Negative electrode for secondary batteries and secondary batteries

Abstract

This secondary battery comprises a positive electrode, a negative electrode including a negative electrode active material layer, and an electrolyte, wherein the negative electrode active material layer includes an alkali metal carbonate compound and a magnesium compound. The alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and includes an alkali metal element as a constituent element, and the magnesium compound includes magnesium as a constituent element.

Description

[Technical Field]

[0001] This technology relates to a negative electrode for secondary batteries and secondary batteries. [Background technology]

[0002] With the widespread use of various electronic devices such as mobile phones, development of rechargeable batteries is progressing as a power source that is small, lightweight, and provides high energy density. These rechargeable batteries contain an electrolyte along with a positive electrode and a negative electrode (negative electrode for rechargeable batteries), and various studies are being conducted on the configuration of these rechargeable batteries.

[0003] Specifically, the negative electrode active material layer contains ceramic nanoparticles (MgO) along with the negative electrode active material (carbon material) (see, for example, Patent Document 1). The anode active material contains (CH2OCO2Li)2 as a lithium ion conductive additive (see, for example, Patent Document 2). At least one of the positive electrode, negative electrode, and non-aqueous electrolyte contains a basic compound, and that basic compound is an anion (NO2 - ) and cations (Mg 2+ ) contains (see, for example, Patent Document 3). The electrode binder contains a polymer compound, and that polymer compound contains anions (NO3 - or NO2 - ) and cations (Mg 2+ ) includes (see, for example, Patent Document 4). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-305545 [Patent Document 2] Special Publication No. 2020-513138 [Patent Document 3] Japanese Patent Publication No. 2015-090860 [Patent Document 4] Japanese Patent Publication No. 2014-077134 [Overview of the Initiative]

[0005] Although various studies have been conducted on the configuration of secondary batteries, the battery characteristics of such secondary batteries are not yet sufficient, so there is room for improvement.

[0006] A negative electrode for a secondary battery and a secondary battery capable of obtaining excellent battery characteristics are desired.

[0007] The negative electrode for a secondary battery according to one embodiment of the present technology includes a negative electrode active material layer, the negative electrode active material layer contains an alkali metal carbonate compound and a magnesium compound, the alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and contains an alkali metal element as a constituent element, and the magnesium compound contains magnesium as a constituent element.

[0008] A secondary battery according to one embodiment of the present technology includes a positive electrode, a negative electrode, and an electrolytic solution, and the negative electrode has the same configuration as that of the negative electrode for a secondary battery according to one embodiment of the present technology described above.

[0009] According to the negative electrode for a secondary battery or the secondary battery according to one embodiment of the present technology, since the negative electrode for a secondary battery includes a negative electrode active material layer and the negative electrode active material layer contains an alkali metal carbonate compound and a magnesium compound, excellent battery characteristics can be obtained.

[0010] Note that the effects of the present technology are not necessarily limited to the effects described here, and may be any of a series of effects related to the present technology described later.

Brief Description of the Drawings

[0012] An embodiment of this technology will be described in detail below with reference to the drawings. The order of description is as follows. 1. Negative electrode for secondary batteries 1-1. Composition 1-2.Operation 1-3. Manufacturing method 1-4. Action and Effects 2. Secondary battery 2-1. Composition 2-2.Operation 2-3. Manufacturing method 2-4. Mechanism of Action and Effects 3. Variant 4. Applications of rechargeable batteries

[0013] <1. Negative electrode for secondary batteries> First, we will describe a negative electrode for a secondary battery (hereinafter simply referred to as "negative electrode") according to one embodiment of this technology.

[0014] The negative electrode described here is used in secondary batteries, which are electrochemical devices. However, negative electrodes may also be used in other electrochemical devices besides secondary batteries. Specific examples of other electrochemical devices include primary batteries and capacitors.

[0015] This negative electrode intercepts and releases electrode reactants during electrode reactions in electrochemical devices. The type of electrode reactant is not particularly limited, but specifically, it is light metals such as alkali metals and alkaline earth metals. Specific examples of alkali metals include lithium, sodium, and potassium, while specific examples of alkaline earth metals include beryllium, magnesium, and calcium.

[0016] The following example uses lithium as the electrode reactant. At the negative electrode, lithium is intercalated and released in an ionic state during the electrode reaction.

[0017] <1-1. Structure> Figure 1 shows a cross-sectional configuration of a negative electrode 100, which is an example of a negative electrode. As shown in Figure 1, this negative electrode 100 includes a negative electrode active material layer 120. Here, the negative electrode 100 further includes a negative electrode current collector 110 that supports the negative electrode active material layer 120.

[0018] [Negative electrode current collector] The negative electrode current collector 110 is a conductive support that supports the negative electrode active material layer 120, and has a pair of surfaces on which the negative electrode active material layer 120 is provided. The negative electrode current collector 110 contains one or more types of conductive materials such as metal materials, and a specific example of such conductive material is copper.

[0019] It is preferable that the surface of the negative electrode current collector 110 is roughened using an electrolytic method or the like. This is because the adhesion of the negative electrode active material layer 120 to the negative electrode current collector 110 is improved by utilizing the so-called anchoring effect.

[0020] However, the negative electrode current collector 110 may be omitted. That is, the negative electrode 100 may consist only of the negative electrode active material layer 120 without the negative electrode current collector 110.

[0021] [Negative electrode active material layer] The negative electrode active material layer 120 contains an alkali metal carbonate compound and a magnesium compound. Here, the negative electrode active material layer 120 further contains a negative electrode active material that intercalates and deintercalates lithium. However, the negative electrode active material layer 120 may further contain one or more of the following other materials: a negative electrode binder and a negative electrode conductive agent.

[0022] Here, the negative electrode active material layer 120 is provided on both sides of the negative electrode current collector 110. However, the negative electrode active material layer 120 may be provided on only one side of the negative electrode current collector 110. The method for forming the negative electrode active material layer 120 is not particularly limited, but specifically, it may be a coating method.

[0023] (Negative electrode active material) The type of negative electrode active material is not particularly limited, but specifically, it is one or more types of materials such as carbon materials and metallic materials. In other words, the negative electrode active material may be carbon material alone, metallic material alone, or both carbon material and metallic material. This is because a high energy density can be obtained. However, the type of negative electrode active material may be other materials other than carbon material and metallic material.

[0024] Carbon materials are a general term for materials that contain carbon as a constituent element. Because the crystal structure of carbon materials hardly changes during lithium intercalation and deintercalation, a high energy density can be stably obtained in the negative electrode active material layer 120. Furthermore, since carbon materials also function as negative electrode conductive agents, the conductivity of the negative electrode active material layer 120 is improved.

[0025] Specific examples of carbon materials include readily graphitizable carbon, non-graphitizable carbon, and graphite. This graphite may be natural graphite, artificial graphite, or both. The interplanar spacing of the (002) planes for non-graphitizable carbon is not particularly limited, but specifically it is 0.37 nm or more. The interplanar spacing of the (002) planes for graphite is not particularly limited, but specifically it is 0.34 nm or less.

[0026] Specific examples of carbon materials include pyrolysis carbons, cokes, glassy carbon fibers, calcined organic polymer compounds, activated carbon, and carbon blacks. These cokes include pitch coke, needle coke, and petroleum coke. Calcined organic polymer compounds are calcined products obtained by calcining (carbonizing) polymer compounds such as phenolic resins and furan resins at an appropriate temperature. In addition, the carbon material may be low-crystalline carbon heat-treated at a temperature of approximately 1000°C or lower, or amorphous carbon. The shape of the carbon material is not particularly limited, but specifically, it may be one or more of the following: fibrous, spherical, granular, and flaky.

[0027] Metallic materials are a general term for materials that contain one or more metallic elements and metalloid elements capable of forming alloys with lithium as constituent elements. Because metallic materials have a higher energy density, a higher energy density can be obtained in the negative electrode active material layer 120.

[0028] This metallic material may be an element, an alloy, a compound, a mixture of two or more of these, or a material containing one or more of these phases. The term "element" as used here refers to a general element, and therefore may contain trace amounts of impurities. In other words, the purity of the element is not necessarily limited to 100%.

[0029] However, the term "alloy" as used herein includes not only materials containing two or more metallic elements as constituent elements, but also materials containing one or more metallic elements and one or more metalloid elements as constituent elements. Furthermore, an "alloy" may also contain one or more nonmetallic elements as constituent elements. The microstructure of metallic materials is not particularly limited, but specifically, it is one or more of the following: solid solutions, eutectic (eutectic mixture), intermetallic compounds, and coexistences of two or more of these.

[0030] Specific examples of metallic and metalloid elements include magnesium, boron, aluminum, gallium, indium, silicon, germanium, tin, lead, bismuth, cadmium, silver, zinc, hafnium, zirconium, yttrium, palladium, and platinum.

[0031] In particular, the metallic material is preferably a silicon-containing material. Because silicon-containing materials have excellent lithium intercalation and deintercalation capabilities, a remarkably high energy density can be obtained in the negative electrode active material layer 120. This silicon-containing material is a general term for materials that contain silicon as a constituent element. That is, the silicon-containing material may be elemental silicon, a silicon alloy, a silicon compound, a mixture of two or more of these, or a material containing one or more of these phases.

[0032] Silicon alloys contain one or more metallic elements other than silicon, such as tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium. Silicon compounds also contain one or more nonmetallic elements other than silicon, such as carbon and oxygen. However, silicon compounds may also contain one or more of the metallic elements described for silicon alloys.

[0033] Specific examples of silicon alloys include SiB4, SiB6, Mg2Si, Ni2Si, TiSi2, MoSi2, CoSi2, NiSi2, CaSi2, CrSi2, Cu5Si, FeSi2, MnSi2, NbSi2, TaSi2, VSi2, WSi2, ZnSi2, and SiC. However, the composition of silicon alloys (the mixing ratio of silicon to metal elements) can be arbitrarily changed.

