Lithium secondary battery and non-aqueous electrolyte used therein

Abstract

In the present invention, a lithium secondary battery includes a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, and a non-aqueous electrolyte. At the negative electrode, lithium metal is deposited during charging, while lithium metal is dissolved during discharging. The non-aqueous electrolyte contains lithium ions, cations of a metal M1 that forms an alloy with lithium, and halide ions.

Description

[Technical Field]

[0001] The present disclosure relates to a lithium secondary battery and a non-aqueous electrolyte used therein. [Background technology]

[0002] Lithium-ion secondary batteries are known as high-capacity secondary batteries. In lithium-ion secondary batteries, for example, carbon materials are used as the negative electrode active material. The carbon materials are charged and discharged by reversibly inserting and extracting lithium ions.

[0003] On the other hand, lithium secondary batteries (also called lithium metal secondary batteries) that use lithium metal as the negative electrode active material have an even higher theoretical capacity density. In lithium secondary batteries, lithium metal is deposited on the negative electrode current collector during charging, and the deposited lithium metal dissolves in the non-aqueous electrolyte during discharging.

[0004] However, it is difficult to control the morphology of lithium metal deposition in lithium secondary batteries. When lithium metal deposits in a dendrite-like form, the specific surface area of ​​the negative electrode increases, increasing the risk of side reactions with the non-aqueous electrolyte. Furthermore, inactive lithium that cannot contribute to charge and discharge is generated, resulting in a decrease in discharge capacity.

[0005] Patent Document 1 proposes a nonaqueous electrolyte battery including a positive electrode having a lithium-containing active material, a negative electrode having an active material capable of doping / dedoping a metal in an ionic state and / or depositing / eluting the metal, and a nonaqueous electrolyte containing an electrolyte salt, characterized in that the nonaqueous electrolyte contains an additive whose redox potential is more noble than the potential at which the metal deposits on the negative electrode and less noble than the potential of the positive electrode active material in a charged state. Lithium iodide is cited as an example of the additive. When lithium metal deposited on the negative electrode becomes insulated from the negative electrode and no longer contributes to charge / discharge, the additive oxidizes and ionizes the lithium metal, thereby preventing deterioration of charge / discharge cycle characteristics.

[0006] Patent Document 2 proposes a nonaqueous electrolyte secondary battery that includes a positive electrode having a positive electrode current collector and a positive electrode composite layer formed on the current collector, a negative electrode having a negative electrode current collector, and a nonaqueous electrolyte, in which lithium metal is deposited on the negative electrode current collector during charging and the lithium metal dissolves in the nonaqueous electrolyte during discharging, the nonaqueous electrolyte containing a lithium salt having an oxalate complex as the anion. By adding a lithium salt having an oxalate complex as the anion to the nonaqueous electrolyte, lithium metal is uniformly deposited on the negative electrode, and swelling of the negative electrode is specifically suppressed. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-243030 [Patent Document 2] International Publication No. 2018 / 179782 Summary of the Invention

[0008] The methods proposed in Patent Documents 1 and 2 are insufficient to improve the charge-discharge cycle characteristics of lithium secondary batteries.

[0009] One aspect of the present disclosure relates to a lithium secondary battery including a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte, wherein lithium metal precipitates in the negative electrode during charging and dissolves during discharging, and the non-aqueous electrolyte includes lithium ions, cations of a metal M1 that form an alloy with lithium, and halide ions.

[0010] Another aspect of the present disclosure relates to a non-aqueous electrolyte for a lithium secondary battery, which includes lithium ions, cations of a metal M1 that forms an alloy with lithium, and halide ions.

[0011] According to the present disclosure, the charge-discharge cycle characteristics of a lithium secondary battery can be improved. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a partial cross-sectional view schematically illustrating an example of a lithium secondary battery according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0013] The lithium secondary battery according to the present disclosure includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte. Lithium metal precipitates in the negative electrode during charging and dissolves during discharging. Specifically, the negative electrode includes at least a negative electrode current collector, and lithium metal precipitates on the negative electrode current collector. The lithium secondary battery according to the present disclosure is also referred to as a lithium metal secondary battery.

