WO2013062056A1 - 非水系二次電池 - Google Patents
非水系二次電池 Download PDFInfo
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- WO2013062056A1 WO2013062056A1 PCT/JP2012/077629 JP2012077629W WO2013062056A1 WO 2013062056 A1 WO2013062056 A1 WO 2013062056A1 JP 2012077629 W JP2012077629 W JP 2012077629W WO 2013062056 A1 WO2013062056 A1 WO 2013062056A1
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Definitions
- the present invention relates to a non-aqueous secondary battery.
- Non-aqueous secondary batteries containing non-aqueous electrolytes are characterized by their light weight, high energy, and long life, and are portable for notebook computers, mobile phones, smartphones, tablet PCs, digital cameras, video cameras, etc. Widely used as a power source for electronic equipment.
- HEV hybrid electric vehicles
- PHEV plug-in Hybrid Electric Vehicle
- the battery components When mounting non-aqueous secondary batteries in vehicles such as automobiles and residential power storage systems, the battery components are chemically and electrochemically stable from the viewpoints of cycle performance and long-term reliability in high-temperature environments. Materials with excellent properties, strength, corrosion resistance, etc. are required. Further, since the use conditions are significantly different from those of the portable electronic device power supply and it must operate even in a cold region, high output performance and long life performance in a low temperature environment are also required as necessary physical properties. On the other hand, in order to meet the needs for higher capacity and higher output expected in the future, it is necessary not only to develop materials, but also to assemble batteries into an optimal state so that each material can fully perform its functions. is there.
- the design must be balanced.
- increasing the capacity of a non-aqueous secondary battery can be achieved by improving the performance of the electrode active material, but in practice it is most important to produce an electrode active material layer with a high volumetric energy density. is there.
- the amount of the electrode active material per unit volume of the battery is relatively larger than other battery materials not related to the battery capacity, such as current collector foils and separators. As a battery, the capacity will be increased.
- an electrode active material layer having a low porosity is obtained, and in this case as well, high capacity is realized as a battery.
- the diffusion path of lithium ions is contrary to the case of aiming for higher capacity. It is necessary to design the electrode active material layer so as to shorten the length. Specifically, there are methods such as decreasing the basis weight of the electrode active material layer and increasing the porosity of the electrode active material layer. By the way, in order to improve the output characteristics, it is also effective to select an electrolytic solution having high ion conductivity.
- a non-aqueous electrolyte as the electrolyte of a lithium ion secondary battery operating at room temperature.
- a high dielectric solvent such as a cyclic carbonate and a low chain carbonate such as a low chain carbonate are preferable.
- a combination with a viscous solvent is a common solvent.
- ordinary high dielectric constant solvents have a high melting point, and depending on the type of electrolyte used, their output characteristics, and further, low temperature characteristics can be degraded.
- a nitrile solvent having an excellent balance between viscosity and relative dielectric constant has been proposed.
- Patent Document 1 reports an electrolytic solution with reduced influence of reductive decomposition, which is obtained by mixing and diluting a cyclic carbonate such as ethylene carbonate and a nitrile solvent such as acetonitrile.
- Patent Documents 2 to 4 report batteries that suppress reductive decomposition of a nitrile solvent by using a negative electrode that is nobler than the reduction potential of the nitrile solvent.
- Patent Document 5 reports a nonaqueous electrolytic solution in which sulfur dioxide and one or more other aprotic polar solvents are added to a nitrile solvent for the purpose of forming a protective film on the negative electrode. Yes.
- Patent Document 1 no solution for high temperature durability performance has been presented, and when the use is continued in a high temperature environment, the battery deteriorates and the capacity of the battery is greatly increased. There is a high possibility that it will decrease or charge / discharge itself will be impossible.
- Patent Documents 2 to 4 when the negative electrodes described in Patent Documents 2 to 4 are used, the characteristics of the lithium ion secondary battery that are high voltage are sacrificed.
- Patent Document 5 uses a highly reactive gas as an additive, the addition itself is very difficult, and self-discharge during charge storage is unavoidable. Further, when the gas is volatilized, the inside of the battery is pressurized, which leaves extremely serious practical problems such as battery expansion and, in some cases, rupture.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a non-aqueous secondary battery that realizes high output performance even when an electrode active material layer having a high volume energy density is designed. .
- the present inventors have found that a non-aqueous secondary battery using a specific non-aqueous electrolyte having an ionic conductivity of 15 mS / cm or more at 25 ° C. Even when an electrode active material layer having a high energy density is designed, it has been found that high output performance can be realized, and the present invention has been completed. That is, the present invention is as follows.
- a non-aqueous secondary battery comprising an electrolyte containing a lithium salt and a non-aqueous solvent, a positive electrode, and a negative electrode, wherein the basis weight of the positive electrode active material layer contained in the positive electrode is 8 to 100 mg / cm 2 , And / or the non-aqueous secondary battery in which the basis weight of the negative electrode active material layer included in the negative electrode is 3 to 46 mg / cm 2 and the ionic conductivity of the electrolyte at 25 ° C. is 15 mS / cm or more. .
- the electrolytic solution has an ionic conductivity at 25 ° C. of 50 mS / cm or less.
- the basis weight of the positive electrode active material layer contained in the positive electrode is 24 to 100 mg / cm 2 and / or the basis weight of the negative electrode active material layer contained in the negative electrode is 10 to 46 mg / cm 2 .
- the non-aqueous secondary battery as described in [2].
- R 1 -AR 2 (1) (Wherein R 1 and R 2 each independently represents an aryl group or an alkyl group optionally substituted with a halogen atom, or an aryl group optionally substituted with an alkyl group or a halogen atom, or , R 1 and R 2 are bonded to each other to form a cyclic structure which may have an unsaturated bond with A, and A is represented by any one of the following formulas (2) to (6) A divalent group having a structure is shown.) [12] The compound represented by the formula (1) includes ethylene sulfite, propylene sulfite, butylene sulfite, pentene sulfite, sulfolane, 3-methylsulfolane, 3-sulfolene, 1,3-propane sultone, 1,4- The non-aqueous secondary battery according to [11] above, comprising one or more compounds selected from the group consisting of butane sultone, 1,3-propanedi
- the lithium salt is an inorganic lithium salt having a fluorine atom.
- the inorganic lithium salt is LiPF 6, a nonaqueous secondary battery of the above-mentioned [14], wherein.
- the inorganic lithium salt is LiBF 4 .
- An organic lithium salt is further contained, and the organic lithium salt and the inorganic lithium salt are represented by the following formula (7): 0 ⁇ X ⁇ 1 (7) (In the formula, X is the molar ratio of the organic lithium salt to the inorganic lithium salt.)
- the non-aqueous secondary battery according to [18], wherein the organic lithium salt is one or more organic lithium salts selected from the group consisting of lithium bis (oxalato) borate and lithium oxalatodifluoroborate.
- the positive electrode contains at least one material selected from the group consisting of materials capable of inserting and extracting lithium ions as a positive electrode active material, and the negative electrode absorbs and releases lithium ions as a negative electrode active material.
- the lithium-containing compound includes at least one compound selected from the group consisting of a metal oxide having lithium and a metal chalcogenide having lithium.
- the negative electrode contains, as the negative electrode active material, one or more materials selected from the group consisting of metallic lithium, a carbon material, and a material containing an element capable of forming an alloy with lithium.
- the negative electrode has lithium ions of 1.4 Vvs.
- the positive electrode mixture of the positive electrode contains at least one compound selected from the group consisting of a positive electrode active material, a conductive additive, a binder, an organic acid, and an organic acid salt.
- non-aqueous secondary battery [26] The non-aqueous secondary battery according to [25], wherein the compound includes a divalent or higher valent organic acid or organic acid salt. [27] The non-aqueous secondary battery according to [25] or [26] above, wherein the positive electrode active material layer produced from the positive electrode mixture has a thickness of 50 to 300 ⁇ m. [28] The positive electrode and / or negative electrode is an electrode obtained by applying a positive electrode active material layer and / or a negative electrode active material layer on an electrode substrate obtained by applying a conductive layer containing a conductive material on an electrode current collector. ] The nonaqueous secondary battery according to any one of [27] to [27].
- the non-aqueous secondary battery of this embodiment includes a non-aqueous secondary battery that includes a non-aqueous electrolyte solution (hereinafter, also simply referred to as “electrolyte solution”) containing a lithium salt and a non-aqueous solvent, a positive electrode, and a negative electrode.
- electrolyte solution a non-aqueous electrolyte solution
- the basis weight of the positive electrode active material layer contained in the positive electrode is 8 to 100 mg / cm 2 and / or the basis weight of the negative electrode active material layer contained in the negative electrode is 3 to 46 mg / cm 2 .
- the ionic conductivity in 25 degreeC of the said electrolyte solution is 15 mS / cm or more.
- non-aqueous secondary battery examples include a positive electrode containing one or more materials selected from the group consisting of materials capable of inserting and extracting lithium ions as a positive electrode active material, and lithium ions as a negative electrode active material. And a negative electrode containing one or more materials selected from the group consisting of a negative electrode material that can be occluded and released and a metallic lithium, and a lithium ion secondary battery.
- Examples of the non-aqueous secondary battery of the present embodiment include a lithium ion secondary battery, and more specifically, a lithium ion secondary battery schematically showing a cross-sectional view in FIG.
- a lithium ion secondary battery 100 shown in FIG. 1 includes a separator 110, a positive electrode active material layer 120 and a negative electrode active material layer 130 sandwiching the separator 110 from both sides, and further (separator 110, positive electrode active material layer 120 and negative electrode).