[0034] Specific examples of silicon compounds include Si3N4, Si2N2O, and SiO2. x(0 < x ≤ 2) and LiSiO etc. However, the range of x may be 0.2 < x < 1.4.

[0035] In particular, the negative electrode active material preferably contains both a carbon material and a silicon-containing material. This is because during the electrode reaction (charging and discharging) of the secondary battery using the negative electrode 100, the damage to the negative electrode active material layer 120 is suppressed while ensuring the battery capacity.

[0036] Specifically, the silicon-containing material which is a metal-based material has the advantage of having a high theoretical capacity, but has the concern of being prone to severe expansion and contraction during charging and discharging. On the other hand, the carbon material has the concern of having a low theoretical capacity, but has the advantage of being less prone to expansion and contraction during charging and discharging. Therefore, by using the carbon material and the silicon-containing material in combination, a high theoretical capacity can be obtained while the expansion and contraction of the negative electrode active material layer 120 during charging and discharging are suppressed. Thereby, as described above, the damage to the negative electrode active material layer 120 is suppressed while ensuring the battery capacity. Specific examples of the damage to the negative electrode active material layer 120 include cracking and peeling of the negative electrode active material layer 120.

[0037] (alkali metal carbonate compound) The alkali metal carbonate compound is contained in the negative electrode active material layer 120 as described above. Thereby, the alkali metal carbonate compound is dispersed in the negative electrode active material layer 120.

[0038] This alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and contains an alkali metal element as a constituent element. The number of carbonate bonds may be only one or two or more. Specific examples of the alkali metal element are lithium, sodium, potassium, etc. as described above. The type of the alkali metal carbonate compound may be only one type or two or more types.

[0039] The reason the negative electrode active material layer 120 contains an alkali metal carbonate compound is that a good film is formed on the surface of the negative electrode active material during charging and discharging. This film is derived from the alkali metal carbonate compound and has a high-density pore structure. Therefore, the film protects the surface of the highly reactive negative electrode active material by covering it, thus ensuring lithium input and output in the negative electrode active material while protecting the surface from the electrolyte (barrier function). Furthermore, the film reinforces the physical strength of the negative electrode active material by following its expansion and contraction during charging and discharging, thus suppressing damage to the negative electrode active material (stress relaxation function).

[0040] (Specific structure) The type of alkali metal carbonate compound is not particularly limited, but it is preferable that the alkali metal carbonate compound contains one or more of the following: lithium carbonate (Li2CO3), a primary alkali metal carbonate compound, and a secondary alkali metal carbonate compound. This is because it facilitates the stable formation of a coating derived from the alkali metal carbonate compound.

[0041] The first alkali metal carbonate compound is one or more of the compounds represented by formula (1). As is clear from formula (1), this first alkali metal carbonate compound has one carbonic acid bond.

[0042] R1-OC(=O)O-M1 ···(1) (R1 is an alkyl group. M1 is an alkali metal element.)

[0043] The type of alkyl group is not particularly limited, but specifically includes methyl, ethyl, and propyl groups. However, alkyl groups may be linear or branched. Details regarding alkali metal elements are as described above.

[0044] Specific examples of alkali metal first carbonate compounds include lithium methyl carbonate (H3C-OC(=O)O-Li), lithium ethyl carbonate (H5C2-OC(=O)O-Li), lithium propyl carbonate (H7C3-OC(=O)O-Li), sodium methyl carbonate (H3C-OC(=O)O-Na), sodium ethyl carbonate (H5C2-OC(=O)O-Na), sodium propyl carbonate (H7C3-OC(=O)O-Na), potassium methyl carbonate (H3C-OC(=O)OK), potassium ethyl carbonate (H5C2-OC(=O)OK), and potassium propyl carbonate (H7C3-OC(=O)OK).

[0045] The second alkali metal carbonate compound is one or more of the compounds represented by formula (2). As is clear from formula (2), this second alkali metal carbonate compound has two carbonic acid bonds.

[0046] M2-OC(=O)O-R2-OC(=O)O-M3 ···(2) (R2 is an alkylene group. M2 and M3 are alkali metal elements, respectively.)

[0047] The type of alkylene group is not particularly limited, but specifically includes methylene, ethylene, and propylene groups. However, the alkylene group may be linear or branched. Details regarding alkali metal elements are as described above.

[0048] Specific examples of alkali metal dicarbonates include dilithium methylenedicarbonate (Li-OC(=O)O-CH2-OC(=O)O-Li), dilithium ethylenedicarbonate (Li-OC(=O)O-C2H4-OC(=O)O-Li), dilithium propylenedicarbonate (Li-OC(=O)O-C3H6-OC(=O)O-Li), disodium methylenedicarbonate (Na-OC(=O)O-CH2-OC(=O)O-Na), and disodium ethylenedicarbonate. Examples include sodium bicarbonate (Na-OC(=O)O-C2H4-OC(=O)O-Na), disodium propylenedicarbonate (Na-OC(=O)O-C3H6-OC(=O)O-Na), dipotassium methylenedicarbonate (K-OC(=O)O-CH2-OC(=O)OK), dipotassium ethylenedicarbonate (K-OC(=O)O-C2H4-OC(=O)OK), and dipotassium propylenedicarbonate (K-OC(=O)O-C3H6-OC(=O)OK).

[0049] In particular, in the first alkali metal carbonate compound shown in formula (1), the alkali metal element (M1) is preferably lithium, and in the second alkali metal carbonate compound shown in formula (2), the alkali metal elements (M2 and M3) are preferably lithium. This is because the coating derived from the alkali metal carbonate compound is more easily and stably formed.

[0050] (Content) The content of alkali metal carbonate compounds in the negative electrode active material layer 120 is not particularly limited, but is preferably 0.2% to 0.8% by weight. This is because a film derived from the alkali metal carbonate compounds is more easily and stably formed.

[0051] Furthermore, if the negative electrode active material layer 120 contains two or more alkali metal carbonate compounds, the "content of alkali metal carbonate compounds in the negative electrode active material layer 120" described here is the sum of the contents of each alkali metal carbonate compound.

[0052] (Verification procedure and calculation procedure) The procedure for confirming whether or not alkali metal carbonate compounds are present in the negative electrode active material layer 120, and the procedure for calculating the content of alkali metal carbonate compounds in the negative electrode active material layer 120, are as described below.

[0053] First, the negative electrode active material layer 120 of the negative electrode 100 is recovered by separating the negative electrode current collector 110 from the negative electrode active material layer 120. If a secondary battery equipped with a negative electrode 100 is used, the negative electrode 100 is recovered by disassembling the secondary battery.

[0054] Next, the negative electrode active material layer 120 is cleaned using a cleaning solvent, and then the negative electrode active material layer 120 is dried. The type of cleaning solvent is not particularly limited, but specifically, it is an organic solvent such as acetone. The environmental conditions during drying are not particularly limited, but specifically, it may be an inert gas atmosphere using argon gas or a dry environment.

[0055] Next, the negative electrode active material layer 120 is added to the extraction solution to perform the extraction process (extraction time = 15 minutes). The type of extraction solution is not particularly limited, but specifically, it is a dimethyl sulfoxide-d6 solution of bis(trifluoromethanesulfonyl)imide lithium (LiN(CF3SO2)2) (LiTFSI DMSO-d6). This yields the extract.

[0056] Next, the extract is analyzed using nuclear magnetic resonance (NMU). Here, proton NMU is used as the NMU. 1 ¹H NMR and carbon-13 nuclear magnetic resonance ( 13 13C NMR is used. If a peak attributed to alkali metal carbonate is detected, it is confirmed that alkali metal carbonate is present in the negative electrode active material layer 120.

[0057] For example, when the alkali metal carbonate compound is the first alkali metal carbonate compound (lithium ethylene carbonate), peaks are detected at 3.44 ppm and 3.72 ppm in the proton nuclear magnetic resonance method, and peaks are detected at 61.0 ppm, 65.8 ppm, and 156.9 ppm in the carbon-13 nuclear magnetic resonance method.

[0058] Also, when the alkali metal carbonate compound is the second alkali metal carbonate compound (dilithium ethylene dicarbonate), a peak is detected at 3.63 ppm in the proton nuclear magnetic resonance method, and peaks are detected at 62.7 ppm and 166.2 ppm in the carbon-13 nuclear magnetic resonance method.

[0059] Subsequently, when the alkali metal carbonate compound is contained in the negative electrode active material layer 120, the weight of the partial structure (alkali metal carbonate compound) in the extract is calculated by comparing the integral value of the signal corresponding to the partial structure of the organic film component with the integral value of the signal of the internal standard substance. The type of the internal standard substance is not particularly limited, but specifically, it is sodium 3-(trimethylsilyl)propionate-d4 or the like.

[0060] Finally, based on the weight of the negative electrode active material layer 120 and the weight of the alkali metal carbonate compound, the content of the alkali metal carbonate compound in the negative electrode active material layer 120 is calculated. In this case, the following calculation formula is used: content (wt%) of the alkali metal carbonate compound in the negative electrode active material layer 120 = (weight of the alkali metal carbonate compound / weight of the negative electrode active material layer 120) × 100.

[0061] When confirming whether the alkali metal carbonate compound is contained in the negative electrode active material layer 120, infrared spectroscopy may be used instead of nuclear magnetic resonance spectroscopy.

[0062] For example, when the alkali metal carbonate compound is the second alkali metal carbonate compound (dilithium ethylene dicarbonate), at 1650 cm -1 , 1395 cm -1 , 1305 cm-1 , 1080cm -1 and 820cm -1 A peak is detected in each of them.

[0063] (Magnesium compounds) As described above, the magnesium compound is contained in the negative electrode active material layer 120. Therefore, the magnesium compound is dispersed within the negative electrode active material layer 120. Thus, the alkali metal carbonate compound and the magnesium compound are dispersed within the negative electrode active material layer 120 while being mixed with each other.