[0014] In a lithium (metal) secondary battery, for example, 70% or more of the rated capacity is achieved by the deposition and dissolution of lithium metal. The movement of electrons at the negative electrode during charging and discharging is mainly due to the deposition and dissolution of lithium metal at the negative electrode. Specifically, 70 to 100% (e.g., 80 to 100% or 90 to 100%) of the movement of electrons (current from another perspective) at the negative electrode during charging and discharging is due to the deposition and dissolution of lithium metal. In other words, the negative electrode according to this embodiment differs from a negative electrode in which the movement of electrons at the negative electrode during charging and discharging is mainly due to the absorption and release of lithium ions by the negative electrode active material (such as graphite).

[0015] Here, the non-aqueous electrolyte contains lithium ions, cations of a metal M1 that forms an alloy with lithium, and halide ions.

[0016] When a nonaqueous electrolyte contains cations of metal M1, which form an alloy with lithium, a region doped with metal M1 (hereinafter also referred to as the doped region) is formed in the lithium metal deposited on the negative electrode at the beginning of charging. With continued charging, it is believed that lithium metal is deposited mainly between the thin layer formed in the doped region (hereinafter also referred to as the doped layer M1) and the negative electrode current collector. As a result, the lithium metal is pressed against the doped layer M1. This pressing effect is believed to suppress the extension of dendritic deposits, thereby suppressing side reactions and a decrease in discharge capacity. This improves the charge-discharge cycle characteristics of lithium secondary batteries.

[0017] However, protruding deposits may occasionally form on the negative electrode during charging. Dendritic deposits of lithium metal grow from the protruding deposits as nuclei. If the protruding deposits (hereinafter also referred to as dendrite precursors) are left unattended, it becomes difficult to suppress the formation of dendritic deposits.

[0018] When halide ions are contained in the non-aqueous electrolyte, they can dissolve (oxidize) dendrite precursors through a redox reaction. Dissolving the dendrite precursors with halide ions makes the lithium metal surface flatter. Furthermore, because halide ions also dissolve dendritic deposits, even if dendritic deposits do form, their extension can be suppressed.

[0019] When halide ions dissolve (oxidize) the dendrite precursors, they themselves are reduced. When the reduced halide ions migrate to the positive electrode and react with the positive electrode active material, they reduce (discharge) the positive electrode active material, and the halide ions are oxidized back to their original state. If the halide ions repeat this reaction excessively, self-discharge of the positive electrode progresses, and the storage characteristics of the lithium secondary battery deteriorate. In this regard, halide ions preferentially react with dendritic lithium, which has a large specific surface area. In addition, if the doped layer M1 is present, the reaction between the halide ions and well-precipitated lithium metal is suppressed by the doped layer M1, making self-discharge of the positive electrode less likely to progress. Therefore, the cycle characteristics are improved while deterioration of storage characteristics is also suppressed.

[0020] Preferred halogens that are the source of halide ions include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). These may be used alone or in combination of two or more. Among these, at least one of bromine and iodine is preferred, with iodine being most preferred, due to its greater effect in dissolving dendrite precursors or dendritic precipitates.

[0021] During the initial stage of charging, an alloy of metal M1 and lithium may be formed as a doped region in the negative electrode. In this case, lithium metal is thought to precipitate between the doped layer M1 (hereinafter also referred to as alloy layer M1) formed mainly of the alloy and the negative electrode current collector. The alloy layer M1 is thought to be a stable layer within the doped layer M1 and to press the lithium metal more stably.

[0022] The metal M1 may be at least one selected from the group consisting of In, Sn, Au, Ag, Pt, Zn, Sb, Bi, Si, and Mg. These metals M1 may react with lithium to form an alloy layer M1 in the early stages of charging. Among these, the metal M1 may be at least one of Sn and Au. Sn and Au are effective in improving charge-discharge cycle characteristics.