- a positive electrode current collector 140 (disposed outside the positive electrode active material layer 120) sandwiching the laminate of the active material layers 130), a negative electrode current collector 150 (arranged outside the negative electrode active material layer 130), and the like are accommodated (Hereinafter, also abbreviated as “electrode” as a generic term for a positive electrode and a negative electrode, and as an “electrode active material layer” as a generic term for a positive electrode active material layer and a negative electrode active material layer).
- the positive electrode is composed of a positive electrode active material layer 120 made from a positive electrode mixture and a positive electrode current collector 140
- the negative electrode is made up of a negative electrode active material layer 130 made from a negative electrode mixture and a negative electrode current collector 150 (hereinafter referred to as positive electrode).
- Electrode mixture As a general term for a mixture and a negative electrode mixture.
- the laminate in which the positive electrode active material layer 120, the separator 110, and the negative electrode active material layer 130 are stacked is impregnated with an electrolytic solution.
- electrolytic solution As these members, those provided in a conventional lithium ion secondary battery can be used as long as the requirements in the present embodiment are satisfied. For example, those described below may be used.
- the electrolyte solution in the present embodiment contains a lithium salt and a non-aqueous solvent, and is not particularly limited as long as the ionic conductivity at 25 ° C. is 15 mS / cm or more.
- the lithium salt and the non-aqueous solvent are known ones. May be.
- the ion conductivity at 25 ° C. is preferably 20 mS / cm or more, and preferably 25 mS / cm or more from the viewpoint of achieving high output performance. Is more preferable.
- the upper limit of the ionic conductivity at 25 ° C. is not particularly limited, but the ionic conductivity may be 50 mS / cm or less from the viewpoint of suppressing unexpected battery deterioration such as elution deterioration and peeling deterioration of various battery members. Preferably, it is 49 mS / cm or less, and more preferably 48 mS / cm or less.
- the ionic conductivity of the electrolytic solution can be controlled, for example, by adjusting the viscosity and / or polarity of the non-aqueous solvent. More specifically, the ionic conductivity of the non-aqueous solvent and the high polarity can be controlled. By mixing with a non-aqueous solvent, the ionic conductivity of the electrolytic solution can be controlled to be high. Further, by using a non-aqueous solvent having a low viscosity and a high polarity, the ionic conductivity of the electrolytic solution can be controlled to be high.
- the ionic conductivity of the electrolytic solution can be measured according to the method described in “(1-1) Measurement of ionic conductivity of non-aqueous electrolytic solution” in Examples described later.
- the non-aqueous electrolyte solution in this embodiment preferably does not contain moisture, but may contain a very small amount of moisture as long as it does not impede the solution of the problems of the present invention.
- the water content is preferably 0 to 100 ppm with respect to the total amount of the nonaqueous electrolytic solution.
- Non-aqueous solvent is not particularly limited as long as a predetermined ion conductivity can be obtained in combination with other components, and examples thereof include alcohols such as methanol and ethanol, and aprotic solvents. An aprotic polar solvent is preferred.
- non-aqueous solvent examples include, for example, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, trans-2,3-butylene carbonate, cis-2,3-butylene carbonate, 1,2-pentylene carbonate, Cyclic carbonates represented by trans-2,3-pentylene carbonate, cis-2,3-pentylene carbonate, trifluoromethylethylene carbonate, fluoroethylene carbonate, 1,2-difluoroethylene carbonate; ⁇ -butyrolactone, ⁇ - Lactones typified by valerolactone; sulfur compounds typified by sulfolane and dimethyl sulfoxide; cyclic ethers typified by tetrahydrofuran, 1,4-dioxane and 1,3-dioxane; ethyl methyl carbonate, di Chain carbonates typified by methyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isoprop
- the non-aqueous solvent those having a low viscosity and a high dielectric constant are preferable, and among them, a nitrile solvent having an excellent balance between viscosity and dielectric constant is preferably included.
- the nitrile solvent preferably contains acetonitrile.
- Acetonitrile has a low viscosity and a high polarity.
- non-aqueous secondary battery By using an electrolytic solution containing such a non-aqueous solvent, it is possible to provide a non-aqueous secondary battery that enables large-current discharge and rapid charging based on its characteristics. Since compounds containing nitrile groups are easily electrochemically reduced and decomposed, when using nitrile solvents, they are mixed with other solvents and / or additives for forming a protective film on the electrode are added. It is preferable to do.
- the non-aqueous solvent preferably contains one or more cyclic aprotic polar solvents, and contains one or more cyclic carbonates. It is more preferable.
- a mixed solvent of two or more non-aqueous solvents is preferable.
- the non-aqueous solvent that is a component of the mixed solvent include the same ones as described above, and examples of the mixed solvent include a mixed solvent of a cyclic carbonate and acetonitrile.
- the content of acetonitrile is not particularly limited as long as predetermined ion conductivity is obtained in combination with other components, but the total amount of the non-aqueous solvent
- the content is preferably 5 to 97% by volume, more preferably 10 to 90% by volume, and still more preferably 25 to 80% by volume.
- the content of acetonitrile is 5% by volume or more, the ionic conductivity tends to increase and high output characteristics tend to be exhibited.
- it is 97% by volume or less problems caused by volatilization are suppressed, and a special method is used. There is a tendency that the reductive decomposition reaction at the negative electrode can be moderated without using.
- the content of acetonitrile in the non-aqueous solvent is within the above range, the cycle performance long-term characteristics and other battery characteristics tend to be further improved while maintaining the excellent performance of acetonitrile. is there.
- the lithium salt is not particularly limited as long as it is a lithium salt that is usually used in an electrolyte solution for a non-aqueous secondary battery as long as a predetermined ion conductivity can be obtained in combination with other components. It may be a thing.
- the lithium salt is preferably contained in the nonaqueous electrolytic solution in the present embodiment at a concentration of 0.1 to 3 mol / L, and more preferably 0.5 to 2 mol / L. When the concentration of the lithium salt is within the above range, the electric conductivity of the electrolytic solution is kept higher, and at the same time, the charge / discharge efficiency of the nonaqueous secondary battery tends to be kept higher.
- the lithium salt in this embodiment it is an inorganic lithium salt.
- the “inorganic lithium salt” refers to a lithium salt that does not contain a carbon atom in an anion and is soluble in acetonitrile, and the “organic lithium salt” described later contains a carbon atom in an anion and is soluble in acetonitrile.
- the inorganic lithium salt is not particularly limited as long as it is used as a normal non-aqueous electrolyte, and may be any one.
- inorganic lithium salts include, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li 2 SiF 6 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , Li 2 B 12 F b H 12-b [B is an integer of 0 to 3], and lithium salt bonded to a polyvalent anion containing no carbon atom.
- inorganic lithium salts are used singly or in combination of two or more.
- an inorganic lithium salt having a fluorine atom is used as the inorganic lithium salt
- a passive film is formed on the surface of the metal foil that is the positive electrode current collector, which is preferable from the viewpoint of suppressing an increase in internal resistance.
- an inorganic lithium salt having a phosphorus atom is used as the inorganic lithium salt, it is more preferable because free fluorine atoms are easily released, and LiPF 6 is particularly preferable.
- it is preferable to use an inorganic lithium salt having a boron atom as the inorganic lithium salt because it is easy to capture an excess free acid component that may cause battery deterioration. From such a viewpoint, LiBF 4 is particularly preferable. .
- the content of the inorganic lithium salt in the non-aqueous electrolyte solution of the present embodiment is preferably 0.1 to 40% by mass and more preferably 1 to 30% by mass with respect to the total amount of the non-aqueous electrolyte solution.
- the content is 5 to 25% by mass.
- the lithium salt in the present embodiment may further contain an organic lithium salt in addition to the inorganic lithium salt.
- organic lithium salt with inorganic lithium salt with high ion conductivity following formula (7): 0 ⁇ X ⁇ 1 (7) It is preferable to satisfy the condition represented by.
- X shows the molar ratio of the organic lithium salt with respect to the inorganic lithium salt contained in a non-aqueous electrolyte solution.
- the content of the organic lithium salt in the non-aqueous electrolyte solution of the present embodiment is preferably 0.1 to 30% by mass, and preferably 0.2 to 20% by mass with respect to the total amount of the non-aqueous electrolyte solution. Is more preferably 0.5 to 15% by mass.
- the content of the organic lithium salt is in the above range, the balance between the function and solubility of the electrolytic solution tends to be ensured.
- organic lithium salt examples include LiN (SO 2 C m F 2m + 1 ) 2 such as LiN (SO 2 CF 3 ) 2 and LiN (SO 2 C 2 F 5 ) 2, where m is an integer of 1 to 8.
- the organic lithium salt represented by the following general formula (8a), (8b), and (8c) can also be used.
- R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 may be the same as or different from each other, and are perfluoroalkyl having 1 to 8 carbon atoms. Indicates a group.
- organic lithium salts are used singly or in combination of two or more, and organic lithium salts having boron atoms are preferred because of their structural stability.
- the organic lithium salt having an organic ligand has an internal structure including a positive electrode because the organic ligand participates in an electrochemical reaction and forms a protective film called Solid Electrolyte Interface (SEI) on the electrode surface. This is preferable from the viewpoint of suppressing an increase in resistance.
- SEI Solid Electrolyte Interface
- LiBOB a borate lithium salt having a halogenated organic acid as a ligand, LiODFB, and LiBMB are preferable, and LiBOB and LiODFB are particularly preferable.
- the electrolytic solution in the present embodiment may further contain an ionic compound composed of a salt formed of an organic cation species other than lithium ions and an anionic species.
- an ionic compound composed of a salt formed of an organic cation species other than lithium ions and an anionic species.