[0064] This magnesium compound contains magnesium as a constituent element. The types of elements other than magnesium contained in the magnesium compound are not particularly limited and can be arbitrarily selected. Furthermore, the magnesium compound may contain only one type of element or two or more.

[0065] The negative electrode active material layer 120 contains a magnesium compound along with the alkali metal carbonate compound because, during charging and discharging, the magnesium compound acts self-sacrificingly, reacting and decomposing preferentially over the alkali metal carbonate compound. As a result, the reaction and decomposition of the alkali metal carbonate compound are suppressed by utilizing the magnesium compound. Therefore, even after repeated charging and discharging, the film derived from the alkali metal carbonate compound is more easily formed stably and continuously, and the function of that film (barrier function and stress relaxation function) is more easily maintained.

[0066] (Specific structure) The type of magnesium compound is not particularly limited, but specific examples of magnesium compounds include magnesium fluoride (MgF2), magnesium oxide (MgO), magnesium nitride (Mg3N2), and magnesium carbonate (MgCO3). This is because the reaction and decomposition of alkali metal carbonate compounds are sufficiently suppressed, thus ensuring that the function of the coating is well maintained.

[0067] Furthermore, the magnesium compound may already be present in the negative electrode active material layer 120 even before the first charge and discharge of the secondary battery.

[0068] Alternatively, the magnesium compound may not be present in the negative electrode active material layer 120 before the first charge and discharge of the secondary battery, but may be present in the negative electrode active material layer 120 only after the charge and discharge of the secondary battery. In other words, although the magnesium compound is not present in the negative electrode active material layer 120 before the first charge and discharge, it may be present in the negative electrode active material layer 120 after the first charge and discharge by utilizing the charge and discharge reaction.

[0069] The types of materials that can be used to form magnesium compounds using this charge-discharge reaction are not particularly limited, but specifically include magnesium nitrate (Mg(NO3)2) and magnesium carbonate (Mg(CO3)2).

[0070] (Content) The magnesium compound content in the negative electrode active material layer 120 is not particularly limited, but is preferably 0.01% to 5% by weight. This is because the reaction and decomposition of alkali metal carbonate compounds are sufficiently suppressed, thereby ensuring that the function of the coating is well maintained.

[0071] If the negative electrode active material layer 120 contains two or more types of magnesium compounds, the "magnesium compound content in the negative electrode active material layer 120" described here is the sum of the content of each magnesium compound.

[0072] (Verification procedure and calculation procedure) The procedure for confirming whether or not a magnesium compound is present in the negative electrode active material layer 120, and the procedure for calculating the magnesium compound content in the negative electrode active material layer 120, are as described below.

[0073] First, the negative electrode active material layer 120 of the negative electrode 100 is recovered by separating the negative electrode current collector 110 from the negative electrode active material layer 120. If a secondary battery equipped with a negative electrode 100 is used, the negative electrode 100 is recovered by disassembling the secondary battery.

[0074] Next, the negative electrode active material layer 120 is cleaned using a cleaning solvent, and then the negative electrode active material layer 120 is allowed to air dry. The type of cleaning solvent is not particularly limited, but specifically, it is an organic solvent such as dimethyl carbonate. The environmental conditions during drying are not particularly limited, but specifically, they are inside a glove box into which an inert gas such as argon gas is introduced.

[0075] Next, after preparing the sample for analysis using conductive carbon double-sided tape (conductive carbon double-sided tape (8mm x 20m), model number 7311) manufactured by Nissin EM Co., Ltd., the sample is moved from inside the glove box into the X-ray photoelectron spectroscopy (XPS) instrument. In this case, the sample is introduced into the XPS instrument while ensuring that it is not exposed to the atmosphere.

[0076] Next, the sample is analyzed using an XPS instrument. If a peak originating from a magnesium compound is detected, it is confirmed that a magnesium compound is present in the negative electrode active material layer 120.

[0077] For example, when the magnesium compound is magnesium oxide, a peak is detected around a bond energy of approximately 50.4 eV, while when the magnesium compound is magnesium fluoride, a peak is detected around a bond energy of approximately 50.9 eV.

[0078] For XPS analysis, the ULVAC-PHI PHI 5000 VersaProbe X-ray photoelectron spectroscopy analyzer can be used. The analysis conditions were as follows: X-ray source = monochromatic Al-Kα rays (1486.6 eV), X-ray spot diameter = 100 μmφ, photoelectron escape angle = 45°, and charge neutralization = neither an electron gun (flood gun) nor an Ar ion gun was used.

[0079] Next, if a magnesium compound is present in the negative electrode active material layer 120, the weight of the magnesium compound is calculated based on the ratio of the peak area derived from the magnesium compound, which is normalized based on relative sensitivity, to the peak area derived from each element contained in the negative electrode active material layer 120.

[0080] Finally, the magnesium compound content in the negative electrode active material layer 120 is calculated based on the weight of the negative electrode active material layer 120 and the weight of the magnesium compound. In this case, the formula used is: magnesium compound content in negative electrode active material layer 120 (weight %) = (weight of magnesium compound / weight of negative electrode active material layer 120) × 100.

[0081] (Negative electrode binder) The negative electrode binder contains one or more materials, such as synthetic rubber and polymer compounds. Specific examples of synthetic rubber include styrene-butadiene rubber, fluorine-based rubber, and ethylene-propylenediene. Specific examples of polymer compounds include polyvinylidene fluoride, polyimide, and carboxymethylcellulose.

[0082] (Negative electrode conductive agent) The negative electrode conductive agent contains one or more types of conductive materials, such as carbon materials. Specific examples of these conductive materials include graphite, carbon black, acetylene black, and Ketjenblack. However, the conductive material is not limited to carbon materials; it may also be a metallic material or a polymer compound.

[0083] <1-2. Operation> In this negative electrode 100, during the electrode reaction, the negative electrode active material layer 120 absorbs lithium in an ionic state, and lithium is also released from the negative electrode active material in an ionic state.

[0084] <1-3. Manufacturing method> When manufacturing the negative electrode 100, the negative electrode active material, alkali metal carbonate compound, and magnesium compound are first mixed together to form a negative electrode mixture. In this case, a negative electrode binder and a negative electrode conductive agent may be included in the negative electrode mixture as needed.

[0085] Next, a paste-like anode mixture slurry is prepared by adding the anode mixture to the solvent. The type of solvent is not particularly limited; it may be an aqueous solvent or an organic solvent. In this case, the solvent containing the anode mixture may be stirred using a stirring device such as a mixer.

[0086] Here, a negative electrode mixture containing a negative electrode active material, an alkali metal carbonate compound, and a magnesium compound was prepared, and then a negative electrode mixture slurry was prepared using this negative electrode mixture. However, it is also possible to prepare a negative electrode mixture containing a negative electrode active material, prepare a negative electrode mixture slurry using this mixture, and then add the alkali metal carbonate compound and the magnesium compound to the negative electrode mixture slurry.

[0087] Finally, the negative electrode active material layer 120 is formed by applying the negative electrode mixture slurry to both sides of the negative electrode current collector 110. After this, the negative electrode active material layer 120 may be compressed and molded using a roll press or the like. In this case, the negative electrode active material layer 120 may be heated, or the compression molding may be repeated multiple times.

[0088] As a result, a negative electrode active material layer 120 is formed on both sides of the negative electrode current collector 110, thus completing the negative electrode 100.

[0089] <1-4. Mechanism and Effects> According to this negative electrode 100, the negative electrode active material layer 120 contains an alkali metal carbonate compound and a magnesium compound.

[0090] In this case, since the negative electrode active material layer 120 contains an alkali metal carbonate compound, as described above, a good film derived from the alkali metal carbonate compound is formed on the surface of the negative electrode active material during charging and discharging of the secondary battery using the negative electrode 100. This suppresses the decomposition reaction of the electrolyte on the surface of the negative electrode active material while ensuring lithium input and output by utilizing the barrier function of the film. Furthermore, damage to the negative electrode active material caused by expansion and contraction is suppressed by utilizing the stress relaxation function of the film.

[0091] Furthermore, since the negative electrode active material layer 120 contains a magnesium compound along with the alkali metal carbonate compound, as described above, the magnesium compound reacts and decomposes preferentially over the alkali metal carbonate compound during charging and discharging, thereby suppressing the reaction and decomposition of the alkali metal carbonate compound. As a result, even after repeated charging and discharging, a film derived from the alkali metal carbonate compound is more easily formed stably and continuously, and the function of that film (barrier function and stress relaxation function) is more easily maintained. Therefore, the decomposition reaction of the electrolyte on the surface of the negative electrode active material is continuously suppressed, and damage to the negative electrode active material due to expansion and contraction is continuously suppressed.

[0092] Because of these factors, the discharge capacity does not decrease easily even after repeated charging and discharging, resulting in excellent battery characteristics in a secondary battery using negative electrode 100.

[0093] In particular, if the alkali metal carbonate compound contains one or more of lithium carbonate, a first alkali metal carbonate compound, and a second alkali metal carbonate compound, a coating derived from that alkali metal carbonate compound is more easily formed stably, thus achieving a higher effect.

[0094] In this case, if the alkali metal element (M1) in formula (1) relating to the first alkali metal carbonate compound is lithium, and the alkali metal elements (M2 and M3) in formula (2) relating to the second alkali metal carbonate compound are lithium, then a coating derived from the alkali metal carbonate compound is more easily formed stably, thus achieving a higher effect.

[0095] Furthermore, if the magnesium compound contains one or more of the following: magnesium fluoride, magnesium oxide, magnesium nitride, and magnesium carbonate, the reaction and decomposition of alkali metal carbonate compounds are more easily suppressed. Therefore, the function of the coating is more easily maintained, resulting in a higher effectiveness.