[0023] The concentration of metal M1 cations in the non-aqueous electrolyte is not limited, but may be, for example, 0.5 mmol / L or more and 100 mmol / L or less, or 5 mmol / L or more and 50 mmol / L or less. When metal M1 is used in the above range, a necessary and sufficient doped region is formed in lithium metal. However, in the battery, the cations of metal M1 are used to form a doped region (e.g., alloy layer M1) by reacting with lithium. Therefore, when analyzing a non-aqueous electrolyte collected from inside a battery, the content of metal M1 cations may be less than 0.5 mmol. On the other hand, it is rare for the cations of metal M1 to be completely consumed. From the perspective of achieving the effects of the present disclosure, it is sufficient that the non-aqueous electrolyte collected from inside the battery contains metal M1 at a concentration equal to or greater than the detection limit.

[0024] Since the lithium metal deposited on the negative electrode forms a doped region of metal M1, metal M1 can be detected when the negative electrode is analyzed. Metal M1 can be detected as an alloy with lithium.

[0025] The concentration of halide ions in the non-aqueous electrolyte is not limited, but may be, for example, 0.5 mmol / L to 100 mmol / L or 5 mmol / L to 50 mmol / L. Using halide ions in this range can achieve a significant effect of dissolving dendrite precursors or dendritic deposits. However, within the battery, halide ions are utilized in oxidation-reduction reactions. Therefore, when analyzing a non-aqueous electrolyte sampled from the battery, the halide ion content may be less than 0.5 mmol.

[0026] The cation of the metal M1 and the halide ion may be derived from a salt represented by the general formula MXn (hereinafter referred to as an MXn salt). Here, M represents an atom of the metal M1 (or M2), and X represents a halogen atom. n is an integer of 1 to 4, for example. Specific examples of MXn salts include InCl3, InBr3, InBr, InI3, InI, SnCl4, SnBr4, SnBr2, SnI4, SnI2, AuCl, AuBr, AuI, AgCl, AgBr, AgI, PtI2, and PtBr2. Among these, SnI4 and AuI are preferred because they are easily ion-dissociated in non-aqueous electrolytes, and it is more preferred to use at least one of SnI4 and AuI.

[0027] The non-aqueous electrolyte may further contain an oxalate complex anion. The oxalate complex anion may be derived from, for example, an oxalate complex salt. The oxalate complex anion decomposes at a higher potential than other components contained in the non-aqueous electrolyte, forming a thin, uniform coating on the surface of lithium metal. The coating derived from the oxalate complex anion significantly improves the storage characteristics of a lithium secondary battery when halide ions are contained in the non-aqueous electrolyte.

[0028] The coating derived from the oxalate complex anion is flexible. The formation of a flexible coating derived from the oxalate complex anion in addition to the doped layer (or alloy layer) M1 is believed to allow the lithium metal to be firmly pressed between the doped layer M1 and the coating. Furthermore, the coating derived from the oxalate complex anion can easily adapt to changes in the surface shape of the lithium metal as it dissolves. This means that the coating is constantly in contact with the lithium metal, enhancing the pressing effect. As a result, the generation of dendrite precursors is significantly suppressed, and the reduction in the dendrite precursors also reduces the amount of reaction between the dendrite precursors and halide ions. These simultaneous effects are believed to significantly suppress the self-discharge of the positive electrode and significantly improve the storage characteristics of lithium secondary batteries.

[0029] As the oxalate complex anion, bisoxalateborate anion (BOB anion), difluorooxalateborate anion (FOB anion), etc. are preferred, and among them, lithium difluorooxalateborate (LiFOB) is desirable because it forms a stable coating on the negative electrode surface even at high temperatures.

[0030] The concentration of the oxalate complex anion in the non-aqueous electrolyte is not limited, but may be, for example, 50 mmol / L or more and 500 mmol / L or less, 50 mmol / L or more and 300 mmol / L or less, or 80 mmol / L or more and 150 mmol / L or less.

[0031] The content of each component of the non-aqueous electrolyte can be determined using, for example, high performance liquid chromatography.

[0032] Hereinafter, the lithium secondary battery according to the present disclosure will be described in more detail for each component.