- Examples of the cation of the ionic compound include tetraethylammonium, tetrabutylammonium, triethylmethylammonium, trimethylethylammonium, dimethyldiethylammonium, trimethylpropylammonium, trimethylbutylammonium, trimethylpentylammonium, trimethylhexylammonium, trimethyloctylammonium, and diethyl.
- Quaternary ammonium cations such as methylmethoxyethylammonium; 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-hexyl-3-methyl Imidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-methyl-3-propylimidazolium, etc.
- pyridinium cation such as 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium
- piperidinium cation such as 1-methyl-1-propylpiperidinium, 1-butyl-1-methylpiperidinium
- Pyrrolidinium cations such as 1-ethyl-1-methylpyrrolidinium, 1-methyl-1-propylpyrrolidinium and 1-butyl-1-methylpyrrolidinium
- sulfonium cations such as diethylmethylsulfonium and triethylsulfonium
- a quaternary phosphonium cation Among these cations, a cation having a nitrogen atom is preferable from the viewpoint of electrochemical stability, and a pyridinium cation is more preferable.
- the anion of the ionic compound is not particularly limited as long as it is usually used as a counter ion of the cation.
- BF 4 ⁇ , PF 6 ⁇ , N (SO 2 CF 3 ) 2 ⁇ , N (SO 2 C 2 F 5 ) 2 ⁇ and SO 3 CF 3 — Among these anions, PF 6 - is preferable because it is excellent in dissociation of ions and suppression of increase in internal resistance.
- the electrolytic solution in the present embodiment may contain an additive for protecting the electrode.
- the additive is not particularly limited as long as it does not inhibit the solution of the problem according to the present invention, and may substantially overlap with a substance that plays a role as a solvent for dissolving a lithium salt, that is, the above non-aqueous solvent.
- the additive is preferably a substance that contributes to the performance improvement of the non-aqueous electrolyte solution and the non-aqueous secondary battery in the present embodiment, but also includes a substance that does not directly participate in the electrochemical reaction, One kind is used alone, or two or more kinds are used in combination.
- the additive include, for example, 4-fluoro-1,3-dioxolan-2-one, 4,4-difluoro-1,3-dioxolan-2-one, cis-4,5-difluoro-1, 3-dioxolan-2-one, trans-4,5-difluoro-1,3-dioxolan-2-one, 4,4,5-trifluoro-1,3-dioxolan-2-one, 4,4,5 , 5-tetrafluoro-1,3-dioxolan-2-one, fluoroethylene carbonate represented by 4,4,5-trifluoro-5-methyl-1,3-dioxolan-2-one; vinylene carbonate, 4 , 5-dimethyl vinylene carbonate, cyclic carbonates containing unsaturated bonds typified by vinyl ethylene carbonate; ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolac Lactones represented by N, ⁇ -valerolactone,
- the content of the additive in the electrolytic solution in the present embodiment is not particularly limited, but is preferably 0.1 to 30% by mass, and preferably 0.2 to 25% by mass with respect to the total amount of the electrolytic solution. More preferably, it is more preferably 0.5 to 20% by mass.
- the additive contributes to the development of high cycle performance, but on the other hand, the contribution to high output performance in a low temperature environment has not been confirmed. As the content of the additive increases, the deterioration of the electrolytic solution is suppressed. However, the lower the additive, the higher the high output characteristics in a low temperature environment.
- the superior performance based on the high ionic conductivity of the non-aqueous electrolyte solution can be more fully satisfied without impairing the basic function as a non-aqueous secondary battery.
- the cycle performance of the electrolytic solution, the high output performance under a low temperature environment, and other battery characteristics tend to be further improved.
- the non-nitrile additive contains one or more compounds selected from the group consisting of compounds represented by the following formula (1) (hereinafter referred to as “compound (1)”).
- compound (1) compounds represented by the following formula (1)
- R 1 and R 2 are each independently an aryl group or an alkyl group which may be substituted with a halogen atom, or an aryl group which may be substituted with an alkyl group or a halogen atom.
- R 1 and R 2 are bonded to each other to form a cyclic structure which may have an unsaturated bond with A, and A is any one of the following formulas (2) to (6): And a divalent group having a structure represented by
- the aryl group represented by R 1 and R 2 or the alkyl group which may be substituted with a halogen atom is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with an aryl group or a halogen atom, and more A phenyl group or an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom is preferable.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
- aryl group serving as a substituent examples include a phenyl group, a naphthyl group, and an anthranyl group, and among them, a phenyl group is preferable.
- a halogen atom which becomes a substituent of an alkyl group a fluorine atom, a chlorine atom and a bromine atom are preferable.
- a plurality of these substituents may be substituted with an alkyl group, and both an aryl group and a halogen atom may be substituted.
- the aryl group optionally substituted with an alkyl group or a halogen atom represented by R 1 and R 2 is preferably a phenyl group, a naphthyl group or an anthranyl group optionally substituted with an alkyl group or a halogen atom, and more Preferred is an alkyl group or a phenyl group which may be substituted with a halogen atom, and more preferred is a phenyl group which may be substituted with a halogen atom.
- the aryl group include a phenyl group, a naphthyl group, and an anthranyl group, and among them, a phenyl group is preferable.
- the alkyl group that serves as a substituent for the aryl group is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
- a halogen atom serving as a substituent for the aryl group a fluorine atom, a chlorine atom and a bromine atom are preferable. A plurality of these substituents may be substituted with an aryl group, and both an alkyl group and a halogen atom may be substituted.
- the cyclic structure formed by R 1 and R 2 bonded to each other together with A is preferably a 4-membered ring or more, and may have any one or more of a double bond and a triple bond.
- R 1 and R 2 bonded to each other are each preferably a divalent hydrocarbon group, preferably having 1 to 6 carbon atoms.
- one or more hydrogen atoms of these groups are any of an alkyl group (for example, a methyl group and an ethyl group), a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom) and an aryl group (for example, a phenyl group). Or may be substituted by one or more.
- R 1 and R 2 may be the same or different from each other.
- Specific examples of the compound (1) in which A is a divalent group having the structure represented by the above formula (2) include dimethyl sulfite, diethyl sulfite, ethyl methyl sulfite, methyl propyl sulfite, ethyl propyl Chain sulfites such as sulfite, diphenyl sulfite, methylphenyl sulfite, ethyl sulfite, dibenzyl sulfite, benzyl methyl sulfite, benzyl ethyl sulfite; ethylene sulfite, propylene sulfite, butylene sulfite, pentene Cyclic sulfites such as sulfite, vinylene sulfite, phenylethylene sulfite, 1-methyl-2-phenylethylene sulfite, and 1-ethyl-2-phenylethylene sulfite
- Specific examples of the compound (1) in which A is a divalent group having the structure represented by the above formula (3) include dimethylsulfone, diethylsulfone, ethylmethylsulfone, methylpropylsulfone, ethylpropylsulfone, diphenylsulfone, Chain sulfones such as methylphenylsulfone, ethylphenylsulfone, dibenzylsulfone, benzylmethylsulfone, benzylethylsulfone; sulfolane, 2-methylsulfolane, 3-methylsulfolane, 2-ethylsulfolane, 3-ethylsulfolane, 2,4 -Cyclic sulfones such as dimethylsulfolane, 3-sulfolene, 3-methylsulfolene, 2-phenylsulfolane, and 3-phenylsulfolane; and chain
- Specific examples of the compound (1) in which A is a divalent group having the structure represented by the above formula (4) include methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, methyl ethanesulfonate, ethane Ethyl sulfonate, propyl ethane sulfonate, methyl benzene sulfonate, ethyl benzene sulfonate, propyl benzene sulfonate, phenyl methane sulfonate, phenyl ethane sulfonate, phenyl propane sulfonate, benzyl methane sulfonate, benzyl ethane sulfonate, propane Chain sulfonate esters such as benzyl sulfonate: cyclic sulfonate esters such as 1,
- Specific examples of the compound (1) in which A is a divalent group having the structure represented by the above formula (5) include dimethyl sulfate, diethyl sulfate, ethyl methyl sulfate, methyl propyl sulfate, ethyl propyl sulfate, methyl phenyl sulfate.
- Chain sulfate such as ethylphenyl sulfate, phenylpropyl sulfate, benzylmethyl sulfate, benzylethyl sulfate; ethylene glycol sulfate, 1,2-propanediol sulfate, 1,3-propanediol sulfate, 1,2- Cyclic sulfates such as butanediol sulfate, 1,3-butanediol sulfate, 2,3-butanediol sulfate, phenylethylene glycol sulfate, methylphenylethylene glycol sulfate, ethylphenylethylene glycol sulfate; and the above Halides Jo sulfate or cyclic sulfate esters.
- Specific examples of the compound (1) in which A is a divalent group having the structure represented by the above formula (6) include dimethyl sulfoxide, diethyl sulfoxide, ethyl methyl sulfoxide, methyl propyl sulfoxide, ethyl propyl sulfoxide, diphenyl sulfoxide, Chain sulfoxides such as methylphenyl sulfoxide, ethylphenyl sulfoxide, dibenzyl sulfoxide, benzylmethyl sulfoxide, benzylethyl sulfoxide; cyclic sulfoxides such as tetramethylene sulfoxide and thiophene 1-oxide; and halides of the above chain sulfoxides and cyclic sulfoxides; Can be mentioned.
- Compound (1) is used singly or in combination of two or more. When two or more compounds (1) are combined, the structures of A in each compound (1) may be the same or different from each other.
- the content of the compound (1) in the non-aqueous electrolyte solution is not particularly limited, but may be 0.05 to 30% by volume with respect to the total amount of components contained in the non-aqueous electrolyte solution excluding the lithium salt. Preferably, it is 0.1 to 20% by volume, more preferably 0.5 to 10% by volume.
