt +It is believed that the SL acting as a medium forms a first bridge structure. The first bridge structure is presumed to be due to a specific molar ratio (SL / LiFSI).

[0075] (Second bridge structure) In the SL-LiFSI electrolyte, as shown in Figure 3, the peak (Raman scattering peak) due to the SNS stretching vibration appears at 720-740 cm when the molar ratio (SL / LiFSI) is 2.6-9.6. -1 When the molar ratio (SL / LiFSI) decreases from 0.5 to 2.0, the temperature rises from 740 to 760 cm -1 In the electrolytes of Examples 1 to 5, the peak derived from the SNS stretching vibration gradually shifted to the higher wavenumber side as the molar ratio (SL / LiFSI) decreased, compared with the electrolytes of Comparative Examples 1 and 2. From these results, it can be seen that in the electrolytes of Examples 1 to 5, the positive ions Li constituting the metal salt + The second bridge structure is thought to be due to the specific molar ratio (SL / LiFSI).

[0076] [Comparison of Examples 1 to 8 with Comparative Examples 1 and 2] The electrolytes of Examples 1 to 8 comprised UiO-67 as a porous insulator having pores, SL as a medium having sulfonyl groups arranged in the pores, and LiFSI as a metal salt, where the metal salt LiFSI was at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 1 to 8 were electrolytes encompassed within the scope of the invention according to claim 1.

[0077] The ionic conductivity of the electrolytes in Examples 1 to 8 was 1.9 × 10 at room temperature. -4 ~10.1×10 -4 It was S / cm.

[0078] The electrolytes of Comparative Examples 1 and 2 were not included in the scope of the invention according to claim 1. Specifically, the electrolytes of Comparative Examples 1 and 2 had a molar ratio of the medium to the metal salt (medium / metal salt) of more than 2.0. The ionic conductivity of the electrolytes of Comparative Examples 1 and 2 was 1.2 × 10 at room temperature. -4 It was S / cm.

[0079] Examples 1 to 8, which fall within the scope of the invention according to claim 1, had higher ionic conductivity at room temperature than Comparative Examples 1 and 2, which do not fall within the scope of the invention according to claim 1. This clearly shows that the invention according to claim 1 is excellent in ionic conductivity.

[0080] <Examples 9 to 14 and Comparative Examples 3 to 5: Porous Insulators> An electrolyte was prepared and a battery was fabricated in the same manner as in Example 1, except that the porous insulator UiO-67 and the molar ratio (medium / metal salt) were changed to the porous insulators (metal organic insulators) and molar ratios shown in Table 2. The ionic conductivity was also measured in the same manner as in Example 1. The results are shown in Table 2.

[0081] [Table 2]

[0082] [Comparison of Examples 9 to 14 with Comparative Examples 3 to 5] The electrolytes of Examples 9 to 14 comprised any one of HKUST-1, ZIF-8, and MIL-100(Fe) as a porous insulator (metal-organic framework) having pores, SL as a medium having sulfonyl groups arranged in the pores, and LiFSI as a metal salt, where the LiFSI as the metal salt was at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 9 to 14 were electrolytes encompassed within the scope of the invention according to claim 1.

[0083] Ion conduction of the electrolytes of Examples 9 to 14 Guidance The rate is 2.2 x 10 at room temperature. -4 ~4.3×10 -4 It was S / cm.

[0084] The electrolytes of Comparative Examples 3 to 5 were not included in the scope of the invention according to claim 1. Specifically, the electrolytes of Comparative Examples 3 to 5 had a molar ratio of the medium to the metal salt (medium / metal salt) of more than 2.0. The ionic conductivity of the electrolytes of Comparative Examples 3 to 5 was 0.77 × 10 at room temperature. -4 ~1.7×10 -4 It was S / cm.

[0085] Examples 9 to 14, which fall within the scope of the invention according to claim 1, had higher ionic conductivity at room temperature than Comparative Examples 3 to 5, which do not fall within the scope of the invention according to claim 1. This clearly shows that the invention according to claim 1 is excellent in ionic conductivity.

[0086] <Examples 15 to 20: Metal salts and media> An electrolyte was prepared and a battery was fabricated in the same manner as in Example 1, except that LiFSI as the metal salt, SL as the medium, and the molar ratio were changed to the metal salt, medium, and molar ratio (medium / metal salt) shown in Table 3. The ionic conductivity was also measured in the same manner as in Example 1. The results are shown in Table 3.