[0096] Furthermore, if the alkali metal carbonate compound content in the negative electrode active material layer 120 is 0.2% to 0.8% by weight, a coating derived from the alkali metal carbonate compound is more easily formed stably, thus achieving a higher effect.

[0097] Furthermore, if the magnesium compound content in the negative electrode active material layer 120 is between 0.01% and 5% by weight, the reaction and decomposition of alkali metal carbonate compounds are more easily suppressed. Therefore, the function of the coating is more easily maintained, and a higher effect can be obtained.

[0098] Furthermore, if the negative electrode active material layer 120 contains a negative electrode active material, and that negative electrode active material contains carbon material and silicon-containing material, then the damage to the negative electrode active material layer 120 is suppressed while the battery capacity is ensured, thus achieving a higher level of performance.

[0099] <2. Secondary battery> Next, a secondary battery according to one embodiment of this technology to which the negative electrode 100 is applied will be described.

[0100] The secondary battery described here is a secondary battery that obtains its capacity by utilizing the intercalation and deintercalation of electrode reactants, and is equipped with an electrolyte along with a positive electrode and a negative electrode.

[0101] The charging capacity of the negative electrode is preferably greater than the discharge capacity of the positive electrode. In other words, the electrochemical capacity per unit area of ​​the negative electrode is preferably greater than the electrochemical capacity per unit area of ​​the positive electrode. This is to suppress the deposition of electrode reactants on the surface of the negative electrode during charging.

[0102] In the following examples, we will use the case where lithium is the electrode reactant, as mentioned above. A secondary battery that obtains battery capacity by utilizing the intercalation and deintercalation of lithium is a so-called lithium-ion secondary battery. In this lithium-ion secondary battery, lithium is intercalated and deintercalated in an ionic state.

[0103] <2-1. Structure> Figure 2 shows a perspective view of the secondary battery, and Figure 3 shows a cross-sectional view of the battery element 20 shown in Figure 2. Figure 4 shows a planar view of the positive electrode 21 shown in Figure 3, and Figure 5 shows a planar view of the negative electrode 22 shown in Figure 3. However, in Figure 2, the outer film 10 and the battery element 20 are shown separated from each other.

[0104] As shown in Figures 2 and 3, this secondary battery comprises an outer film 10, a battery element 20, a plurality of positive terminals 31, a plurality of negative terminals 32, a positive lead 41, a negative lead 42, and sealing films 51 and 52.

[0105] The secondary battery described here, as mentioned above, uses a flexible or pliable outer film 10 as an outer component, and is therefore a so-called laminate film type secondary battery.

[0106] [Exterior film] As shown in Figure 2, the outer film 10 is an outer component that houses the battery element 20, and has a sealed bag-like structure in which the battery element 20 is housed. In this way, the outer film 10 houses the electrolyte together with the positive electrode 21 and negative electrode 22, which will be described later.

[0107] Here, the outer film 10 is a single film-like component that is folded in the folding direction F. The outer film 10 is provided with a recessed portion 10U (a so-called deep-drawn portion) for housing the battery element 20.

[0108] Specifically, the outer film 10 is a three-layer laminate film in which a fusion layer, a metal layer, and a surface protection layer are laminated in this order from the inside out. When the outer film 10 is folded, the outer edges of the opposing fusion layers are fused together. The fusion layer contains a polymer compound such as polypropylene. The metal layer contains a metallic material such as aluminum. The surface protection layer contains a polymer compound such as nylon.

[0109] However, the composition (number of layers) of the outer film 10 is not particularly limited; it may consist of one or two layers, or four or more layers.

[0110] [Battery element] As shown in Figures 2 to 5, the battery element 20 is a power generation element that includes a positive electrode 21, a negative electrode 22, a separator 23, and an electrolyte (not shown), and is housed inside the outer film 10.

[0111] Here, the battery element 20 is a so-called multilayer electrode body, and the positive electrode 21 and negative electrode 22 are stacked alternately with separators 23 in between. The number of each of the positive electrode 21, negative electrode 22, and separator 23 is not particularly limited and can be set arbitrarily.

[0112] (positive electrode) The positive electrode 21 includes a positive electrode current collector 21A and a positive electrode active material layer 21B, as shown in Figures 3 and 4. In Figure 4, the positive electrode active material layer 21B is shaded.

[0113] The positive electrode current collector 21A has a pair of surfaces on which the positive electrode active material layer 21B is provided. This positive electrode current collector 21A contains a conductive material such as a metal material, a specific example of which is aluminum.

[0114] The positive electrode active material layer 21B contains one or more types of positive electrode active materials that intercalate and deintercalate lithium. However, the positive electrode active material layer 21B may further contain one or more types of other materials such as positive electrode binders and positive electrode conductive agents.

[0115] Here, the positive electrode active material layer 21B is provided on both sides of the positive electrode current collector 21A. However, the positive electrode active material layer 21B may be provided on only one side of the positive electrode current collector 21A on the side where the positive electrode 21 faces the negative electrode 22. The method for forming the positive electrode active material layer 21B is not particularly limited, but specifically, it may be a coating method.

[0116] The type of positive electrode active material is not particularly limited, but specifically, it is a lithium-containing compound. This lithium-containing compound is a compound that contains lithium along with one or more transition metal elements as constituent elements, and may further contain one or more other elements as constituent elements. The type of other element is not particularly limited as long as it is an element other than lithium and the transition metal elements, but specifically, it is an element belonging to groups 2 to 15 of the long-period periodic table. The type of lithium-containing compound is not particularly limited, but specifically, it is an oxide, a phosphoric acid compound, a silicate compound, and a borate compound.

[0117] Specific examples of oxides include LiNiO2, LiCoO2, and LiCo 0.98 Al 0.01 Mg 0.01 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, LiLiLi 0.8 Co 0.15 Al 0.05 O2, LiLiLi 0.33 Co 0.33 Mn 0.33 O2, Li 1.2 Mn 0.52 Co 0.175 Ni 0.1 O2, Li 1.15 (Mn 0.65Ni 0.22 Co 0.13 Examples include O2 and LiMn2O4. Specific examples of phosphorylated compounds include LiFePO4, LiMnPO4, and LiFe 0.5 Mn 0.5 PO4 and LiFe 0.3 Mn 0.7 Examples include PO4.

[0118] Details regarding the positive electrode binder and positive electrode conductive agent are the same as the details regarding the negative electrode binder and negative electrode conductive agent described above.

[0119] Here, as shown in Figure 4, a portion of the positive electrode current collector 21A protrudes, and therefore the positive electrode current collector 21A includes a portion that protrudes outward from the positive electrode active material layer 21B (hereinafter referred to as the "protruding portion of the positive electrode current collector 21A"). Since the positive electrode active material layer 21B is not provided in this protruding portion of the positive electrode current collector 21A, this protruding portion functions as the positive electrode terminal 31. Details of the positive electrode terminal 31 will be described later.

[0120] On both sides of the positive electrode current collector 21A (excluding the positive electrode terminal 31), the positive electrode active material layer 21B is provided only on a portion of the positive electrode current collector 21A. Therefore, the portion of the positive electrode current collector 21A that is not covered by the positive electrode active material layer 21B is exposed.

[0121] Specifically, the positive electrode current collector 21A includes a coated portion 21AX and an uncoated portion 21AY, as shown in Figure 4. The coated portion 21AX is located in the center of the positive electrode current collector 21A and is the portion where the positive electrode active material layer 21B is formed. The uncoated portion 21AY is located around the coated portion 21AX and is a frame-shaped portion where the positive electrode active material layer 21B is not formed. As a result, the coated portion 21AX is covered by the positive electrode active material layer 21B, while the uncoated portion 21AY is exposed and not covered by the positive electrode active material layer 21B.

[0122] (Negative electrode) The negative electrode 22 has a configuration similar to that of the negative electrode 100. Specifically, as shown in Figures 3 and 5, the negative electrode 22 includes a negative electrode current collector 22A and a negative electrode active material layer 22B. In Figure 5, the negative electrode active material layer 22B is shaded.

[0123] The configuration of the negative electrode current collector 22A is the same as that of the negative electrode current collector 110, and the configuration of the negative electrode active material layer 22B is the same as that of the negative electrode active material layer 120. That is, the negative electrode active material layer 22B contains an alkali metal carbonate compound and a magnesium compound.

[0124] Here, as shown in Figure 5, a portion of the negative electrode current collector 22A protrudes, and therefore the negative electrode current collector 22A includes a portion that protrudes outward from the negative electrode active material layer 22B (hereinafter referred to as the "protruding portion of the negative electrode current collector 22A").

[0125] The direction of protrusion of the protruding portion of the negative electrode current collector 22A is the same as the direction of protrusion of the protruding portion of the positive electrode current collector 21A. Furthermore, the position of the protruding portion of the negative electrode current collector 22A is such that it does not overlap with the protruding portion of the positive electrode current collector 21A when the positive electrode 21 and the negative electrode 22 are stacked alternately via the separator 23.

[0126] Since the negative electrode active material layer 22B is not provided on the protruding portion of the negative electrode current collector 22A, this protruding portion functions as the negative electrode terminal 32. Details of the negative electrode terminal 32 will be described later.

[0127] On both sides of the negative electrode current collector 22A (excluding the negative electrode terminal 32), the negative electrode active material layer 22B is provided over the entire negative electrode current collector 22A. Therefore, the entire negative electrode current collector 22A is not exposed but covered by the negative electrode active material layer 22B.