[0033] (positive electrode) The positive electrode includes a positive electrode active material. The positive electrode typically includes a positive electrode current collector and a positive electrode mixture held on the positive electrode current collector. The positive electrode mixture includes a positive electrode active material as an essential component, and may include optional components such as a binder, a thickener, and a conductive agent. The positive electrode typically includes a layer of positive electrode mixture (hereinafter referred to as a positive electrode mixture layer) held on the positive electrode current collector. The positive electrode mixture layer can be formed by applying a positive electrode slurry, in which the components of the positive electrode mixture are dispersed in a dispersion medium, to the surface of the positive electrode current collector and drying the applied layer. The dried coating may be rolled, if necessary.

[0034] As the positive electrode active material, for example, a lithium transition metal composite oxide having a layered rock salt structure is used. Among them, a lithium transition metal composite oxide containing Ni, Co, and at least one of Al and Mn (hereinafter also referred to as composite oxide NC) is promising because it exhibits high capacity and high voltage.

[0035] The composition of the composite oxide NC is, for example, Li α Ni (1-x1-x2-x3-y)Co x1 Mn x2 Al x3 M y O 2+β (0.95 ≤ α ≤ 1.05, 0.5 ≤ 1 - x1 - x2 - x3 - y ≤ 0.95, 0 < x1 ≤ 0.04, 0 ≤ x2 ≤ 0.1, 0 ≤ x3 ≤ 0.1, 0 < x2 + x3 ≤ 0.2, 0 ≤ y ≤ 0.1, -0.05 ≤ β ≤ 0.05). However, M is at least one selected from the group consisting of Ti, Zr, Nb, Mo, W, Fe, Zn, B, Si, Mg, Ca, Sr, and Y. The ratio (atomic ratio) of Ni, indicated by (1 - x1 - x2 - x3 - y), preferably satisfies 0.8 ≤ 1 - x1 - x2 - x3 - y ≤ 0.95, and more preferably satisfies 0.9 ≤ 1 - x1 - x2 - x3 - y ≤ 0.95, from the viewpoint of increasing the capacity.

[0036] Examples of the binder include fluororesins (e.g., polytetrafluoroethylene, polyvinylidene fluoride), polyolefin resins (e.g., polyethylene, polypropylene), polyamide resins (e.g., aramid resins), polyimide resins (e.g., polyimide, polyamideimide), acrylic resins (e.g., polyacrylic acid, polymethacrylic acid, acrylic acid - methacrylic acid copolymer, ethylene - acrylic acid copolymer, or salts thereof), vinyl resins (e.g., polyvinyl acetate), and rubbery materials (e.g., styrene - butadiene copolymer rubber (SBR)).

[0037] Examples of the thickener include cellulose derivatives such as cellulose ether. Examples of the cellulose derivative include CMC and its modified products, methyl cellulose, etc. The modified products of CMC include salts of CMC. Examples of the salt include alkali metal salts (e.g., sodium salt), ammonium salts, etc.

[0038] Examples of the conductive agent include conductive fibers and conductive particles. Examples of the conductive fiber include carbon fiber, carbon nanotube, metal fiber, etc. Examples of the conductive particle include conductive carbon (carbon black, graphite, etc.), metal powder, etc.

[0039] The positive electrode current collector is selected depending on the type of nonaqueous electrolyte secondary battery. A metal foil may be used as the positive electrode current collector. Examples of materials for the metal foil include stainless steel, aluminum, aluminum alloy, and titanium. The thickness of the positive electrode current collector is not particularly limited, but may be, for example, 1 to 50 μm, or 5 to 30 μm.

[0040] (Negative electrode) The negative electrode includes a negative electrode current collector. During charging, lithium metal is deposited on the negative electrode current collector, and during discharging, the lithium metal dissolves. The lithium ions that form the lithium metal are supplied from a non-aqueous electrolyte, and the lithium ions are supplied from the positive electrode to the non-aqueous electrolyte. The negative electrode may include a lithium ion absorption layer (a layer that develops capacity by the absorption and desorption of lithium ions by a negative electrode active material (such as graphite)) supported on the negative electrode current collector. In this case, the open circuit potential of the negative electrode at full charge may be 70 mV or less relative to lithium metal (lithium dissolution and deposition potential). When the open circuit potential of the negative electrode at full charge is 70 mV or less relative to lithium metal, lithium metal is present on the surface of the lithium ion absorption layer at full charge. In other words, the negative electrode develops capacity by the deposition and dissolution of lithium metal.