[0087] [Table 3]

[0088] The electrolytes of Examples 15 to 20 comprised UiO-67 as a porous insulator having pores, any one of SL, DMSO, MSL, and EMS as a medium having sulfonyl groups arranged in the pores, and LiTFSI, LiBF, LiClO, and LiFSI as a metal salt, the metal salt being at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 15 to 20 were electrolytes encompassed within the scope of the invention according to claim 1.

[0089] The ionic conductivity of the electrolytes in Examples 15 to 20 was 2.7 × 10 at room temperature. -4 ~3.5×10 -4 It was S / cm.

[0090] <Examples 21 to 28 and Comparative Examples 6 to 7: EC-LiFSI / UiO-67 System> (ionic conductivity) The medium was changed from sulfolane (SL) to ethylene carbonate (EC) (Kishida Chemical Co., Ltd.). ) The electrolyte solutions of Examples 21 to 28 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that the molar ratio (EC / LiFSI) was changed to the above and the molar ratio (EC / LiFSI) shown in Table 4 was used. The appearance of the electrolyte solutions obtained in the electrolyte solution preparation process was also observed. The results are shown in Table 4.

[0091] [Table 4]

[0092] Table 4 shows the molar ratio (EC / LiFSI) and ionic conductivity at room temperature. Figure 5 was created based on Table 4. Figure 5 shows the relationship between the molar ratio (EC / LiFSI) and ionic conductivity at room temperature. For the EC-LiFSI electrolyte, as shown in Figure 5, the ionic conductivity at room temperature simply increased as the molar ratio (EC / LiFSI) increased from 0.1 to 0.5, decreased as the molar ratio (EC / LiFSI) increased from 0.5 to 4.0, and remained almost the same as the molar ratio (EC / LiFSI) increased from 4.0 to 10.0.

[0093] The electrolytes of Examples 21 to 28 comprised UiO-67 as a porous insulator having pores, EC as a medium disposed in the pores, and LiFSI as a metal salt, the LiFSI as the metal salt being at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 21 to 28 were electrolytes encompassed within the scope of the invention according to claim 1.

[0094] The ionic conductivity of the electrolytes in Examples 21 to 28 was 3.7 × 10 at room temperature. -4 ~10×10 -4 It was S / cm.

[0095] The electrolytes of Comparative Examples 6 and 7 were not included in the scope of the invention according to claim 1. Specifically, the electrolytes of Comparative Examples 6 and 7 had a molar ratio of the medium to the metal salt (medium / metal salt) of more than 2.0. The ionic conductivity of the electrolytes of Comparative Examples 6 and 7 was 2.7 × 10 at room temperature. -4 ~2.9×10 -4 It was S / cm.

[0096] Examples 21 to 28, which fall within the scope of the invention according to claim 1, had higher ionic conductivity at room temperature than Comparative Examples 6 to 7, which do not fall within the scope of the invention according to claim 1. This clearly shows that the invention according to claim 1 is excellent in ionic conductivity.

[0097] Furthermore, the integral value of the graph showing ionic conductivity in Fig. 5 was larger than the integral value of the graph showing ionic conductivity in Fig. 4. This shows that the electrolytes of Examples 21 to 28 exhibit higher ionic conductivities than the electrolytes of Examples 1 to 8 (i.e., the EC-LiSFI electrolytes have higher ionic conductivities than the SL-LiSFI electrolytes).

[0098] (Structural analysis by Raman spectroscopy) -First bridge structure- Furthermore, the electrolytes of Examples 23, 25 to 26 and Comparative Example 6 were subjected to structural analysis by Raman spectroscopy in the same manner as in Example 1. -1 In the Raman spectrum shown in FIG. 6, the vertical axis represents the Raman intensity (unit: arbitrary intensity), and the horizontal axis represents the Raman shift (unit: cm -1 The Raman spectrum shown in Figure 6 shows the peak at 900-910 cm -1 This peak is due to the ring breathing vibration of ethylene carbonate (EC) (heterocyclic breathing vibration). -1 The peak located nearby was attributed to the peak shifted to the higher wavenumber side.