[0128] Specifically, the negative electrode active material layer 22B includes a facing portion 22BX and an unfacing portion 22BY, as shown in Figure 5. The facing portion 22BX is the portion facing the coated portion 21AX. That is, the facing portion 22BX is the portion that is involved in the charge-discharge reaction because it is facing the positive electrode active material layer 21B. The unfacing portion 22BY is the portion facing the uncoated portion 21AY. That is, the unfacing portion 22BY is not facing the positive electrode active material layer 21B but is facing the positive electrode current collector 21A, and therefore is not involved in the charge-discharge reaction. In Figure 5, to make the formation range of the coated portion 21AX (positive electrode active material layer 21B) easier to understand, the formation range of the coated portion 21AX (the boundary between the facing portion 22BX and the unfacing portion 22BY) is shown with a dashed line.

[0129] The reason why the negative electrode active material layer 22B is provided on the entire surface of both sides of the negative electrode current collector 22A, while the positive electrode active material layer 21B is provided only on a portion of both sides (the covering portion 21AX) of the positive electrode current collector 21A, is to suppress the deposition of lithium released from the positive electrode active material layer 21B on the surface of the negative electrode 22 during charging.

[0130] (Separator) As shown in Figure 3, the separator 23 is an insulating porous membrane interposed between the positive electrode 21 and the negative electrode 22, allowing lithium ions to pass through while preventing contact (short circuit) between the positive electrode 21 and the negative electrode 22. This separator 23 contains a polymer compound such as polyethylene.

[0131] (electrolyte) The electrolyte is a liquid electrolyte. This electrolyte is impregnated into the positive electrode 21, the negative electrode 22, and the separator 23, and contains a solvent and an electrolyte salt.

[0132] Here, the solvent contains one or more types of non-aqueous solvents (organic solvents), and the electrolyte containing these non-aqueous solvents is a so-called non-aqueous electrolyte. These non-aqueous solvents include esters and ethers, and more specifically, carbonate ester compounds, carboxylic acid ester compounds, and lactone compounds. This is because it improves the dissociation of the electrolyte salt and also improves the mobility of ions.

[0133] Carbonate ester compounds include cyclic carbonate esters and linear carbonate esters. Specific examples of cyclic carbonate esters include ethylene carbonate and propylene carbonate, while specific examples of linear carbonate esters include dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate.

[0134] Carboxylic acid ester compounds include linear carboxylic acid esters. Specific examples of linear carboxylic acid esters include ethyl acetate, ethyl propionate, propyl propionate, and trimethylethyl acetate.

[0135] Lactone compounds include lactones, among others. Specific examples of lactones include γ-butyrolactone and γ-valerolactone.

[0136] The ethers may also be 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxolane, and 1,4-dioxane.

[0137] The electrolyte salt contains one or more types of light metal salts, such as lithium salts. Specific examples of lithium salts include lithium hexafluoride phosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium tris(trifluoromethanesulfonyl)methide (LiC(CF3SO2)3), lithium bis(oxalato)borate (LiB(C2O4)2), lithium monofluorophosphate (Li2PFO3), and lithium difluorophosphate (LiPF2O2). This is because it allows for high battery capacity.

[0138] The electrolyte salt content is not particularly limited, but specifically, it is between 0.3 mol / kg and 3.0 mol / kg relative to the solvent. This is because it allows for high ionic conductivity.

[0139] The electrolyte may also contain one or more of the additives. The types of additives are not particularly limited, but specifically include unsaturated cyclic carbonate esters, fluorinated cyclic carbonate esters, sulfonic acid esters, phosphate esters, acid anhydrides, nitrile compounds, and isocyanate compounds.

[0140] Specific examples of unsaturated cyclic carbonate esters include vinylene carbonate, vinylethylene carbonate, and methyleneethylene carbonate. Specific examples of fluorinated cyclic carbonate esters include monofluoroethylene carbonate and difluoroethylene carbonate. Specific examples of sulfonic acid esters include propanesultone and propensultone. Specific examples of phosphate esters include trimethyl phosphate and triethyl phosphate. Specific examples of acid anhydrides include succinic anhydride, 1,2-ethanedisulfonic anhydride, and 2-sulfobenzoic anhydride. Specific examples of nitrile compounds include succinonitrile. Specific examples of isocyanate compounds include hexamethylene diisocyanate.

[0141] [Positive terminal and negative terminal] As shown in Figure 4, the positive electrode terminal 31 is electrically connected to the positive electrode 21, and more specifically, to the positive electrode current collector 21A. In the battery element 20, as described above, the positive electrode 21 and the negative electrode 22 are alternately stacked via a separator 23, so the battery element 20 contains multiple positive electrodes 21. As a result, the secondary battery has multiple positive electrode terminals 31.

[0142] The positive electrode terminal 31 contains a conductive material such as a metal material, and the type of conductive material is not particularly limited. Specifically, the positive electrode terminal 31 contains the same material as the material used to form the positive electrode current collector 21A.

[0143] Here, as described above, the protruding portion of the positive electrode current collector 21A functions as the positive electrode terminal 31, and therefore the positive electrode terminal 31 is physically integrated with the positive electrode current collector 21A. This is because the connection resistance between the positive electrode current collector 21A and the positive electrode terminal 31 decreases, which in turn reduces the overall electrical resistance of the secondary battery.

[0144] As described later, the multiple positive terminals 31 are joined to each other using a joining method such as welding, thus forming a single lead-shaped joint 31Z as shown in Figure 2.

[0145] As shown in Figure 5, the negative electrode terminal 32 is electrically connected to the negative electrode 22, and more specifically, to the negative electrode current collector 22A. In the battery element 20, as described above, the positive electrode 21 and the negative electrode 22 are alternately stacked via a separator 23, so the battery element 20 contains multiple negative electrodes 22. As a result, the secondary battery has multiple negative electrode terminals 32.

[0146] The negative electrode terminal 32 contains a conductive material such as a metal material, and the type of conductive material is not particularly limited. Specifically, the negative electrode terminal 32 contains the same material as the material used to form the negative electrode current collector 22A.

[0147] Here, as described above, the protruding portion of the negative electrode current collector 22A functions as the negative electrode terminal 32, and therefore the negative electrode terminal 32 is physically integrated with the negative electrode current collector 22A. This is because the connection resistance between the negative electrode current collector 22A and the negative electrode terminal 32 decreases, which in turn reduces the overall electrical resistance of the secondary battery.

[0148] As described later, the multiple negative electrode terminals 32 are joined to each other using a joining method such as welding, thus forming a single lead-shaped joint 32Z as shown in Figure 2.

[0149] [Positive lead and negative lead] The positive electrode lead 41 is connected to the junction 31Z, as shown in Figure 2, and is led out to the outside of the outer film 10. This positive electrode lead 41 contains a conductive material such as a metallic material, specifically a material similar to the material used to form the positive electrode current collector 21A. The shape of the positive electrode lead 41 is not particularly limited, but is specifically one of a thin plate shape or a mesh shape.

[0150] As shown in Figure 2, the negative electrode lead 42 is connected to the joint 32Z and leads out to the outside of the outer film 10. This negative electrode lead 42 contains a conductive material such as a metallic material, specifically the same material as the material used to form the negative electrode current collector 22A. The direction in which the negative electrode lead 42 is led out is the same as the direction in which the positive electrode lead 41 is led out. Furthermore, the details regarding the shape of the negative electrode lead 42 are the same as the details regarding the shape of the positive electrode lead 41.

[0151] [Sealing film] The sealing film 51 is inserted between the outer film 10 and the positive lead 41, and the sealing film 52 is inserted between the outer film 10 and the negative lead 42. However, one or both of the sealing films 51 and 52 may be omitted.

[0152] This sealing film 51 is a sealing member that prevents outside air and other elements from entering the interior of the outer film 10. The sealing film 51 contains a polymer compound such as polyolefin that adheres to the positive electrode lead 41, and a specific example of such a polymer compound is polypropylene.

[0153] The structure of the sealing film 52 is the same as that of the sealing film 51, except that it is a sealing member that adheres to the negative electrode lead 42. That is, the sealing film 52 contains a polymer compound such as a polyolefin that adheres to the negative electrode lead 42.

[0154] <2-2. Operation> This rechargeable battery operates as described below.

[0155] During charging, lithium is released from the positive electrode 21 of the battery element 20, and this lithium is absorbed into the negative electrode 22 via the electrolyte. Conversely, during discharging, lithium is released from the negative electrode 22 of the battery element 20, and this lithium is absorbed into the positive electrode 21 via the electrolyte. During both charging and discharging, lithium is absorbed and released in an ionic state.

[0156] <2-3. Manufacturing method> Figure 6 shows a perspective view corresponding to Figure 2 to illustrate the manufacturing method of the secondary battery. However, in Figure 6, instead of the battery element 20, a laminate 20Z used to fabricate the battery element 20 is shown. Details of the laminate 20Z will be described later.

[0157] When manufacturing a secondary battery, the positive electrode 21 and negative electrode 22 are prepared according to the example procedure described below, and the electrolyte is prepared. Then, the secondary battery is assembled using the positive electrode 21, negative electrode 22, and electrolyte, and the secondary battery is stabilized. In the following, Figures 1 to 5, which have already been described, will be referred to as needed.

[0158] [Fabrication of the positive electrode] First, a paste-like positive electrode mixture slurry is prepared by adding a mixture (positive electrode mixture) containing a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent to a solvent. This solvent may be an aqueous solvent or an organic solvent. Next, the positive electrode mixture slurry is applied to both sides (excluding the positive electrode terminal 31) of the positive electrode current collector 21A, which has the positive electrode terminal 31 integrated into it, to form a positive electrode active material layer 21B. Finally, the positive electrode active material layer 21B is compression molded using a roll press or the like. In this case, the positive electrode active material layer 21B may be heated, or the compression molding may be repeated multiple times. As a result, a positive electrode 21 is manufactured by forming a positive electrode active material layer 21B on both sides of the positive electrode current collector 21A.