[0041] Here, "fully charged" refers to a state in which the battery is charged to a state of charge of, for example, 0.98 × C or more, where C is the rated capacity of the battery. The open circuit potential of the negative electrode at full charge can be measured by disassembling a fully charged battery under an argon atmosphere, removing the negative electrode, and assembling a cell with lithium metal as the counter electrode. The nonaqueous electrolyte in the cell may have the same composition as the nonaqueous electrolyte in the disassembled battery.

[0042] The lithium ion occlusion layer is a layer of a negative electrode mixture containing a negative electrode active material. The negative electrode mixture may contain a binder, a thickener, a conductive agent, etc. in addition to the negative electrode active material.

[0043] Examples of the negative electrode active material include a carbonaceous material, a Si-containing material, and a Sn-containing material. The negative electrode may contain one type of negative electrode active material or a combination of two or more types. Examples of the carbonaceous material include graphite, easily graphitizable carbon (soft carbon), and hardly graphitizable carbon (hard carbon).

[0044] The binder, conductive agent, etc. may be, for example, those exemplified for the positive electrode. The shape and thickness of the negative electrode current collector can be selected from the shapes and ranges described for the positive electrode current collector. Examples of the material for the negative electrode current collector (metal foil) include stainless steel, nickel, nickel alloy, copper, and copper alloy.

[0045] (non-aqueous electrolyte) The term "non-aqueous electrolyte" encompasses liquid non-aqueous electrolytes (i.e., non-aqueous electrolyte solutions), gel electrolytes, and solid electrolytes, but excludes aqueous electrolytes. A gel electrolyte may be a non-fluid electrolyte formed by combining a non-aqueous electrolyte solution with a gelling agent or a matrix material. A non-aqueous electrolyte solution includes a non-aqueous solvent, a lithium salt that dissolves in the non-aqueous solvent, and an additive. The additive includes a cation of metal M1. The additive includes halide ions, including those derived from lithium salts. The additive includes oxalate complex anions, including those derived from lithium salts.

[0046] Examples of non-aqueous solvents constituting the non-aqueous electrolyte include cyclic carbonates, chain carbonates, cyclic carboxylic acid esters, chain carboxylic acid esters, and chain ethers. Examples of cyclic carbonates include propylene carbonate (PC) and ethylene carbonate (EC). Examples of chain carbonates include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC). Examples of cyclic carboxylic acid esters include γ-butyrolactone (GBL) and γ-valerolactone (GVL). Examples of chain carboxylic acid esters include methyl formate, ethyl formate, propyl formate, methyl acetate (MA), ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate. Examples of chain ethers include dialkyl ethers and difluoroalkyl ethers each having 1 to 4 carbon atoms. One type of non-aqueous solvent may be used alone, or two or more types may be used in combination.

[0047] Examples of lithium salts that constitute the non-aqueous electrolyte include LiClO4, LiBF4, LiPF6, LiAlCl4, LiSbF6, LiSCN, LiCF3SO3, LiCF3CO2, LiAsF6, and LiB 10 Cl 10Examples of the borate include lithium bis(1,2-benzenediolate(2-)-O,O')borate, lithium bis(2,3-naphthalenediolate(2-)-O,O')borate, lithium bis(2,2'-biphenyldiolate(2-)-O,O')borate, and lithium bis(5-fluoro-2-oleate-1-benzenesulfonic acid-O,O')borate. Examples of imide salts include lithium bisfluorosulfonylimide (LiN(FSO2)2) (hereinafter also referred to as LiFSI), lithium bistrifluoromethanesulfonyl imide (LiN(CF3SO2)2), lithium trifluoromethanesulfonate fluorosulfonylimide (LiN(CF3SO2)(FSO2)), lithium trifluoromethanesulfonate nonafluorobutanesulfonate imide (LiN(CF3SO2)(C4F9SO2)), and lithium bispentafluoroethanesulfonate imide (LiN(C2F5SO2)2). The nonaqueous electrolyte may contain one type of lithium salt or a combination of two or more types.