[0099] In the EC-LiFSI electrolyte, as shown in FIG. 6, when the molar ratio (EC / LiFSI) is 0.3 to 1.0 (Examples 23, 25, and 26), there is mainly one peak (Raman scattering peak) originating from the breathing vibration of the heterocycle of EC, and the peak is located between 900 and 910 cm. -1 That is, in the electrolytes of Examples 23, 25 and 26, the peak derived from the respiratory oscillation was observed to be shifted to the higher wavenumber side. In contrast, when the molar ratio (EC / LiFSI) was 10 (Comparative Example 6), two peaks were present due to the breathing vibration, each at 895 cm -1 Around 900-910cm -1That is, for the electrolyte of Comparative Example 6, the peak derived from the respiratory vibration was mainly observed, and a peak shifted to the higher wavenumber side was slightly observed.

[0100] From the results of FIG. 6, in the electrolytes of Examples 23 and 25 to 26, Li constituting the metal salt + and, It is believed that the EC serving as a medium forms a first bridge structure, and this bridge structure is presumed to be due to the molar ratio (EC / LiFSI).

[0101] -Second bridge structure- 7 shows the 680 to 800 cm of the electrolytes of Examples 23, 25 to 26 and Comparative Example 6. -1 In the Raman spectrum shown in FIG. 7, the vertical axis represents the Raman intensity (unit: arbitrary intensity), and the horizontal axis represents the Raman shift (unit: cm -1 The Raman spectrum shown in Figure 7 shows the peak at 740-760 cm -1 This peak was due to the SNS stretching vibration of the FSI anion in the range of 710 to 740 cm. -1 The peak located nearby was attributed to a peak shifted to the higher wavenumber side.

[0102] In the EC-LiFSI electrolyte, when the molar ratio (EC / LiFSI) was 0.3 to 1.0 (Examples 23, 25, and 26), the peaks (Raman scattering peaks) derived from the SNS stretching vibration of the FSI anion were mainly peaks that were shifted to higher wavenumbers. That is, in the electrolytes of Examples 23, 25, and 26, the peaks derived from the deflection vibration were mainly peaks that were shifted to higher wavenumbers. In contrast, when the molar ratio (EC / LiFSI) was 10 (Comparative Example 6), the peak derived from the stretching vibration was mainly present. That is, in the electrolyte of Comparative Example 6, the peak derived from the breathing vibration was mainly observed.

[0103] From the results of FIG. 7, in the electrolytes of Examples 23 and 25 to 26, Li constituting the metal salt + and, It is believed that the FSI anions form a second bridge structure, and this second bridge structure is presumed to be due to the molar ratio (EC / LiFSI).

[0104] Examples 29 to 32: EC-LiFSI / MOF system Sulfolane (SL) as a medium was dissolved in ethylene carbonate (EC) (Kishida Chemical Co., Ltd.). ) The electrolytes of Examples 29 to 32 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that the molar ratio (SL / LiSFI) was changed to the molar ratio (EC / LiFSI) shown in Table 5, and UiO-67 as the porous insulator was changed to a metal-organic framework (MOF) shown in Table 5. The results are shown in Table 5.

[0105] [Table 5]

[0106] The electrolytes of Examples 29 to 32 comprised any one of HKUST-1, ZIF-8, MIL-100(Fe), and MIL-53 as a porous insulator (metal-organic framework) having pores, EC as a medium disposed in the pores, and LiFSI as a metal salt, wherein the LiFSI as the metal salt was at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 29 to 32 were electrolytes encompassed within the scope of the invention according to claim 1.

[0107] <Examples 33 to 40 and Comparative Examples 8 and 9: EC-LiFSI / Zeolite System> The electrolytes of Examples 33 to 40 and Comparative Examples 8 and 9 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that the sulfolane (SL) used as the medium was changed to ethylene carbonate (EC) (manufactured by Kishida Chemical Co., Ltd.), the molar ratio (SL / LiSFI) was changed to the molar ratio (EC / LiFSI) shown in Table 6, the UiO-67 used as the porous insulator was changed to HS-690 zeolite, and the drying temperature of the porous insulator under vacuum was changed from 250°C to 300°C. The appearance of the electrolyte solution obtained in the electrolyte solution preparation step was also observed. The results are shown in Table 6.

[0108] [Table 6]

[0109] The electrolytes of Examples 33 to 40 comprised HS-690 as a porous insulator (zeolite) having pores, EC as a medium disposed in the pores, and LiFSI as a metal salt, the LiFSI as the metal salt being at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 29 to 32 were electrolytes encompassed within the scope of the invention according to claim 1. The ionic conductivity of the electrolytes in Examples 33 to 40 was 9.7 × 10 at room temperature. -4 ~54×10 -4 It was S / cm.