[0159] [Fabrication of the negative electrode] The negative electrode 22 is formed using the same procedure as that used to manufacture the negative electrode 100 described above. Specifically, first, a paste-like negative electrode slurry is prepared by adding a mixture (negative electrode mixture) containing the negative electrode active material, alkali metal carbonate compound, magnesium compound, and negative electrode binder to a solvent. Next, the negative electrode slurry is applied to both sides (excluding the negative electrode terminal 32) of the negative electrode current collector 22A, which has the negative electrode terminal 32 integrated into it, to form the negative electrode active material layer 22B. Finally, the negative electrode active material layer 22B is compression molded. As a result, the negative electrode active material layer 22B is formed on both sides of the negative electrode current collector 22A, and the negative electrode 22 is manufactured.

[0160] [Preparation of electrolyte solution] The electrolyte salt is added to the solvent. This disperses or dissolves the electrolyte salt in the solvent, thus preparing the electrolyte solution.

[0161] [Assembly of rechargeable batteries] First, a laminate 20Z is fabricated by alternately stacking the positive electrode 21 and the negative electrode 22 via a separator 23, as shown in Figure 6. This laminate 20Z has the same configuration as the battery element 20, except that the positive electrode 21, the negative electrode 22, and the separator 23 are not impregnated with electrolyte.

[0162] Next, a joint 31Z is formed by joining multiple positive electrode terminals 31 to each other using a joining method such as welding, and then a positive electrode lead 41 is connected to the joint 31Z using a joining method such as welding. Furthermore, a joint 32Z is ​​formed by joining multiple negative electrode terminals 32 to each other using a joining method such as welding, and then a negative electrode lead 42 is connected to the joint 32Z using a joining method such as welding.

[0163] Next, after housing the laminate 20Z inside the recessed portion 10U, the outer film 10 (fusion layer / metal layer / surface protection layer) is folded so that the outer films 10 face each other. Subsequently, using an adhesive method such as heat fusion, the outer edges of two sides of the opposing fusion layers are bonded together, thereby housing the laminate 20Z inside the bag-shaped outer film 10.

[0164] Finally, after injecting the electrolyte into the bag-shaped outer film 10, the outer edges of the remaining sides of the opposing fused layers are bonded together using an adhesive method such as heat fusion. In this case, a sealing film 51 is inserted between the outer film 10 and the positive electrode lead 41, and a sealing film 52 is inserted between the outer film 10 and the negative electrode lead 42.

[0165] As a result, the electrolyte is impregnated into the laminated body 20Z, and the battery element 20, which is a laminated electrode body, is fabricated. Therefore, the battery element 20 is sealed inside the bag-shaped outer film 10, and a secondary battery is assembled.

[0166] [Stabilization of secondary batteries] The assembled secondary battery is then charged and discharged. Various conditions such as ambient temperature, number of charge / discharge cycles, and charge / discharge conditions can be set arbitrarily. As a result, a coating is formed on the surfaces of the positive electrode 21 and the negative electrode 22, thereby electrochemically stabilizing the state of the secondary battery. Thus, the secondary battery is completed.

[0167] <2-4. Action and Effects> In this secondary battery, since the negative electrode 22 has the same configuration as the negative electrode 100, excellent battery characteristics can be obtained for the reasons mentioned above.

[0168] In particular, if the secondary battery is a lithium-ion secondary battery, a sufficient battery capacity can be stably obtained by utilizing the intercalation and deintercalation of lithium, thus achieving a higher level of effectiveness.

[0169] Other effects and behaviors related to the secondary battery are the same as those related to the negative electrode 100.

[0170] <3. Variant> The configurations of the negative electrode 100 and the secondary battery described above can be modified as appropriate, as explained below. However, any two or more of the variations described below may be combined with each other.

[0171] [Example 1] In Figure 4, the protruding portion of the positive electrode current collector 21A also serves as the positive electrode terminal 31, and therefore the positive electrode terminal 31 is physically integrated with the positive electrode current collector 21A. However, since the positive electrode terminal 31 is physically separated from the positive electrode current collector 21A, it may be a separate component from the positive electrode current collector 21A. In this case, the positive electrode terminal 31 may be connected to the positive electrode current collector 21A using a joining method such as welding.

[0172] In this case as well, since the positive terminal 31 is electrically connected to the positive electrode 21, the same effect can be obtained. However, in order to reduce the overall electrical resistance of the secondary battery in accordance with the decrease in connection resistance, it is preferable that the positive terminal 31 is physically integrated with the positive electrode current collector 21A.

[0173] Similarly, in Figure 5, the protruding portion of the negative electrode current collector 22A also serves as the negative electrode terminal 32, and therefore the negative electrode terminal 32 is physically integrated with the negative electrode current collector 22A. However, since the negative electrode terminal 32 is physically separated from the negative electrode current collector 22A, it may be a separate component from the negative electrode current collector 22A. In this case, the negative electrode terminal 32 may be connected to the negative electrode current collector 22A using a joining method such as welding.

[0174] In this case as well, since the negative terminal 32 is electrically connected to the negative electrode 22, the same effect can be obtained. However, in order to reduce the overall electrical resistance of the secondary battery in accordance with the decrease in connection resistance, it is preferable that the negative terminal 32 is physically integrated with the negative electrode current collector 22A.

[0175] [Differentiation 2] Figure 2 shows a battery element 20 which is a laminated electrode body. However, although not specifically shown here, a battery element which is a wound electrode body may also be used. In this case, the positive electrode 21 has a strip-shaped structure, and the positive electrode terminal 31 is electrically connected to the positive electrode current collector 21A, while the negative electrode 22 has a strip-shaped structure, and the negative electrode terminal 32 is electrically connected to the negative electrode current collector 22A. As a result, the positive electrode 21 and the negative electrode 22 are wound facing each other via a separator 23. The number of positive electrode terminals 31 may be one or two or more. Similarly, the number of negative electrode terminals 32 may be one or two or more.

[0176] In this case as well, since the secondary battery can be charged and discharged using the battery element 20, the same effect can be obtained.

[0177] [Difference 3] A porous membrane separator 23 was used. However, although not specifically shown in the diagram, a laminated separator containing a polymer compound layer may also be used.

[0178] Specifically, the laminated separator includes a porous membrane having a pair of surfaces and a polymer compound layer provided on one or both sides of the porous membrane. This improves the adhesion of the separator to the positive electrode 21 and the negative electrode 22, thereby suppressing displacement of the battery element 20. As a result, swelling of the secondary battery is suppressed even if side reactions such as electrolyte decomposition occur. The polymer compound layer contains a polymer compound such as polyvinylidene fluoride. This is because it provides excellent physical strength and excellent electrochemical stability.

[0179] Furthermore, one or both of the porous membrane and the polymer compound layer may contain one or more types of insulating particles from a selection of multiple insulating particles. This is because the multiple insulating particles promote heat dissipation when the secondary battery generates heat, thereby improving the safety (heat resistance) of the secondary battery. The insulating particles contain one or more types of insulating materials, such as inorganic materials and resin materials. Specific examples of inorganic materials include aluminum oxide, aluminum nitride, boehmite, silicon oxide, titanium oxide, magnesium oxide, and zirconium oxide. Specific examples of resin materials include acrylic resin and styrene resin.

[0180] When fabricating a laminated separator, a precursor solution containing a polymer compound and a solvent is prepared, and then the precursor solution is applied to one or both sides of a porous membrane. In this case, if necessary, multiple insulating particles may be added to the precursor solution.

[0181] Even when using this stacked separator, lithium ions can move between the positive electrode 21 and the negative electrode 22, thus achieving a similar effect. In this case, as mentioned above, the safety of the secondary battery is improved, resulting in an even greater effect.

[0182] [Differentiation Example 4] A liquid electrolyte solution was used. However, although not specifically illustrated here, a gel-like electrolyte layer may also be used.

[0183] In the battery element 20 using an electrolyte layer, the positive electrode 21 and the negative electrode 22 are alternately stacked via a separator 23 and the electrolyte layer. This electrolyte layer is interposed between the positive electrode 21 and the separator 23, as well as between the negative electrode 22 and the separator 23.

[0184] Specifically, the electrolyte layer contains a polymer compound along with the electrolyte, and the electrolyte is held in place by the polymer compound. This prevents leakage of the electrolyte. The composition of the electrolyte is as described above. The polymer compound includes polyvinylidene fluoride, etc. When forming the electrolyte layer, a precursor solution containing the electrolyte, polymer compound, and solvent is prepared, and then the precursor solution is applied to one or both sides of the positive electrode 21 and the negative electrode 22, respectively.

[0185] Even when this electrolyte layer is used, lithium ions can move between the positive electrode 21 and the negative electrode 22 via the electrolyte layer, thus achieving a similar effect. In this case, in particular, as mentioned above, leakage of the electrolyte is prevented, resulting in an even greater effect.

[0186] <4. Applications of rechargeable batteries> The uses (examples of applications) of secondary batteries are not particularly limited. Secondary batteries used as power sources may be the primary power source or the auxiliary power source in electronic devices and electric vehicles, etc. A primary power source is a power source that is used preferentially regardless of the presence or absence of other power sources. An auxiliary power source may be a power source used in place of the primary power source, or a power source that can be switched from the primary power source.

[0187] Specific examples of secondary battery applications are described below: Electronic devices such as video cameras, digital still cameras, mobile phones, notebook computers, headphone stereos, portable radios, and portable information terminals; backup power supplies and storage devices such as memory cards; power tools such as electric drills and electric saws; battery packs installed in electronic devices; medical electronic devices such as pacemakers and hearing aids; electric vehicles (including hybrid vehicles); and power storage systems such as household or industrial battery systems that store power in preparation for emergencies. In these applications, one secondary battery may be used, or multiple secondary batteries may be used.

[0188] The battery pack may use individual cells or a battery pack. An electric vehicle is a vehicle that runs using a secondary battery as a power source, and may also be a hybrid vehicle equipped with other power sources in addition to the secondary battery. In a household power storage system, the electricity stored in the secondary battery, which is the power storage source, can be used to power household electrical appliances, etc.