- Some of the compounds (1) are solid at room temperature (25 ° C.), but in that case, the saturated dissolution amount in acetonitrile or less, preferably 60% by mass or less of the saturated dissolution amount, more preferably the saturated dissolution amount. It is used in the range of 30% by mass or less.
- the compound (1) preferably has a cyclic structure.
- one or more compounds selected from the group consisting of tetramethylene sulfoxide it is possible to continuously exhibit higher performance even under harsh use environments such as high-temperature charge / discharge and charge storage. .
- the electrolytic solution in the present embodiment uses carbonates, that is, one or more compounds selected from the group consisting of compounds having CO 3 in the molecule in combination with the compound (1) from the viewpoint of improving the durability of SEI. It is preferable.
- the carbonates are preferably organic carbonates, more preferably cyclic carbonates, and further preferably compounds having an intercarbon unsaturated double bond.
- vinylene carbonate is used as a main component, that is, a carbonate containing the largest amount
- the durability of SEI is dramatically improved by a synergistic effect with the compound (1). This is because such carbonates tend to undergo copolymerization decomposition reaction, that is, copolymer formation with other additives, and the compound (1) plays a role as a comonomer. This is thought to be due to the increase in properties and poor solubility.
- the factor is not limited to this.
- the non-aqueous electrolyte in the present embodiment may further contain a dinitrile compound, that is, a compound having two nitrile groups in the molecule.
- the dinitrile compound has the effect of reducing corrosion of metal parts such as battery cans and electrodes. The reason for this is considered to be that the use of a dinitrile compound forms a protective film that suppresses corrosion on the surface of the metal portion with reduced corrosion.
- the factor is not limited to this.
- the dinitrile compound is not particularly limited as long as it does not hinder the solution of the problems of the present invention, but preferably has methylene chains, more preferably 1 to 12 methylene chains, linear, branched, Any of the shapes may be used.
- Examples of the dinitrile compound include succinonitrile, glutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, 1,8-dicyanooctane, 1,9-dicyanononane.
- Linear dinitrile compounds such as 1,10-dicyanodecane, 1,11-dicyanoundecane, 1,12-dicyanododecane; tetramethylsuccinonitrile, 2-methylglutaronitrile, 2,4-dimethylglutaronitrile 2,2,4,4-tetramethylglutaronitrile, 1,4-dicyanopentane, 2,5-dimethyl-2,5-hexanedicarbonitrile, 2,6-dicyanoheptane, 2,7-dicyanooctane Branched dinitrile compounds such as 2,8-dicyanononane and 1,6-dicyanodecane; , 2-dicyanobenzene, 1,3-dicyanobenzene, aromatic dinitrile compounds such as 1,4-dicyano benzene. These are used singly or in combination of two or more.
- the content of the dinitrile compound in the nonaqueous electrolytic solution in the present embodiment is not particularly limited, but is preferably 0.01 to 1 mol / L with respect to the total amount of components contained in the electrolytic solution excluding the lithium salt. 0.02 to 0.5 mol / L is more preferable, and 0.05 to 0.3 mol / L is still more preferable.
- the cycle performance tends to be further improved without impairing the basic function as the non-aqueous secondary battery.
- the dinitrile compound tends to have a low dipole moment when the number of methylene chains is an even number, but surprisingly a higher addition effect was experimentally recognized than when the number of methylene chains was an odd number. Therefore, the dinitrile compound preferably contains one or more compounds selected from the group consisting of compounds represented by the following general formula (9).
- R 10 and R 11 each independently represent a hydrogen atom or an alkyl group, and a represents an integer of 1 to 6.
- the alkyl group preferably has 1 to 10 carbon atoms.
- Positive electrode and positive electrode current collector> A positive electrode will not be specifically limited if it acts as a positive electrode of a non-aqueous secondary battery, A well-known thing may be used.
- the positive electrode contains one or more materials selected from the group consisting of materials capable of occluding and releasing lithium ions as the positive electrode active material, high voltage and high energy density tend to be obtained. preferable. Examples of such materials include lithium-containing compounds represented by the following general formulas (10a) and (10b), and metal oxides and metal chalcogenides having a tunnel structure and a layered structure.
- the chalcogenide refers to sulfide, selenide, and telluride.
- M represents one or more metal elements including at least one transition metal element
- x represents a number from 0 to 1.1
- y represents a number from 0 to 2.
- lithium-containing compound represented by the general formulas (10a) and (10b) examples include lithium cobalt oxides typified by LiCoO 2 ; typified by LiMnO 2 , LiMn 2 O 4 , and Li 2 Mn 2 O 4.
- the lithium-containing compound other than (10a) and (10b) is not particularly limited as long as it contains lithium, and includes, for example, a composite oxide containing lithium and a transition metal element, and lithium and a transition metal element.
- a metal phosphate compound and a metal silicate compound containing lithium and a transition metal element (for example, Li t M u SiO 4 , M is as defined in the above formula (10a), t is a number from 0 to 1, and u is 0 Represents the number of ⁇ 2.).
- lithium, cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), vanadium ( V) and composite oxides containing at least one transition metal element selected from the group consisting of titanium (Ti) and metal phosphate compounds are preferred.
- the lithium-containing compound is preferably a metal oxide having lithium or a metal chalcogenide having lithium, and a metal phosphate compound having lithium, for example, represented by the following general formulas (11a) and (11b), respectively.
- the compound which is made is mentioned.
- metal oxides having lithium and metal chalcogenides having lithium are more preferable.
- Li v M I D 2 (11a ) Li w M II PO 4 (11b)
- D represents oxygen or a chalcogen element
- M I and M II each represent one or more transition metal elements
- the values of v and w differ depending on the charge / discharge state of the battery, but usually v is 0.05 to 1.10, w represents a number from 0.05 to 1.10.
- the compound represented by the general formula (11a) generally has a layered structure
- the compound represented by the general formula (11b) generally has an olivine structure.
- a part of the transition metal element is substituted with Al, Mg, other transition metal elements or included in the crystal grain boundary, or one of the oxygen atoms.
- Those obtained by substituting a part with a fluorine atom or the like may be used, and further, at least part of the surface of the positive electrode active material may be coated with another positive electrode active material.
- Examples of the metal oxide or metal chalcogenide having a tunnel structure and a layered structure include, for example, MnO 2 , FeO 2 , FeS 2 , V 2 O 5 , V 6 O 13 , TiO 2 , TiS 2 , MoS 2 and NbSe.
- 2 includes oxides, sulfides and selenides of metals other than lithium.
- Examples of other positive electrode active materials include sulfur and conductive polymers represented by polyaniline, polythiophene, polyacetylene, and polypyrrole.
- the positive electrode active material may be used alone or in combination of two or more.
- the number average particle size (primary particle size) of the positive electrode active material is preferably 0.05 to 100 ⁇ m, more preferably 1 to 10 ⁇ m.
- the number average particle size of the positive electrode active material can be measured by a wet particle size measuring device (for example, a laser diffraction / scattering particle size distribution meter, a dynamic light scattering particle size distribution meter).
- 100 particles observed with a transmission electron microscope are randomly extracted and analyzed with image analysis software (for example, image analysis software manufactured by Asahi Kasei Engineering Co., Ltd., trade name “A Image-kun”). It can also be obtained by calculating an average. In this case, when the number average particle diameter differs between measurement methods for the same sample, a calibration curve created for the standard sample may be used.
- the positive electrode mixture of the non-aqueous secondary battery in this embodiment is a positive electrode active material, a conductive additive, a binder, and at least one compound selected from the group consisting of an organic acid and an organic acid salt (hereinafter referred to as “organic”). It may also be abbreviated as “acid compound”). Cathode mixtures containing organic acid compounds function extremely stably, with little risk of embrittlement and poor binding to the electrode current collector, even when non-ionic electrolytes with high ionic conductivity are used. This is preferable.
- the non-aqueous secondary battery by which the increase in internal resistance resulting from positive electrode deterioration was suppressed significantly can be provided.
- Organic acids and organic acid salts have a role of increasing the binding force between the positive electrode active materials and between the positive electrode active material layer and the electrode current collector, and the type thereof is not particularly limited as long as the organic solvent is soluble.
- the at least one compound selected from the group consisting of an organic acid and an organic acid salt is a divalent or higher organic compound from the viewpoint that the fluidity of the positive electrode mixture is high and the increase in viscosity with time is suppressed. It is preferable to include an acid or an organic acid salt.
- organic acid compounds include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, and acrylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelain.
- Aliphatic saturated dicarboxylic acids such as acid and sebacic acid; aliphatic unsaturated dicarboxylic acids such as maleic acid and fumaric acid; aromatic dicarboxylic acids such as phthalic acid; tricarboxylic acids such as citric acid; and lithium salts of the above carboxylic acids; A sodium salt and an ammonium salt are mentioned.
- oxalic acid and malonic acid are preferred because there is a tendency that unevenness of the surface of the dry cathode active material layer is less likely to occur by suppressing an increase in the viscosity of the cathode mixture slurry.
- the said compound may be used individually by 1 type, or may use 2 or more types together.
- the addition amount of the organic acid compound is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, and more preferably 0.1 to 2 parts by mass per 100 parts by mass of the positive electrode active material. More preferably, it is part.
- the addition amount of the organic acid compound is preferably 0.01 parts by mass or more from the viewpoint of binding force, and is 3 parts by mass or less from the viewpoint of slurry viscosity, dispersibility, and uniformity of the dry cathode active material layer. It is preferable.