[0110] The electrolytes of Comparative Examples 8 and 9 were not included in the scope of the invention according to claim 1. Specifically, the electrolytes of Comparative Examples 8 and 9 had a molar ratio of the medium to the metal salt (medium / metal ratio) of more than 2.0. The ionic conductivity of the electrolytes of Comparative Examples 8 and 9 was 2.5 × 10 at room temperature. -4 ~2.8×10 -4 It was S / cm.

[0111] Examples 33 to 40, which fall within the scope of the invention according to claim 1, had higher ionic conductivities at room temperature than Comparative Examples 8 to 9, which fall outside the scope of the invention according to claim 1.

[0112] In addition, the electrolyte was changed to that of Example 37, and Li4Ti5O 12 A battery of Example 37 was produced in the same manner as the battery of Example 1 (cell for measuring ionic conductivity), except that LiFePO4 was used as the positive electrode. The battery of Example 37 thus obtained was charged and discharged at a current of 0.1 C. It was found that the battery of Example 37 was capable of being charged and discharged at about 1.8 V.

[0113] <Examples 41 to 44: EC-LiFSI / Zeolite System> The electrolytes of Examples 41 to 46 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that the sulfolane (SL) used as the medium was changed to ethylene carbonate (EC) (manufactured by Kishida Chemical Co., Ltd.), the molar ratio (SL / LiSFI) was changed to the molar ratio (EC / LiFSI) shown in Table 7, and the UiO-67 used as the porous insulator was changed to zeolite (any of HS-320(H), HSZ-360HUA, HSZ-660HOA, HSZ-385HUA, HSZ-980HOA, and HSZ-390HUA). The results are shown in Table 7.

[0114] [Table 7]

[0115] The electrolytes of Examples 41 to 46 comprised any one of HS-320(H), HSZ-360HUA, HSZ-660HOA, HSZ-385HUA, HSZ-980HOA, and HSZ-390HUA as a porous insulator (zeolite) having pores, EC as a medium disposed in the pores, and LiFSI as a metal salt, where the LiFSI as the metal salt was at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, and the molar ratio of the medium to the metal salt (medium / metal salt) was 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 41 to 46 were electrolytes encompassed within the scope of the invention according to claim 1.

[0116] The ionic conductivity of the electrolytes in Examples 41 to 46 was 1.1 × 10 at room temperature. -3 ~8.5×10 -3 S / cm, which increased with increasing Si / Al ratio. This trend suggests that the larger the Si / Al ratio, the more silanol groups are present on the inner walls of the pores of the porous insulator, resulting in the carrier (Li + ) hopping sites will increase.

[0117] The ionic conductivity of the electrolytes (EC-LiFSi / zeolite system, molar ratio 0.3) in Examples 41 to 46 was 1.1 × 10 -3 ~8.5×10 -3 On the other hand, the ionic conductivity of the electrolyte of Example 6 (EC-LiFSi / metal organic framework, molar ratio 0.3) is 1.01 × 10 -3 S / cm. This shows that ion conductivity can be improved more when the porous insulator is a zeolite system than when it is a metal organic framework system.

[0118] <Examples 48 to 63: Alkali metal salt-medium / zeolite (HS-690) system> The electrolytes of Examples 48 to 63 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that sulfolane (SL) as the medium was changed to a medium listed in Table 8, LiSFI as the metal salt was changed to an alkali metal salt listed in Table 8, and UiO-67 as the porous insulator was changed to zeolite (HS-690). The results are shown in Table 8.

[0119] [Table 8]

[0120] The electrolytes of Examples 48 to 63 comprised HS-690 as a porous insulator (zeolite) having pores, any one of PC, VC, FEC, EC, GBL, diglyme, and DME as a medium disposed in the pores, and any one of LiFSI, LiTFSI, LiPF6, LiBF4, and LiClO4 as a metal salt, with a molar ratio of the medium to the metal salt (medium / metal salt) of 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 48 to 63 were electrolytes encompassed within the scope of the invention according to claim 1.