[0189] Here, we will specifically explain one example of a secondary battery application. The configuration of the application example described below is merely an example and can be modified as needed.

[0190] Figure 7 shows the block configuration of the battery pack. The battery pack described here is a single rechargeable battery pack (a so-called soft pack) and is installed in electronic devices such as smartphones.

[0191] As shown in Figure 7, this battery pack comprises a power supply 71 and a circuit board 72. The circuit board 72 is connected to the power supply 71 and includes a positive terminal 73, a negative terminal 74, and a temperature detection terminal 75.

[0192] The power supply 71 includes one rechargeable battery. In this rechargeable battery, the positive lead is connected to the positive terminal 73, and the negative lead is connected to the negative terminal 74. Since the power supply 71 can be connected to the outside via the positive terminal 73 and the negative terminal 74, it can be charged and discharged. The circuit board 72 includes a control unit 76, a switch 77, a thermal resistance element (PTC element) 78, and a temperature detection unit 79. However, the PTC element 78 may be omitted.

[0193] The control unit 76 includes a central processing unit (CPU) and memory, and controls the operation of the entire battery pack. This control unit 76 detects and controls the usage status of the power supply 71 as needed.

[0194] Furthermore, when the voltage of the power supply 71 (secondary battery) reaches the overcharge detection voltage or over-discharge detection voltage, the control unit 76 disconnects the switch 77 to prevent charging current from flowing through the current path of the power supply 71. The overcharge detection voltage is not particularly limited, but specifically it is 4.20V ± 0.05V, and the over-discharge detection voltage is not particularly limited, but specifically it is 2.40V ± 0.1V.

[0195] The switch 77 includes a charge control switch, a discharge control switch, a charging diode, and a discharging diode, and switches the connection between the power supply 71 and external equipment according to the instructions of the control unit 76. This switch 77 includes a field-effect transistor (MOSFET) using a metal oxide semiconductor, and the charge / discharge current is detected based on the ON resistance of the switch 77.

[0196] The temperature detection unit 79 includes a temperature detection element such as a thermistor. This temperature detection unit 79 measures the temperature of the power supply 71 using the temperature detection terminal 75 and outputs the temperature measurement result to the control unit 76. The temperature measurement result measured by the temperature detection unit 79 is used when the control unit 76 performs charge / discharge control in the event of abnormal heat generation and when the control unit 76 performs correction processing when calculating the remaining capacity. [Examples]

[0197] An example of this technology will be described below.

[0198] <Examples 1-17 and Comparative Examples 1-3> As explained below, after manufacturing the rechargeable batteries, their battery characteristics were evaluated.

[0199] [Manufacturing of secondary batteries] The secondary batteries (laminated film type lithium-ion secondary batteries) shown in Figures 2 to 5 were manufactured using the following procedure.

[0200] (Fabrication of the positive electrode) First, the positive electrode active material (LiNi, a lithium-containing compound (oxide)) 0.8 Co 0.15 Al 0.05 A positive electrode mixture was prepared by mixing 94 parts by mass of O2, 3 parts by mass of a positive electrode binder (polyvinylidene fluoride), and 3 parts by mass of a positive electrode conductive agent (Ketjenbrak, an amorphous carbon powder). Next, the positive electrode mixture was added to a solvent (N-methyl-2-pyrrolidone, an organic solvent), and the organic solvent was stirred to prepare a paste-like positive electrode mixture slurry. Subsequently, using a coating apparatus, the positive electrode mixture slurry was applied to both sides (excluding the positive electrode terminal 31) of the positive electrode current collector 21A (aluminum foil with a thickness of 20 μm), on which the positive electrode terminal 31 was integrated, and then the positive electrode mixture slurry was dried to form the positive electrode active material layer 21B. Finally, the positive electrode active material layer 21B was compression molded using a roll press. This completed the production of the positive electrode 21.

[0201] (Fabrication of the negative electrode) First, 60 parts by mass of negative electrode active material (artificial graphite, a carbon material) and negative electrode active material (silicon-containing material, silicon dioxide (SiO2) xA negative electrode mixture was prepared by mixing 30 parts by mass of the compound with 10 parts by mass of a negative electrode binder (styrene-butadiene rubber). Subsequently, the negative electrode mixture was added to a solvent (an organic solvent, N-methyl-2-pyrrolidone), and the organic solvent was stirred to prepare a paste-like negative electrode mixture slurry.

[0202] Next, alkali metal carbonate compounds and magnesium compounds were added to the negative electrode mixture slurry, and the slurry was stirred.

[0203] As alkali metal carbonate compounds, lithium carbonate (Li2CO3), a primary alkali metal carbonate compound, and a secondary alkali metal carbonate compound were used. As primary alkali metal carbonate compounds, lithium methyl carbonate (LMC), lithium ethyl carbonate (LEC), and lithium propyl carbonate (LPC) were used. As secondary alkali metal carbonate compounds, dilithium ethylene dicarbonate (LEDC) and dilithium propylene dicarbonate (LPDC) were used.

[0204] The magnesium compounds used were magnesium fluoride (MgF2), magnesium oxide (MgO), magnesium nitride (Mg3N2), and magnesium carbonate (MgCO3).

[0205] Here, as an example of a method for synthesizing alkali metal dicarbonates, the method for synthesizing dilithium ethylenedicarbonate will be specifically explained. In synthesizing dilithium ethylenedicarbonate, an organic solvent (ethylene carbonate) and a tetrahydrofuran solution of lithium naphthalenide were mixed together, and the mixture was left to stand (standing time = 1 day). As a result, the ethylene carbonate and lithium naphthalenide reacted with each other, and dilithium ethylenedicarbonate was synthesized.

[0206] Next, using a coating apparatus, a negative electrode mixture slurry was applied to both sides (excluding the negative electrode terminal 32) of the negative electrode current collector 22A (a copper foil with a thickness of 15 μm) on which the negative electrode terminal 32 was integrated. Then, the negative electrode mixture slurry was dried to form the negative electrode active material layer 22B. Finally, the negative electrode active material layer 22B was compression molded using a roll press. This completed the production of the negative electrode 22.

[0207] For comparison, a negative electrode 22 was prepared using the same procedure, except that neither alkali metal carbonate nor magnesium compound was used.

[0208] (Preparation of electrolyte solution) First, the electrolyte salt (LiPF6) was added to the solvent, and then the solvent was stirred. The solvent used was a mixture of cyclic carbonate esters ethylene carbonate and propylene carbonate, chain carbonate esters dimethyl carbonate and ethylmethyl carbonate, and fluorinated cyclic carbonate ester monofluoroethylene carbonate. The solvent composition (mass ratio) was ethylene carbonate:propylene carbonate:dimethyl carbonate:ethylmethyl carbonate:monofluoroethylene carbonate = 27.5:5:60:5:2.5. The electrolyte salt content was 1.5 mol / kg relative to the solvent.

[0209] (Assembly of secondary batteries) First, a laminate 20Z was fabricated by stacking the positive electrode 21 and the negative electrode 22 on top of each other via a separator 23 (a microporous polyethylene film with a thickness of 15 μm).

[0210] Next, a joint 31Z was formed by welding multiple positive terminals 31 to each other, and then a positive lead 41 (aluminum foil) was welded to the joint 31Z. Similarly, a joint 32Z was formed by welding multiple negative terminals 32 to each other, and then a negative lead 42 (copper foil) was welded to the joint 32Z.

[0211] Next, the outer film 10 (fusion layer / metal layer / surface protection layer) was folded so as to sandwich the laminate 20Z housed in the recess 10U. Then, the outer edges of two sides of the fusion layer were heat-fused together to house the laminate 20Z inside the bag-shaped outer film 10. The outer film 10 used was an aluminum laminate film in which a fusion layer (polypropylene film with a thickness of 30 μm), a metal layer (aluminum foil with a thickness of 40 μm), and a surface protection layer (nylon film with a thickness of 25 μm) were laminated in this order from the inside.

[0212] Finally, after injecting the electrolyte into the bag-shaped outer film 10, the outer edges of the remaining side of the fusion layer were heat-fused together in a reduced-pressure environment. In this case, a sealing film 51 (polypropylene film with a thickness of 5 μm) was inserted between the outer film 10 and the positive electrode lead 41, and a sealing film 52 (polypropylene film with a thickness of 5 μm) was inserted between the outer film 10 and the negative electrode lead 42. As a result, the electrolyte was impregnated into the laminate 20Z, and the battery element 20, which is a laminated electrode body, was fabricated.

[0213] Therefore, since the battery element 20 was sealed inside the outer film 10, the secondary battery was assembled.

[0214] After the secondary battery was completed, the content (weight %) of alkali metal carbonate compounds and magnesium compounds in the negative electrode active material layer 120 were calculated and the results are shown in Table 1. Details regarding the calculation procedure are as described above.

[0215] (Stabilization of secondary batteries) A secondary battery was subjected to one charge-discharge cycle in a normal temperature environment (temperature = 25°C). During charging, constant current charging was performed at a current of 0.1C until the voltage reached 4.2V, and then constant voltage charging was performed at that voltage of 4.2V until the current reached 0.05C. During discharging, constant current discharge was performed at a current of 0.1C until the voltage reached 2.5V. 0.1C is the current value required to completely discharge the battery capacity (theoretical capacity) in 10 hours, and 0.05C is the current value required to completely discharge the battery capacity in 20 hours.

[0216] As a result, a coating was formed on the surfaces of both the positive electrode 21 and the negative electrode 22, thereby electrochemically stabilizing the state of the secondary battery. Thus, a laminate film type secondary battery was completed.

[0217] [Evaluation of battery characteristics] When the cycle characteristics were evaluated as part of the battery's characteristics, the results shown in Table 1 were obtained.