- a positive electrode containing a positive electrode active material and, if necessary, a conductive additive, a binder, and an organic acid compound can be obtained, for example, as follows. That is, first, a conductive additive and an organic acid compound are added to the positive electrode active material and mixed uniformly in a dry state, and then a binder is added and dispersed in a solvent to prepare a positive electrode mixture-containing slurry. To do.
- the solid content concentration in the positive electrode mixture-containing slurry is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
- this positive electrode mixture-containing slurry is applied to a positive electrode current collector and dried to form a coating layer.
- the positive electrode active material layer is formed by compressing the coating layer obtained after drying with a roll press or the like.
- the thickness of the positive electrode active material layer after compression is preferably 10 to 300 ⁇ m, more preferably 20 to 280 ⁇ m, and still more preferably 30 to 250 ⁇ m.
- the thickness of the positive electrode active material layer after compression is preferably 50 to 300 ⁇ m, more preferably 60 to 280 ⁇ m, and more preferably 80 to More preferably, it is 250 ⁇ m.
- the basis weight of the positive electrode active material layer included in the positive electrode is adjusted to a range of 8 to 100 mg / cm 2 .
- the basis weight is preferably 9 to 50 mg / cm 2 , more preferably 10 to 26 mg / cm 2 , but the output performance of the non-aqueous secondary battery From the viewpoint of improving the volume energy density while maintaining balance, the basis weight is preferably 24 to 100 mg / cm 2 , more preferably 25 to 80 mg / cm 2 , and 26 to 60 mg / cm 2 . More preferably.
- the non-aqueous secondary battery in the present embodiment uses an electrolytic solution having an ionic conductivity of 15 mS / cm or more, even when an electrode active material layer having a high volume energy density is designed, the non-aqueous secondary battery that realizes high output performance A secondary battery can be provided.
- the basis weight indicates the mass of the electrode active material contained per 1 cm 2 of the electrode area, and the electrode active material layer is formed on both sides of the current collector. Is formed, the mass of the electrode active material contained per 1 cm 2 of electrode area on each side is shown.
- the amount of the electrode active material per unit volume of the battery is relatively greater than other battery materials not related to the battery capacity, such as current collector foils and separators. The capacity of the battery will be increased.
- the basis weight when the electrode active material layer is formed on one surface of the current collector can be calculated by the following equation (12).
- Weight per unit area [mg / cm 2 ] (electrode mass [mg] ⁇ electrode current collector mass [mg]) ⁇ electrode area [cm 2 ] (12)
- the basis weight of the electrode active material layer is determined by a doctor blade method when an electrode mixture-containing slurry obtained by dispersing an electrode mixture in which an electrode active material, a binder and a conductive additive are mixed in a solvent is applied to a current collector.
- it can be adjusted by controlling the coating thickness of the active material layer.
- it can adjust also by controlling the density
- the porosity of the positive electrode active material layer in the present embodiment is not particularly limited. However, in the non-aqueous secondary battery, it is 20 to 45% from the viewpoint of improving the volume energy density while maintaining a balance with the output performance. Preferably, it is 22 to 42%, more preferably 25 to 35%. When the porosity is 20% or more, the diffusion of lithium ions in the positive electrode active material layer is hardly inhibited, and the output characteristics tend to be secured. In addition, when the porosity of the positive electrode active material layer is 45% or less, it is possible to suppress the peeling deterioration of the positive electrode active material layer and the drainage of the non-aqueous electrolyte, and to ensure durability while achieving high output. Tend to be able to.
- the porosity of the electrode active material layer can be obtained by the following formula (13).
- Porosity [%] (1 ⁇ Actual electrode density [g / cm 3 ] / Theoretical electrode density [g / cm 3 ]) ⁇ 100 (13)
- the actual electrode density can be determined by dividing the electrode active material layer mass by the electrode active material layer volume.
- the electrode active material layer mass is a value calculated by subtracting the mass of the electrode current collector from the mass of the electrode punched out with a punch, and the electrode active material layer volume is This is a value calculated by multiplying the area of the electrode active material layer thickness obtained by subtracting the thickness of the electrode current collector from the electrode thickness measured with a micrometer.
- the theoretical electrode density can be determined by adding and multiplying the density and composition ratio of each material constituting the electrode, such as an electrode active material, a conductive additive, and a binder.
- the particle density is a value obtained by dividing the mass of the particle by the volume of the particle including the closed cavity inside the particle, and does not include the dent, crack or open cavity on the particle surface.
- the porosity of the electrode active material layer can be adjusted, for example, by controlling the bulk density of the electrode active material or compressing the electrode.
- the compression of the electrode is performed by a compression means such as a roll press, and the pressing pressure is not particularly limited, but is preferably 2 to 8 MPa, more preferably 4 to 7 MPa. Since an electrode active material layer having a low porosity can be obtained by pressing the electrode at a high pressure, it is preferable from the viewpoint of increasing the battery capacity. Moreover, since the binding force of the electrode active material layer is increased, it is also preferable from the viewpoint of suppressing electrode deterioration when a non-aqueous electrolyte having high ionic conductivity is used.
- Examples of the conductive aid include carbon black typified by graphite, acetylene black and ketjen black, and carbon fiber.
- the number average particle size (primary particle size) of the conductive assistant is preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 1 ⁇ m, and is measured by the same method as the number average particle size of the positive electrode active material.
- Examples of the binder include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, styrene butadiene rubber, and fluorine rubber.
- the solvent is not particularly limited, and a conventionally known solvent can be used. Examples thereof include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and water.
- the positive electrode current collector is made of a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil. Moreover, the carbon coat may be given or it may be processed into the mesh form.
- the thickness of the positive electrode current collector is preferably 5 to 40 ⁇ m, more preferably 7 to 35 ⁇ m, and still more preferably 9 to 30 ⁇ m.
- a negative electrode will not be specifically limited if it acts as a negative electrode of a non-aqueous secondary battery, A well-known thing may be used.
- the negative electrode preferably contains at least one material selected from the group consisting of a material capable of inserting and extracting lithium ions as a negative electrode active material and metallic lithium.
- metallic lithium examples of such materials include amorphous carbon (hard carbon), artificial graphite, natural graphite, pyrolytic carbon, coke, glassy carbon, fired bodies of organic polymer compounds, mesocarbon microbeads, carbon Examples thereof include carbon materials represented by fiber, activated carbon, graphite, carbon colloid, and carbon black.
- coke examples include pitch coke, needle coke, and petroleum coke.
- the fired body of an organic polymer compound is obtained by firing and polymerizing a polymer material such as phenol resin or furan resin at an appropriate temperature.
- the carbon material may contain different elements or compounds such as O, B, P, N, S, Si, SiC, SiO, SiO 2 , and B 4 C.
- the content of the different element or the different compound is preferably 0 to 10% by mass with respect to the carbon material.
- examples of materials capable of inserting and extracting lithium ions include materials containing elements capable of forming an alloy with lithium. This material may be a single metal or a semi-metal, an alloy or a compound, and may have at least a part of one or more of these phases. Good.
- alloy in addition to what consists of 2 or more types of metal elements, what has 1 or more types of metal elements and 1 or more types of metalloid elements is contained in "alloy".
- the alloy may have a nonmetallic element as long as it has metal properties as a whole.
- metal elements and metalloid elements capable of forming an alloy with lithium include titanium (Ti), tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si), and zinc ( Zn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr) and yttrium (Y). .
- the metal elements and metalloid elements of Group 4 or Group 14 in the long-period periodic table are preferable, and particularly preferable is titanium or silicon that has a large ability to occlude and release lithium and can obtain a high energy density. And tin.
- tin for example, as a second constituent element other than tin, silicon, magnesium (Mg), nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium, bismuth, Examples thereof include those having one or more elements selected from the group consisting of antimony and chromium (Cr).
- silicon alloy examples include, as the second constituent element other than silicon, tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium. Those having one or more elements selected from the above are listed.
- titanium compound examples include those having oxygen (O) or carbon (C).
- tin compound examples include those having oxygen (O) or carbon (C).
- C carbon
- the compound having the second constituent element described above is used. You may do it.
- the negative electrode has a negative active material of 0.4 to 3 V vs.
- metal compounds include metal oxides, metal sulfides, and metal nitrides.
- the metal oxide examples include titanium oxide, lithium titanium oxide (lithium titanium-containing composite oxide), tungsten oxide (for example, WO 3 ), and amorphous tin oxide (for example, SnB 0.4 P 0.6 O 3). .1), tin silicon oxide (e.g., SnSiO 3) and silicon oxide (SiO) and the like. Among these, titanium oxide and lithium titanium oxide are preferable.
- lithium titanium oxide examples include spinel lithium titanate ⁇ for example, Li 4 + c Ti 5 O 12 (c can be changed within a range of ⁇ 1 ⁇ c ⁇ 3 by charge / discharge reaction) ⁇ , titanium having a ramsdellite structure Lithium acid ⁇ for example, Li 2 + d Ti 3 O 7 (d can be changed within the range of ⁇ 1 ⁇ d ⁇ 3 by charge / discharge reaction) ⁇ .
- titanium oxide any one containing or not containing Li before charging / discharging can be used.
- titanium oxides that do not contain Li before charge / discharge, that is, synthesis include, for example, titanium oxide (eg, TiO 2 , H 2 Ti 12 O 25 ), Ti and P, V, Sn, Cu, Ni, and Fe.
- titanium composite oxide examples include TiO 2 —P 2 O 5 , TiO 2 —V 2 O 5 , TiO 2 —P 2 O 5 —SnO 2 , TiO 2 —P 2 O 5 —MeO (Me is Cu, At least one element selected from the group consisting of Ni and Fe).