[0048] The concentration of the lithium salt in the non-aqueous electrolyte is, for example, 0.5 mol / L or more and 2 mol / L or less.

[0049] (separator) It is usually desirable to interpose a separator between the positive electrode and the negative electrode. The separator has high ion permeability and adequate mechanical strength and insulating properties. The separator may be, for example, a microporous thin film, a woven fabric, a nonwoven fabric, or a laminate of at least two selected from these. The separator is preferably made of polyolefin (e.g., polypropylene, polyethylene).

[0050] (others) An example of the structure of a lithium secondary battery is a structure in which an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween and a nonaqueous electrolyte are housed in an outer casing. Alternatively, instead of a wound electrode group, other types of electrode groups may be used, such as a stacked electrode group in which a positive electrode and a negative electrode are stacked with a separator interposed therebetween. The lithium secondary battery may be in any shape, such as a cylindrical shape, a prismatic shape, a coin shape, a button shape, or a laminate shape.

[0051] The configuration of one example of a lithium secondary battery according to the present disclosure is shown in a partial cross-sectional view schematically in Figure 1. The lithium secondary battery 100 shown in Figure 1 is a cylindrical secondary battery.

[0052] The lithium secondary battery 100 is a wound type battery and includes a wound electrode group 40 and a non-aqueous electrolyte. The electrode group 40 includes a strip-shaped positive electrode 10, a strip-shaped negative electrode 20, and a separator 30. The separator 30 is disposed between the positive electrode 10 and the negative electrode 20. A positive electrode lead 13 is connected to the positive electrode 10. A negative electrode lead 23 is connected to the negative electrode 20.

[0053] One end of the positive electrode lead 13 is connected to the positive electrode 10, and the other end is connected to the sealing body 50. The sealing body 50 includes a positive electrode terminal 50a. Typically, the sealing body 50 includes a mechanism that operates as a safety valve when the internal pressure of the battery increases.

[0054] One end of the negative electrode lead 23 is connected to the negative electrode 20, and the other end is connected to the bottom of the case (case body) 60. The case 60 functions as a negative electrode terminal. The case 60 is a cylindrical can with a bottom. The case 60 is made of metal, for example, iron. The inner surface of the iron case 60 is usually nickel-plated. An upper insulating ring 81 and a lower insulating ring 82 made of resin are arranged on the top and bottom of the electrode group 40, respectively. The electrode group 40 and a non-aqueous electrolyte are arranged inside the case 60. The case 60 is sealed with a sealing body 50 and a gasket 70.

[0055] [Example] The present disclosure will be specifically described below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0056] Examples 1 to 4 and Comparative Examples 1 to 4 A lithium secondary battery was fabricated and evaluated according to the following procedure.

[0057] (1) Preparation of the positive electrode Positive electrode active material particles (composition: LiNi 0.9 Co 0.05 Al 0.05 100 parts by mass of acetylene black, 1 part by mass of polyvinylidene fluoride, and an appropriate amount of N-methyl-2-pyrrolidone (NMP) were mixed to obtain a positive electrode slurry. The positive electrode slurry was then applied to one side of an aluminum foil, the coating was dried, and the foil was rolled to form a positive electrode mixture layer (thickness 95 μm, density 3.6 g / cm) on both sides of the aluminum foil. 3 ) was formed to obtain a positive electrode.

[0058] (2) Preparation of the negative electrode The negative electrode was prepared by cutting electrolytic copper foil (thickness: 10 μm) into a predetermined electrode size.