[0218] To evaluate the cycle characteristics, the secondary battery was first left in a low-temperature environment (temperature = 5°C) for 3 hours. Subsequently, the discharge capacity (discharge capacity in the first cycle) was measured by charging and discharging the secondary battery in the same environment.

[0219] Next, the secondary battery was repeatedly charged and discharged in the same environment until the total number of cycles reached 300, and the discharge capacity (discharge capacity at the 300th cycle) was measured.

[0220] Finally, the capacity retention rate (%) was calculated based on the formula: Capacity retention rate (%) = (Discharge capacity at 300 cycles / Discharge capacity at 1 cycle) × 100, which is an indicator for evaluating cycle characteristics.

[0221] During charging, the current is 3mA / cm². 2 After constant current charging at a current density until the voltage reaches 4.2V, the current density at that 4.2V is 0.7mA / cm². 2 Constant voltage charging was performed until the value reached 3 mA / cm². During discharge, the discharge rate was 3 mA / cm². 2A constant current discharge was performed at the specified current density until the voltage reached 3.0V.

[0222] [Table 1]

[0223] [Consideration] As shown in Table 1, the capacity retention rate varied considerably depending on the configuration of the negative electrode 22.

[0224] In the following, the volume retention rate in the case where the negative electrode active material layer 22B does not contain both alkali metal carbonate compounds and magnesium compounds (Comparative Example 1) will be used as the comparison standard.

[0225] Specifically, when the negative electrode active material layer 22B contained only an alkali metal carbonate compound (Comparative Example 2), the capacity retention rate increased slightly. Similarly, when the negative electrode active material layer 22B contained only a magnesium compound (Comparative Example 3), the capacity retention rate also increased slightly. Therefore, it is expected that even when the negative electrode active material layer 22B contains both an alkali metal carbonate compound and a magnesium compound, the capacity retention rate will only increase slightly.

[0226] However, when the negative electrode active material layer 22B contained both alkali metal carbonate compounds and magnesium compounds (Examples 1-17), results contrary to the above predictions were obtained. Specifically, when the negative electrode active material layer 22B contained both alkali metal carbonate compounds and magnesium compounds, the capacity retention rate increased significantly.

[0227] Here, I will explain in detail the results that contradicted the above predictions.

[0228] First, when the negative electrode active material layer 22B contained only alkali metal carbonate compounds (Comparative Example 2), the increase in capacity retention rate was approximately 31.6%. Furthermore, when the negative electrode active material layer 22B contained only magnesium compounds (Comparative Example 3), the increase in capacity retention rate was approximately 94.7%. Therefore, it is expected that when the negative electrode active material layer 22B contains both alkali metal carbonate compounds and magnesium compounds, the increase in capacity retention rate will be approximately 126.3% (=31.6% + 94.7%). While this increase rate (=approximately 126.3%) exceeds 100%, and thus appears sufficient at first glance, it is still insufficient when considering the need to improve cycle characteristics as much as possible.

[0229] In contrast, actual testing revealed that when the negative electrode active material layer 22B contained both alkali metal carbonate and magnesium compounds (Example 7), the increase in capacity retention rate was approximately 326.3%. This increase rate (= approximately 326.3%) is about 2.5 times the previously predicted increase rate (= approximately 126.3%), and is significantly higher than expected. Therefore, it is a sufficient value when considering how to improve the cycle characteristics as much as possible.

[0230] In particular, the advantageous tendency that the capacity retention rate is significantly higher when the negative electrode active material layer 22B contains both alkali metal carbonate compounds and magnesium compounds is a special tendency that cannot be easily derived without actual verification.

[0231] When the negative electrode active material layer 22B contained both alkali metal carbonate compounds and magnesium compounds (Examples 1-17), the following tendencies were particularly observed. Firstly, a high capacity retention rate was obtained even when the type of alkali metal carbonate compound (lithium carbonate, first alkali metal carbonate compound, and second alkali metal carbonate compound) was changed. Secondly, a high capacity retention rate was obtained even when the type of magnesium compound was changed. Thirdly, a high capacity retention rate was obtained when the alkali metal carbonate compound content in the negative electrode active material layer 22B was 0.2% to 0.8% by weight. Fourthly, a high capacity retention rate was obtained when the magnesium compound content in the negative electrode active material layer 22B was 0.01% to 5% by weight.

[0232] [summary] As shown in Table 1, a high capacity retention rate was obtained when the negative electrode active material layer 22B of the negative electrode 22 contained an alkali metal carbonate compound and a magnesium compound. Therefore, the cycle characteristics were improved, and excellent battery characteristics were obtained in the secondary battery.

[0233] Although the present technology has been described above with reference to one embodiment and one example, the configuration of the present technology is not limited to the configuration described in the one embodiment and one example, and can be modified in various ways.

[0234] Specifically, the explanation described the case where the battery structure of the rechargeable battery is of the laminated film type. However, the battery structure of the rechargeable battery is not particularly limited, and other battery structures such as cylindrical, prismatic, coin-type, and button-type batteries are also acceptable.

[0235] Furthermore, the cases where the element structure of the battery element is of the stacked type and the wound type have been described. However, the element structure of the battery element is not particularly limited, and other element structures such as the zigzag type may also be used. In this zigzag type, the positive electrode and the negative electrode are folded in a zigzag pattern, facing each other via a separator.

[0236] Furthermore, while we have described the case where the electrode reactant is lithium, the electrode reactant is not particularly limited. Specifically, as mentioned above, the electrode reactant may be other alkali metals such as sodium and potassium, or alkaline earth metals such as beryllium, magnesium, and calcium. In addition, the electrode reactant may be other light metals such as aluminum.

[0237] The effects described herein are illustrative only, and therefore the effects of this technology are not limited to those described herein. Accordingly, other effects may be obtained with respect to this technology.

[0238] Furthermore, this technology can also be configured as follows: <1> Positive electrode and, A negative electrode containing a negative electrode active material layer, Electrolyte and Equipped with, The negative electrode active material layer comprises an alkali metal carbonate compound and a magnesium compound. The alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and contains an alkali metal element as a constituent element. The aforementioned magnesium compound contains magnesium as a constituent element. Secondary battery. <2> The alkali metal carbonate compound comprises at least one of lithium carbonate (Li2CO3), the compound represented by formula (1), and the compound represented by formula (2). <1> The secondary battery described above. R1-OC(=O)O-M1 ···(1) (R1 is an alkyl group. M1 is an alkali metal element.) M2-OC(=O)O-R2-OC(=O)O-M3 ···(2) (R2 is an alkylene group. M2 and M3 are alkali metal elements, respectively.) <3> In formula (1) above, the alkali metal element is lithium, In the formula (2), the alkali metal element is lithium. The secondary battery according to <2>. <4> The magnesium compound contains at least one of magnesium fluoride, magnesium oxide, magnesium nitride, and magnesium carbonate. The secondary battery according to any one of <1> to <3>. <5> The content of the alkali metal carbonate compound in the negative electrode active material layer is 0.2% by weight or more and 0.8% by weight or less. The secondary battery according to any one of <1> to <4>. <6> The content of the magnesium compound in the negative electrode active material layer is 0.01% by weight or more and 5% by weight or less. The secondary battery according to any one of <1> to <5>. <7> The negative electrode active material layer contains a negative electrode active material. The negative electrode active material contains a carbon material and a silicon-containing material. The secondary battery according to any one of <1> to <6>. <8> It is a lithium ion secondary battery. The secondary battery according to any one of <1> to <7>. <9> It includes a negative electrode active material layer. The negative electrode active material layer contains an alkali metal carbonate compound and a magnesium compound. The alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and contains an alkali metal element as a constituent element. The magnesium compound contains magnesium as a constituent element. A negative electrode for a secondary battery.

Claims

1. Positive electrode and, A negative electrode containing a negative electrode active material layer, Electrolyte and Equipped with, The negative electrode active material layer comprises a negative electrode active material, an alkali metal carbonate compound, and a magnesium compound. The alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and contains an alkali metal element as a constituent element. The aforementioned magnesium compound contains magnesium as a constituent element. The content of the alkali metal carbonate compound in the negative electrode active material layer is 0.2% by weight or more and 0.8% by weight or less. The content of the magnesium compound in the negative electrode active material layer is 0.01% by weight or more and 5% by weight or less. Secondary battery.

2. The alkali metal carbonate compound is lithium carbonate (Li 2 CO 3 ), comprising at least one of the compounds represented by formula (1) and the compound represented by formula (2), The secondary battery according to claim 1. R1-OC(=O)O-M1...(1) (R1 is an alkyl group. M1 is an alkali metal element.) M2-OC(=O)O-R2-OC(=O)O-M3...(2) (R2 is an alkylene group. M2 and M3 are alkali metal elements, respectively.)

3. In formula (1) above, the alkali metal element is lithium, In formula (2) above, the alkali metal element is lithium. The secondary battery according to claim 2.

4. The magnesium compound comprises at least one of magnesium fluoride, magnesium oxide, magnesium nitride, and magnesium carbonate. A secondary battery according to any one of claims 1 to 3.

5. The negative electrode active material includes a carbon material and a silicon-containing material. A secondary battery according to any one of claims 1 to 3.

6. Lithium-ion rechargeable batteries, A secondary battery according to any one of claims 1 to 3.

7. Equipped with a negative electrode active material layer, The negative electrode active material layer comprises a negative electrode active material, an alkali metal carbonate compound, and a magnesium compound. The alkali metal carbonate compound has a carbonate bond (-OC(=O)O-) and contains an alkali metal element as a constituent element. The aforementioned magnesium compound contains magnesium as a constituent element. The content of the alkali metal carbonate compound in the negative electrode active material layer is 0.2% by weight or more and 0.8% by weight or less. The content of the magnesium compound in the negative electrode active material layer is 0.01% by weight or more and 5% by weight or less. Negative electrode for secondary batteries.

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