- the titanium composite oxide preferably has a low crystallinity and has a microstructure in which the crystal phase and the amorphous phase coexist or exist alone. By having such a microstructure, cycle performance can be greatly improved.
- Examples of the titanium oxide containing Li before charge / discharge that is, the titanium oxide containing Li from the time of synthesis include Li e TiO 2 (e is 0 ⁇ e ⁇ 1.1).
- metal sulfide examples include titanium sulfide (for example, TiS 2 ), molybdenum sulfide (for example, MoS 2 ), and iron sulfide (for example, FeS, FeS 2 , Li f FeS 2 (f is 0 ⁇ f ⁇ 1)). It is done.
- metal nitride examples include lithium cobalt nitride (for example, Li g Co h N, 0 ⁇ g ⁇ 4, 0 ⁇ h ⁇ 0.5).
- the negative electrode uses 0.4 V vs. lithium ion as the negative electrode active material. It is preferable to contain a material that occludes at a lower potential than Li / Li + .
- Examples of such materials include amorphous carbon (hard carbon), artificial graphite, natural graphite, graphite, pyrolytic carbon, coke, glassy carbon, a fired body of an organic polymer compound, mesocarbon microbeads, carbon fiber,
- amorphous carbon hard carbon
- artificial graphite natural graphite, graphite, pyrolytic carbon, coke, glassy carbon
- a fired body of an organic polymer compound mesocarbon microbeads, carbon fiber
- mesocarbon microbeads carbon fiber
- carbon materials represented by activated carbon, graphite, carbon colloid and carbon black metallic lithium, metal oxide, metal nitride, lithium alloy, tin alloy, silicon alloy, intermetallic compound, organic compound, inorganic compound, metal complex And organic polymer compounds.
- the negative electrode active material may be used alone or in combination of two or more.
- the number average particle diameter (primary particle diameter) of the negative electrode active material is preferably 0.1 to 100 ⁇ m, more preferably 1 to 10 ⁇ m.
- the number average particle size of the negative electrode active material is measured by the same method as the number average particle size of the positive electrode active material.
- the negative electrode is obtained, for example, as follows. That is, first, a negative electrode mixture-containing slurry is prepared by dispersing, in a solvent, a negative electrode mixture prepared by adding a conductive additive or a binder to the negative electrode active material as necessary.
- the solid content concentration in the negative electrode mixture-containing slurry is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass.
- this negative electrode mixture-containing slurry is applied to the negative electrode current collector and dried to form a coating layer.
- the negative electrode active material layer is formed by compressing the coating layer obtained after drying with a roll press or the like.
- the thickness of the negative electrode active material layer after compression is preferably 10 to 300 ⁇ m, more preferably 20 to 280 ⁇ m, and still more preferably 30 to 250 ⁇ m.
- the basis weight of the negative electrode active material layer included in the negative electrode is adjusted to be in the range of 3 to 46 mg / cm 2 .
- the basis weight is preferably 4 to 23 mg / cm 2 , more preferably 5 to 12 mg / cm 2 , but the output performance of the non-aqueous secondary battery From the viewpoint of improving the volume energy density while maintaining a balance, the basis weight is preferably 10 to 46 mg / cm 2 , more preferably 11 to 37 mg / cm 2 , and 12 to 27 mg / cm 2 . More preferably.
- the non-aqueous secondary battery in the present embodiment uses an electrolytic solution having an ionic conductivity of 15 mS / cm or more, even when an electrode active material layer having a high volume energy density is designed, the non-aqueous secondary battery that realizes high output performance A secondary battery can be provided.
- the porosity of the negative electrode active material layer in the present embodiment is not particularly limited, but from the viewpoint of improving the volume energy density while maintaining a balance with the output performance in the nonaqueous secondary battery in the present embodiment, 20 to It is preferably 45%, more preferably 22 to 42%, still more preferably 25 to 35%.
- the porosity is 20% or more, the diffusion of lithium ions in the negative electrode active material layer is hardly inhibited, and the output characteristics tend to be secured.
- the porosity of the negative electrode active material layer is 45% or less, the negative electrode active material layer can be prevented from degrading and the non-aqueous electrolyte from draining, and the durability can be ensured while realizing high output. Tend to be able to.
- Examples of the conductive aid include carbon black typified by graphite, acetylene black and ketjen black, and carbon fiber.
- the number average particle size (primary particle size) of the conductive assistant is preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 1 ⁇ m, and is measured by the same method as the number average particle size of the positive electrode active material.
- Examples of the binder include PVDF, PTFE, polyacrylic acid, styrene butadiene rubber, and fluorine rubber.
- the solvent is not particularly limited, and a conventionally known solvent can be used, and examples thereof include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, water and the like.
- the negative electrode current collector is made of a metal foil such as a copper foil, a nickel foil, or a stainless steel foil. Moreover, the carbon coat may be given or it may be processed into the mesh form.
- the thickness of the negative electrode current collector is preferably 5 to 40 ⁇ m, more preferably 6 to 35 ⁇ m, and even more preferably 7 to 30 ⁇ m.
- the positive electrode and the negative electrode included in the non-aqueous secondary battery in this embodiment are electrodes in which a conductive layer containing a conductive material is applied on an electrode current collector, and a positive electrode active material layer or a negative electrode active material layer is formed thereon. It is also one of the preferable embodiments.
- the presence of the conductive layer on the electrode current collector can maintain high conductivity, and the adhesive strength between the active material layer and the current collector can be increased, so that the electrode has high strength while maintaining high output performance and high performance.
- a non-aqueous secondary battery having durability can be manufactured.
- the conductive layer is prepared by preparing a conductive mixture-containing slurry by dispersing a conductive mixture mixed with a conductive material and a binder in a solvent, and then applying this conductive mixture-containing slurry to the positive electrode and the negative electrode current collector. And after drying and forming a conductive mixture layer, it can produce by pressing it as needed and adjusting thickness.
- the conductive material contained in the conductive layer is not particularly limited as long as it has conductivity.
- the carbonaceous material such as activated carbon, non-graphitizable carbon and graphitizable carbon, and amorphous carbon such as polyacene-based material.
- examples thereof include carbon blacks such as ketjen black and acetylene black, carbon nanotubes, fullerenes, carbon nanophones, and fibrous carbonaceous materials.
- graphite and acetylene black can be suitably used from the viewpoints of high conductivity and ease of forming a conductive layer.
- the number average particle diameter of the conductive material is preferably 20 nm to 1 ⁇ m, and more preferably 20 to 500 nm.
- the number average particle diameter of the conductive material can be measured by the same method as the number average particle diameter of the positive electrode active material.
- resins include alkane polymers such as polyethylene, polypropylene, poly-1,1-dimethylethylene; unsaturated polymers such as polybutadiene and polyisoprene; polystyrene, polymethylstyrene, polyvinylpyridine, poly-N.
- -Polymers having a ring such as vinylpyrrolidone; acrylic derivatives such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide Polymers: Fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethylene; CN group-containing polymers such as polyacrylonitrile and polyvinylidene cyanide; polyvinyl acetate, polyvinyl alcohol Polyvinyl alcohol polymers such as; polyvinyl chloride, halogen-containing polymers such as polyvinylidene chloride; a conductive polymer such as polyaniline. Moreover, mixtures, modified bodies, derivatives, random copolymers, alternating copolymers, graft copolymers, block copolymers, and the like of the above polymers can also be used
- the solid content concentration in the conductive mixture slurry comprising the conductive material, the binder and the solvent is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
- the thickness of the conductive layer is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 10 ⁇ m.
- the thickness of the conductive layer is 0.05 ⁇ m or more, the resistance between the electrode active material layer and the electrode current collector tends to decrease, and when the thickness is 10 ⁇ m or less, the energy density as the power storage element decreases little. Tend to be.
- the resistance between the electrode active material layer and the electrode current collector is suppressed, and further the adhesion between the electrode active material layer and the electrode current collector is increased. Can do.
- the nonaqueous secondary battery in the present embodiment preferably includes a separator between the positive electrode and the negative electrode from the viewpoint of providing safety such as prevention of short circuit between the positive and negative electrodes and shutdown.
- a separator the same separator as that used in known nonaqueous secondary batteries may be used, and an insulating thin film having high ion permeability and excellent mechanical strength is preferable.
- the separator include a woven fabric, a nonwoven fabric, and a synthetic resin microporous membrane. Among these, a synthetic resin microporous membrane is preferable.
- the synthetic resin microporous membrane for example, a microporous membrane containing polyethylene or polypropylene as a main component or a polyolefin microporous membrane such as a microporous membrane containing both of these polyolefins is suitably used.
- the non-woven fabric include porous films made of heat resistant resin such as ceramic, polyolefin, polyester, polyamide, liquid crystal polyester, and aramid.
- the separator may be a single microporous membrane or a laminate of a plurality of microporous membranes, or a laminate of two or more microporous membranes.
- the battery exterior of the non-aqueous secondary battery in the present embodiment is not particularly limited, any battery exterior of a battery can and a laminate film exterior body can be used.
- the battery can for example, a metal can made of steel or aluminum can be used.
- a laminate film outer package for example, two laminated films of a three-layer structure of hot melt resin / metal film / resin are stacked with the hot melt resin side facing inward, and the ends are sealed by heat sealing. What stopped can be used.
- a positive electrode terminal (or a lead tab connected to the positive electrode terminal) and a negative electrode terminal (or a lead tab connected to the negative electrode terminal) are connected to the positive electrode current collector and the negative electrode current collector, respectively.
- the laminate film exterior body may be sealed with the end of the (or lead tab) being pulled out of the exterior body.