[0121] <Examples 64 to 69: EC-LiFSI / mesoporous silica system> The electrolytes of Examples 64 to 69 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that sulfolane (SL) as the medium was changed to a medium listed in Table 9 and Ui0-67 as the porous insulator was changed to mesoporous silica listed in Table 9. The results are shown in Table 9.

[0122] [Table 9]

[0123] The electrolytes of Examples 64 to 69 contained any one of MCM-48, SBA-15, MCM-41, and SBA-16 as a porous insulator (mesoporous silica) having pores, EC as a medium disposed in the pores, and LiFSI as a metal salt, with the molar ratio of the medium to the metal salt (medium / metal salt) being 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 64 to 69 were electrolytes encompassed within the scope of the invention according to claim 1.

[0124] The ionic conductivity of the electrolytes (EC-LiFSi / mesoporous silica system, molar ratio 0.5) in Examples 65 and 67 to 69 was 3.1 × 10 -3 ~3.7×10 -3 On the other hand, the ionic conductivity of the electrolyte of Example 5 (EC-LiFSi / metal organic framework, molar ratio 0.5) is 0.94 × 10 -3S / cm. This shows that when the porous insulator is a mesoporous silica system, the ionic conductivity can be improved more than when it is a metal organic framework system.

[0125] <Examples 71 to 80 and Comparative Example 10: SL-LiFSI / Zeolite System> The electrolytes of Examples 71 to 80 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that Ui0-67 as the porous insulator was changed to a zeolite shown in Table 10 and the molar ratio (SL-LiFSI) was changed to a molar ratio shown in Table 10. The results are shown in Table 10.

[0126] [Table 10]

[0127] The electrolytes of Examples 71 to 80 comprised any one of HS-690, HS-642, HS-320(Na), HSZ-980HOA, and HSZ-840HOA as a porous insulator (zeolite) having pores, SL as a medium disposed in the pores, and LiFSI as a metal salt, with the molar ratio of the medium to the metal salt (medium / metal salt) being 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 71 to 80 were electrolytes encompassed within the scope of the invention according to claim 1. The ionic conductivity of the electrolytes in Examples 71 to 80 was 3.3 × 10 at room temperature. -4 ~42×10 -4 It was S / cm.

[0128] The electrolyte of Comparative Example 10 was an electrolyte not included in the scope of the invention according to claim 1. Specifically, the molar ratio of the medium to the metal salt (medium / metal ratio) of the electrolyte of Comparative Example 10 was greater than 2.0. The ionic conductivity of the electrolyte of Comparative Example 10 was 1.1 × 10 at room temperature. -4 It was S / cm.

[0129] Examples 71 to 80, which fall within the scope of the invention according to claim 1, had higher ionic conductivities at room temperature than Comparative Example 10, which does not fall within the scope of the invention according to claim 1.

[0130] Furthermore, the integral value of the graph (not shown) showing the ionic conductivity of Examples 71 to 75 (SL-LiFSI / zeolite-based, molar ratio 0.1 to 1.0) in Table 10 was larger than the integral value of the graph ( FIG. 4 ) showing the ionic conductivity of Examples 4 to 8 (SL-LiFSI / metal organic framework-based, molar ratio 0.1 to 1.0) in Table 1. This shows that the electrolytes of Examples 71 to 75 exhibit higher ionic conductivity than the electrolytes of Examples 4 to 8 (in other words, zeolite-based electrolytes have higher ionic conductivity than metal organic framework-based electrolytes).

[0131] <Examples 81 to 87 and Comparative Example 11: SL-LiFSI / Mesoporous Silica System> The electrolytes of Examples 81 to 87 and Comparative Example 11 were prepared and their ionic conductivities were measured in the same manner as in Example 1, except that Ui0-67 as the porous insulator was changed to the mesoporous silica shown in Table 11 and the molar ratio (SL / LiFSI) was changed to the molar ratio shown in Table 11. The results are shown in Table 11.

[0132] [Table 11]

[0133] The electrolytes of Examples 81 to 87 comprised any one of MCM-48, SBA-15, MCM-41, and SBA-16 as a porous insulator (mesoporous silica) having pores, SL as a medium disposed in the pores, and LiFSI as a metal salt, with the molar ratio of the medium to the metal salt (medium / metal salt) being 0.1 or more and 2.0 or less. In other words, the electrolytes of Examples 81 to 87 were electrolytes encompassed within the scope of the invention according to claim 1. The ionic conductivity of the electrolytes in Examples 81 to 87 was 18×10 at room temperature. -4 ~120×10 -4 It was S / cm.