[0059] (3) Preparation of non-aqueous electrolyte A nonaqueous electrolyte was prepared by dissolving LiN(FSO2)2 (i.e., LiFSI) at a concentration of 1 mol / L in a mixed nonaqueous solvent containing DME (dimethoxyethane) and 1,1,1-trifluoroethyl-2,2,3,3-tetrafluoroethyl ether in a volume ratio of 1:3, and then dissolving the additives shown in Tables 1 and 2 (MXn salts (AuI, SnI4, LiI), LiFOB) at the concentrations shown in Tables 1 and 2. LiFOB is lithium difluorooxalatoborate.

[0060] (4) Fabrication of lithium secondary batteries An aluminum tab was attached to the positive electrode, and a nickel tab was attached to the negative electrode. Next, the positive electrode, negative electrode, and separator were arranged so that the separator was disposed between the positive electrode and negative electrode, and they were then spirally wound together. The wound electrode group was housed in a bag-shaped exterior body formed of a laminate sheet including an aluminum layer. After a nonaqueous electrolyte was injected into the exterior body, the exterior body was sealed to obtain a lithium secondary battery (evaluation cell).

[0061] (5) Battery evaluation (Charge / discharge cycle characteristics) The evaluation cell was charged at a constant current of 0.3 It at a temperature of 25°C until the voltage reached 4.1 V, and then charged at a constant voltage of 4.1 V until the current reached 0.05 It. The cell was then discharged at a constant current of 0.3 It until the voltage reached 2.5 V. This charge-discharge cycle was repeated 100 times, and the ratio of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle was calculated as the capacity retention rate (R 100 The results are shown in Table 1. Cells A1 to A4 are examples, and cells B1 to B3 are comparative examples.

[0062] [Table 1]

[0063] It can be seen from Table 1 that when a non-aqueous electrolyte containing an MXn salt was used, the capacity retention rate was significantly improved compared to the comparative example.

[0064] (Storage characteristics) Some of the evaluation cells were charged at a constant current of 0.3 It at a temperature of 25°C until the voltage reached 4.1 V, and then charged at a constant voltage of 4.1 V until the current reached 0.05 It. The charged cells were then stored at 25°C for 10 days, and then discharged at a constant current of 0.3 It until the voltage reached 2.5 V. The ratio of the discharge capacity after 10 days of storage to the discharge capacity at the first cycle was defined as the post-storage capacity retention rate (R St25 The results are shown in Table 2. Cell B4 is a comparative example.

[0065] [Table 2]

[0066] From Table 2, it can be seen that particularly good storage characteristics are obtained when MXn salts and LiFOB are used in combination, and that the storage characteristics behave completely differently depending on the presence or absence of a cation of a metal M1 other than lithium. [Industrial Applicability]

[0067] The present disclosure can be used in lithium secondary batteries. [Explanation of symbols]

[0068] 10 positive electrode 13 Positive lead 20 negative electrode 23 Negative lead 30 Separator 40 electrode groups 50 Sealing body 50a positive terminal 60 Case (Case Body) 70 Gasket 81 Upper insulating ring 82 Lower insulating ring 100 Lithium secondary battery

Claims

1. a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte; In the negative electrode, lithium metal is precipitated during charging, and the lithium metal is dissolved during discharging, the non-aqueous electrolyte contains lithium ions, cations of a metal M1 that forms an alloy with lithium, halide ions, and oxalate complex anions; In the negative electrode, the lithium metal and the metal M1 form an alloy.

2. 2. The lithium secondary battery according to claim 1, wherein the metal M1 is at least one selected from the group consisting of In, Sn, Au, Ag, Pt, Zn, Sb, Bi, Si, and Mg.

3. 3. The lithium secondary battery according to claim 1, wherein the concentration of the cation of the metal M1 in the non-aqueous electrolyte is 100 mmol / L or less.

4. 4. The lithium secondary battery according to claim 1, wherein the concentration of the halide ions in the non-aqueous electrolyte is 0.5 mmol / L or more and 100 mmol / L or less.

5. A lithium secondary battery according to claim 1, wherein the concentration of the oxalate complex anion in the non-aqueous electrolyte is 50 mmol / L or more and 300 mmol / L or less.

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