- the non-aqueous secondary battery in the present embodiment uses the above-described electrolytic solution, a positive electrode body composed of a positive electrode and a positive electrode current collector, a negative electrode body composed of a negative electrode and a negative electrode current collector, and a separator as necessary. It is produced by a known method. For example, a long positive electrode body and a negative electrode body can be wound in a stacked state in which a long separator is interposed therebetween to form a wound structure. Moreover, they are cut into a plurality of sheets having a certain area and shape, and formed into a laminate having a laminated structure in which separator sheets are interposed between a plurality of positive electrode sheets and a negative electrode sheet that are alternately laminated. can do. Further, a long separator can be folded in a zigzag manner, and a positive electrode sheet and a negative electrode sheet can be alternately inserted between the zippered separators to form a laminate having a laminated structure.
- the laminate is accommodated in a battery case (battery exterior), the electrolytic solution according to the present embodiment is injected into the battery case, and the laminate is immersed in the electrolytic solution and sealed.
- the non-aqueous secondary battery in the embodiment can be produced.
- a gel electrolyte membrane is prepared in advance, and using a sheet-like positive electrode body, a negative electrode body, the electrolyte membrane, and a separator as necessary, After forming a laminated body having a laminated structure as described above, it can be housed in a battery case to produce a non-aqueous secondary battery.
- the shape of the non-aqueous secondary battery in the present embodiment is not particularly limited, and for example, a cylindrical shape, an elliptical shape, a rectangular tube shape, a button shape, a coin shape, a flat shape, and a laminate shape are suitably employed.
- the non-aqueous secondary battery in the present embodiment can function as a battery by the first charge, but is stabilized when a part of the non-aqueous electrolyte is decomposed during the first charge.
- the initial charge is preferably performed at 0.001 to 0.3C, more preferably 0.002 to 0.25C, and 0.003 to 0.2C. More preferably, it is also preferable that the initial charging is performed via the constant voltage charging in the middle. In addition, the constant current which discharges rated capacity in 1 hour is 1C.
- the electrochemical property of the lithium salt dissolved in the electrolyte It is very effective to perform the first charge in consideration of the reaction.
- the non-aqueous secondary battery in the present embodiment can be used as a battery pack by connecting a plurality of non-aqueous secondary batteries in series or in parallel.
- the voltage range used per battery is preferably 2 to 5 V, more preferably 2.5 to 5 V, and 2.75 V to 5 V. It is particularly preferred.
- CT-57101B (trade name) manufactured by Toa DKK Co., Ltd., connected to the non-aqueous electrolyte solution is inserted into the container containing the non-aqueous electrolyte solution, and the non-aqueous electrolyte solution at 25 ° C. The ionic conductivity of was measured.
- Porosity measurement of electrode active material layer The porosity of the electrode active material layer was determined by the following formula (13).
- Porosity [%] (1 ⁇ Actual electrode density [g / cm 3 ] / Theoretical electrode density [g / cm 3 ]) ⁇ 100 (13)
- the actual electrode density was determined by dividing the electrode active material layer mass by the electrode active material layer volume.
- the electrode active material layer mass was calculated by subtracting the mass of the electrode current collector separately punched with the same area from the mass of the electrode punched with a punching punch so that the area was 2 cm 2.
- the layer volume was calculated by multiplying the electrode active material layer thickness obtained by subtracting the thickness of the electrode current collector measured separately from the thickness of the electrode measured with a micrometer by the area.
- the theoretical electrode density was determined by adding the density and the composition ratio of the electrode active material, the conductive additive and the binder constituting the electrode.
- Thickness of the electrode active material layer was determined by subtracting the thickness of the electrode current collector measured separately from the thickness of the electrode measured with a micrometer.
- the positive electrode was produced as follows. (2-1) Production of Positive Electrode (P1) Lithium cobaltate (LiCoO 2 ; density 4.95 g / cm 3 ) having a number average particle diameter of 7.4 ⁇ m as a positive electrode active material and a number average particle diameter of 48 nm as a conductive assistant Acetylene black (density 1.95 g / cm 3 ) and polyvinylidene fluoride (PVdF; density 1.75 g / cm 3 ) as a binder were mixed at a mass ratio of 89.3: 5.2: 5.5, A positive electrode mixture was obtained.
- P1 Lithium cobaltate (LiCoO 2 ; density 4.95 g / cm 3 ) having a number average particle diameter of 7.4 ⁇ m as a positive electrode active material and a number average particle diameter of 48 nm as a conductive assistant
- N-methyl-2-pyrrolidone as a solvent was added to the obtained positive electrode mixture so as to have a solid content of 68% by mass and further mixed to prepare a positive electrode mixture-containing slurry.
- This positive electrode mixture-containing slurry was applied to one surface of an aluminum foil having a thickness of 20 ⁇ m and a width of 200 mm to be a positive electrode current collector by a doctor blade method while adjusting the basis weight to 6.1 mg / cm 2. Removed dry. Then, it rolled by the roll press so that an actual electrode density might be 2.77 g / cm ⁇ 3 >, and the positive electrode (P1) which consists of a positive electrode active material layer and a positive electrode electrical power collector was obtained. The theoretical electrode density was calculated to be 4.62 g / cm 3 . Table 1 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- the positive electrode mixture-containing slurry was applied by a doctor blade method while adjusting the basis weight to 10.0 mg / cm 2 , and the actual electrode density was adjusted to 2.50 g /
- a positive electrode (P5) was obtained in the same manner as in (2-1) except that the film was rolled to cm 3 .
- Table 1 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- N-methyl-2-pyrrolidone as a solvent was added to the obtained positive electrode mixture so as to have a solid content of 68% by mass and further mixed to prepare a positive electrode mixture-containing slurry.
- the positive electrode mixture-containing slurry was applied to one surface of an aluminum foil having a thickness of 20 ⁇ m and a width of 200 mm to be a positive electrode current collector by a doctor blade method while adjusting the basis weight to 12.0 mg / cm 2. Was removed by drying. Then, it rolled by the roll press so that an actual electrode density might be 3.24 g / cm ⁇ 3 >, and the positive electrode (P8) which consists of a positive electrode active material layer and a positive electrode electrical power collector was obtained. The theoretical electrode density was calculated to be 4.44 g / cm 3 . Table 2 shows the basis weight, the electrode active material layer thickness, the actual electrode density, and the porosity.
- a positive electrode (P11) was obtained in the same manner as (2-8) except that it was not rolled by a roll press.
- Table 2 shows the basis weight, the electrode active material layer thickness, the actual electrode density, and the porosity.
- the positive electrode mixture-containing slurry was applied by the doctor blade method while adjusting the basis weight to be 12.0 mg / cm 2 , and the actual electrode density was 3.02 g /
- a positive electrode (P12) was obtained in the same manner as (2-8) except that the film was rolled to cm 3 .
- Table 2 shows the basis weight, the electrode active material layer thickness, the actual electrode density, and the porosity.
- the mixture is uniformly in a dry state.
- a binder and N-methyl-2-pyrrolidone as a solvent were added so as to have a solid content of 68% by mass, and further mixed to prepare a positive electrode mixture-containing slurry.
- the positive electrode mixture-containing slurry was applied to one surface of an aluminum foil having a thickness of 20 ⁇ m and a width of 200 mm to be a positive electrode current collector by a doctor blade method while adjusting the basis weight to be 24.9 mg / cm 2. Was removed by drying.
- N-methyl-2-pyrrolidone as a solvent was added to the obtained positive electrode mixture so as to have a solid content of 70% by mass and further mixed to prepare a positive electrode mixture-containing slurry.
- the positive electrode mixture-containing slurry was applied by the doctor blade method while adjusting the basis weight to be 48.2 mg / cm 2 , and the roll press was adjusted to roll the actual electrode density to 2.47 g / cm 3 .
- a positive electrode (P20) was obtained in the same manner as (2-8).
- Table 3 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- Negative electrode production The negative electrode was produced as follows. (3-1) Production of Negative Electrode (N1) Graphite carbon powder having a number average particle size of 25 ⁇ m (trade name “MCMB25-28”, manufactured by Osaka Gas Chemical Co., Ltd .; density 2.25 g / cm 3 ) as a negative electrode active material Acetylene black (density 1.95 g / cm 3 ) having a number average particle diameter of 48 nm as a conductive assistant and polyvinylidene fluoride (PVdF; density 1.75 g / cm 3 ) as a binder, 93.0: 2.0 : It mixed by the mass ratio of 5.0, and obtained the negative mix.
- N1 Negative Electrode
- MCMB25-28 manufactured by Osaka Gas Chemical Co., Ltd .
- density 2.25 g / cm 3 a negative electrode active material
- Acetylene black density 1.95 g / cm 3
- PVdF polyvinylidene flu
- N-methyl-2-pyrrolidone as a solvent was added to the obtained negative electrode mixture so as to have a solid content of 45% by mass and further mixed to prepare a negative electrode mixture-containing slurry.
- the negative electrode mixture-containing slurry was applied to one side of a copper foil having a thickness of 18 ⁇ m and a width of 200 mm to be a negative electrode current collector by a doctor blade method while adjusting the basis weight to 2.3 mg / cm 2. Removed dry. Then, it rolled by the roll press so that an actual electrode density might be 1.15 g / cm ⁇ 3 >, and the negative electrode (N1) which consists of a negative electrode active material layer and a negative electrode collector was obtained. The theoretical electrode density was calculated to be 2.22 g / cm 3 . Table 4 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- Negative Electrode (N2) The negative electrode mixture-containing slurry was applied by the doctor blade method while adjusting the basis weight to 4.1 mg / cm 2 , and the actual electrode density was adjusted by adjusting the roll press. A negative electrode (N2) was obtained in the same manner as (3-1) except that rolling was performed to 1.41 g / cm 3 .