[0134] The electrolyte of Comparative Example 11 was an electrolyte not included in the scope of the invention according to claim 1. Specifically, the electrolyte of Comparative Example 11 had a molar ratio of the medium to the metal salt (medium / metal salt ) was greater than 2.0. The ionic conductivity of the electrolyte of Comparative Example 11 was 0.82 × 10 at room temperature. -4 It was S / cm.

[0135] Examples 81 to 87, which fall within the scope of the invention according to claim 1, had higher ionic conductivities at room temperature than Comparative Example 11, which does not fall within the scope of the invention according to claim 1.

[0136] Furthermore, the integral value of the graph (not shown) showing the ionic conductivity of Examples 81 to 84 (SL-LiFSI / mesoporous silica system, molar ratio 0.2 to 1.0) in Table 11 was larger than the integral value of the graph (FIG. 4) showing the ionic conductivity of Examples 4 to 7 (SL-LiFSI / metal organic framework system, molar ratio 0.2 to 1.0) in Table 1. This demonstrates that the electrolytes of Examples 81 to 84 exhibit higher ionic conductivity than the electrolytes of Examples 4 to 7 (that is, mesoporous silica-based electrolytes have higher ionic conductivity than metal organic framework-based electrolytes).

[0137] Aspects of the electrolyte and battery according to the present disclosure are as follows. <1> A porous insulator having pores, and a medium and a metal salt disposed in the pores, the metal salt is at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, An electrolyte, wherein the molar ratio of the medium to the metal salt (medium / metal salt) is 0.1 or more and 2.0 or less. <2> The medium is a sulfonyl-based medium selected from the group consisting of sulfolane, dimethyl sulfone, 3-methyl sulfone, and ethyl methyl sulfone; a carbonate-based medium selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate; a chain ether medium selected from the group consisting of 1,2-diethoxyethane and diglyme; a lactone medium selected from the group consisting of γ-butyrolactone and δ-valerolactone; and A cyclic ether medium selected from the group consisting of 1,3-dioxolane and 1,3-dioxane. At least one of the following: <1> The electrolyte according to claim 1. <3> The metal salt is a lithium salt. <1> or <2> The electrolyte according to claim 1. <4> The porous insulator is at least one selected from the group consisting of a metal organic framework, a zeolite, and a mesoporous silica. <1> ~ <3> 10. The electrolyte according to claim 9 . <5> The positive ions constituting the metal salt are Li + , K. + , Na + , or Mg 2+ That is, <1> ~ <4> 10. The electrolyte according to claim 9 . <6> the anion constituting the metal salt is at least one selected from the group consisting of a bis(fluorosulfonyl)imide ion, a TFSI ion, a tetrafluoroborate ion, and a perchlorate ion; <1> ~ <5> 10. The electrolyte according to claim 9 . <7> It is a solid electrolyte, <1> ~ <6> 10. The electrolyte according to claim 9 , <8> the medium is a sulfonyl-based medium having at least one sulfonyl group selected from the group consisting of sulfolane, dimethyl sulfone, 3-methyl sulfone, and ethyl methyl sulfone; In the Raman spectrum, the peak due to the SO deformation vibration of the sulfonyl group shifts to a higher wavenumber side. <1> ~ <7> 10. The electrolyte according to claim 9 . <9> the negative ion constituting the metal salt is a bis(fluorosulfonyl)imide ion or a bis(trifluoromethanesulfonyl)imide ion, In the Raman spectrum, a peak derived from the SNS stretching vibration of the negative ion constituting the metal salt is shifted to a higher wavenumber side. <1> ~ <8> 10. The electrolyte according to claim 9 . <10> The porous insulator is either zeolite or mesoporous silica. <1> ~ <9> 10. The electrolyte according to claim 9 , <11> the porous insulator is either zeolite or mesoporous silica, The SiAl ratio of the zeolite and the mesoporous silica is 5.0 or more. <1> ~ <10> 10. The electrolyte according to claim 9 . <12> The medium is at least one carbonate-based medium selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate. <1> ~ <11> 10. The electrolyte according to claim 9 . <13> the medium is at least one carbonate-based medium selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate; In the Raman spectrum, the peak due to the breathing vibration of the heterocycle of the carbonate-based medium is shifted to a higher wavenumber side. <1> ~ <12> 10. The electrolyte according to claim 9 , <14> <1> ~ <13> A battery comprising the electrolyte according to any one of claims 1 to 5. [Industrial Applicability]

[0138] Batteries including the electrolyte according to the present disclosure can be used in a variety of fields where electricity storage is anticipated. By way of example only, batteries (particularly secondary batteries) including the electrolyte according to the present disclosure can be used in the electrical, information, and communications fields where electrical and electronic devices are used (for example, the electrical and electronic device fields or mobile device fields including mobile phones, smartphones, laptop computers, digital cameras, activity monitors, arm computers, electronic paper, wearable devices, and small electronic devices such as RFID tags, card-type electronic money, and smart watches), household and small industrial applications (for example, power tools, golf carts, and household, nursing care, and industrial robots), large industrial applications (for example, forklifts, elevators, and port cranes), transportation systems (for example, hybrid cars, electric cars, buses, trains, electrically assisted bicycles, and electric motorcycles), power system applications (for example, various power generation systems, road conditioners, smart grids, and general household-installed power storage systems), medical applications (medical devices such as earphones and hearing aids), pharmaceutical applications (dose management systems), as well as the IoT field and space and deep-sea applications (for example, space probes, submersible research vessels, and the like).

Claims

1. A porous insulator having pores, and a medium and a metal salt disposed in the pores, the metal salt is at least one selected from the group consisting of alkali metal salts and alkaline earth metal salts, An electrolyte, wherein the molar ratio of the medium to the metal salt (medium / metal salt) is 0.1 or more and 2.0 or less.

2. The medium is a sulfonyl medium selected from the group consisting of sulfolane, dimethyl sulfone, 3-methyl sulfone, and ethyl methyl sulfone; a carbonate-based medium selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate; a chain ether medium selected from the group consisting of 1,2-diethoxyethane and diglyme; a lactone medium selected from the group consisting of gamma-butyrolactone and delta-valerolactone; and a cyclic ether medium selected from the group consisting of 1,3-dioxolane and 1,3-dioxane; The electrolyte of claim 1 , wherein the electrolyte is at least one of:

3. 10. The electrolyte of claim 1, wherein the metal salt is a lithium salt.

4. 2. The electrolyte according to claim 1, wherein the porous insulator is at least one selected from the group consisting of a metal organic framework, a zeolite, and a mesoporous silica.

5. The positive ions constituting the metal salt are Li ＋ , K. ＋ , Na ＋ , or Mg ２＋ 2. The electrolyte of claim 1 , wherein:

6. 2. The electrolyte according to claim 1, wherein the negative ion constituting the metal salt is at least one selected from the group consisting of a bis(fluorosulfonyl)imide ion, a bis(trifluoromethanesulfonyl)imide ion, a tetrafluoroborate ion, and a perchlorate ion.

7. 10. The electrolyte of claim 1 which is a solid electrolyte.

8. the medium is a sulfonyl-based medium having at least one sulfonyl group selected from the group consisting of sulfolane, dimethyl sulfone, 3-methyl sulfone, and ethyl methyl sulfone; In the Raman spectrum, the SO ２ The electrolyte according to claim 1, wherein a peak derived from bending vibration is shifted to a higher wavenumber side.

9. the negative ion constituting the metal salt is a bis(fluorosulfonyl)imide ion or a bis(trifluoromethanesulfonyl)imide ion, 2. The electrolyte according to claim 1, wherein in a Raman spectrum, a peak derived from SNS stretching vibration of an anion constituting the metal salt is shifted to a higher wave number side.

10. The electrolyte of claim 1 , wherein the porous insulator is one of zeolite and mesoporous silica.

11. the porous insulator is either zeolite or mesoporous silica, 2. The electrolyte of claim 1, wherein the zeolite and the mesoporous silica have a Si / Al ratio of 5.0 or greater.

12. 10. The electrolyte of claim 1, wherein the medium is a carbonate-based medium selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate.

13. the medium is at least one carbonate-based medium selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, and fluoroethylene carbonate; 2. The electrolyte according to claim 1, wherein in the Raman spectrum, a peak derived from the breathing vibration of the heterocycle of the carbonate-based medium is shifted to a higher wavenumber side.

14. A battery comprising the electrolyte according to any one of claims 1 to 13.

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