- Table 4 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- N-methyl-2-pyrrolidone as a solvent was added to the obtained negative electrode mixture so as to have a solid content of 45% by mass and further mixed to prepare a negative electrode mixture-containing slurry.
- the negative electrode mixture-containing slurry was applied to one side of a copper foil having a thickness of 18 ⁇ m and a width of 200 mm to be a negative electrode current collector by a doctor blade method while adjusting the basis weight to be 29.4 mg / cm 2. Removed dry. Then, it rolled so that an actual electrode density might be 1.86 g / cm ⁇ 3 > with a roll press, and the negative electrode (N6) which consists of a negative electrode active material layer and a negative electrode collector was obtained. The theoretical electrode density was calculated to be 3.04 g / cm 3 . Table 4 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- a negative electrode mixture was obtained. Water was added to the obtained negative electrode mixture as a solvent so as to have a solid content of 45% by mass, and further mixed to prepare a negative electrode mixture-containing slurry.
- the negative electrode mixture-containing slurry was applied to one side of a copper foil having a thickness of 10 ⁇ m and a width of 200 mm to be a negative electrode current collector by a doctor blade method while adjusting the basis weight to 5.5 mg / cm 2. Removed dry. Then, it rolled by the roll press so that an actual electrode density might be 1.62 g / cm ⁇ 3 >, and the negative electrode (N7) which consists of a negative electrode active material layer and a negative electrode collector was obtained. The theoretical electrode density was calculated to be 2.20 g / cm 3 . Table 5 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- Negative Electrode (N12) The negative electrode mixture-containing slurry was applied by a doctor blade method while adjusting the basis weight to 10.0 mg / cm 2 , and the actual electrode density was adjusted by adjusting the roll press. A negative electrode (N12) was obtained in the same manner as (3-7) except that rolling was performed to 1.35 g / cm 3 .
- Table 5 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- a negative electrode mixture was obtained. Water was added to the obtained negative electrode mixture as a solvent so as to have a solid content of 48% by mass, and further mixed to prepare a negative electrode mixture-containing slurry.
- the negative electrode mixture-containing slurry was applied by a doctor blade method while adjusting the basis weight to be 21.4 mg / cm 2 , and the roll press was adjusted to roll the actual electrode density to 1.24 g / cm 3 .
- a negative electrode (N14) was obtained in the same manner as (3-7) except that. Table 5 shows the basis weight, electrode active material layer thickness, actual electrode density, and porosity.
- VC vinylene carbonate
- FEC 4-fluoro-1,3-dioxolan-2-one
- ES ethylene sulfite
- 1,3-PS 1,3 Propane sultone
- TMSO tetramethylene sulfoxide
- SL is sulfolane
- 3-SLE 3-sulfolene
- LiPF 6 lithium hexafluorophosphate
- LiBF 4 is lithium tetrafluoroborate
- LiBOB represents lithium bisoxalate borate.
- the battery cap was fitted and crimped with a caulking machine.
- the overflowing electrolyte was wiped clean with a waste cloth. It was kept at 25 ° C. for 24 hours, and the laminate was sufficiently adjusted with the electrolyte solution to obtain a coin-type non-aqueous secondary battery.
- a negative electrode (N6) other than the negative electrode (N6) means a current value that is expected to be discharged from a fully charged state of 4.2 V to 3.0 V at a constant current and finished in one hour.
- Table 9 shows current values corresponding to 1 C for the positive electrodes (P1) to (P20).
- the discharge capacity at this time was set to 3C discharge capacity.
- charging was performed with a constant voltage of 4.2 V for a total of 3 hours. Thereafter, the battery was discharged to 3.0 V with a constant current corresponding to 5C.
- the discharge capacity at this time was set to 5C discharge capacity.
- charging was performed with a constant voltage of 4.2 V for a total of 3 hours. Thereafter, the battery was discharged to 3.0 V at a constant current corresponding to 10C.
- the discharge capacity at this time was 10 C discharge capacity.
- the discharge capacity of (6-1) is 0.3C discharge capacity and the 0.3C discharge capacity is 100%
- the 1C, 3C, 5C, or 10C discharge capacity is 40% or more, respectively. % And less than 40% were judged as ⁇ , and less than 20% were judged as x.
- the discharge capacity at this time was set to 3C discharge capacity.
- charging was performed with a constant voltage of 2.7 V for a total of 3 hours. Thereafter, the battery was discharged to 1.5 V with a constant current corresponding to 5C.
- the discharge capacity at this time was set to 5C discharge capacity.
- charging was performed with a constant voltage of 2.7 V for a total of 3 hours. Thereafter, the battery was discharged to 1.5 V with a constant current corresponding to 10 C.
- the discharge capacity at this time was 10 C discharge capacity.
- the discharge capacity of (6-3) is 0.3C discharge capacity and the 0.3C discharge capacity is 100%
- the 1C, 3C, 5C, or 10C discharge capacity is 40% or more. % And less than 40% were judged as ⁇ , and less than 20% were judged as x.
- AC impedance measurement of small non-aqueous secondary batteries (AC resistance measurement 1)
- the AC impedance was measured using a frequency response analyzer 1400 (trade name) manufactured by Solartron and a potentio-galvanostat 1470E (trade name) manufactured by Solartron.
- the non-aqueous secondary battery to be measured is repeatedly charged and discharged as described in (6-10) above, and the battery after the first charge / discharge treatment and after 25 cycles and 100 cycles is subjected to a constant current corresponding to 1C. After charging and reaching 4.0V, the battery was charged at 4.0V for a total of 3 hours.
- the measurement conditions were an amplitude of ⁇ 5 mV and a frequency of 0.1 to 20 kHz. AC impedance values at 0.1 kHz and 20 kHz were obtained.
- the ambient temperature of the battery when measuring AC impedance was 25 ° C.
- the battery was charged with a constant current corresponding to 1 C and reached 4.2 V, and then charged with 4.2 V for a total of 3 hours, and discharged to 3.0 V with a constant current corresponding to 0.3 C.
- the discharge capacity at this time was 0.3 C recovery capacity.
- the battery was charged with a constant current corresponding to 1 C and reached 4.2 V, and then charged with 4.2 V for a total of 3 hours, and discharged to 3.0 V with a constant current corresponding to 1.5 C.
- the discharge capacity at this time was 1.5 C recovery capacity.
- Examples 1 to 10, Comparative Examples 1 to 7 The method according to (5-1) above, wherein the positive electrodes (P1) to (P5), (P20), the negative electrodes (N1) to (N4), (N14), and the electrolytes (S1) to (S4) are combined.
- a small non-aqueous secondary battery was produced according to the above. These batteries were first charged and discharged by the method described in (6-1) above, and the measurements described in (6-5) above were performed. The results are shown in Table 10.
- the non-aqueous secondary battery of the present embodiment shows a high discharge capacity compared to the conventional non-aqueous secondary battery even when an electrode with a high basis weight is used at a high output. .
- Examples 11 to 18, Comparative Example 8 A combination of the positive electrodes (P8) to (P12), the negative electrodes (N7) to (N10), and the electrolytes (S1) and (S5) to (S7), and a small non-aqueous system according to the method described in (5-1) above A secondary battery was produced. These batteries were subjected to initial charge / discharge treatment by the method described in (6-1) above, and the measurements described in (6-6) above were performed. The results are shown in Table 11.
- the non-aqueous secondary battery of this embodiment has high output characteristics.
- the comparative example 8 since the existing carbonate type electrolyte solution was used, sufficient output characteristics were not obtained.
- Example 17 although the electrolyte solution (S7) having high ionic conductivity was used, the discharge capacity retention rate during 10C discharge was less than 65%. Although it is sufficient as practical performance, it is presumed that an electrode having an originally insufficient electrode active material layer binding force was affected by a highly polar solvent because it was not rolled by a roll press.
- Examples 25 to 33 A small non-aqueous secondary battery was fabricated by combining the positive electrode (P13), the negative electrode (N11), and the electrolytes (S28) to (S36) according to the method described in (5-1) above. These batteries were subjected to initial charge / discharge treatment by the method described in (6-1) above, and the measurements described in (6-9) above were performed. The results are shown in Table 13.
- a secondary battery was produced. These batteries were subjected to initial charge / discharge treatment by the method described in (6-1) or (6-2), and the measurements described in (6-9) and (6-10) were performed. The results are shown in Table 14.
- a small non-aqueous secondary battery was produced by combining the positive electrode (P13), the negative electrode (N11), and the electrolytes (S41) and (S42) according to the method described in (5-1) above. These batteries were subjected to the initial charge / discharge treatment according to the method described in (6-2) and the measurement described in (6-9) above, but the discharge capacity retention rate was low, and other measurements were not performed. It was. The results are shown in Table 14.
- Examples 52 to 61, Comparative Example 14 Combining the positive electrodes (P15) to (P20), the negative electrodes (N12) to (N14), and the electrolytes (S1), (S10) to (S12), (S25) to (S27), the above (5-1)
- a small non-aqueous secondary battery was produced according to the method described in 1. These batteries were subjected to the initial charge / discharge treatment by the method described in (6-4) above, and the measurements described in (6-7), (6-11) and (6-13) above were performed. The results are shown in Table 16.
- Example 62 to 65 Comparative Example 15
- a positive electrode (P14), (P19), a negative electrode (N13), and electrolytes (S20) to (S24) were combined to produce a coin-type non-aqueous secondary battery according to the method described in (5-2) above.
- These batteries were subjected to initial charge / discharge treatment by the method described in (6-4) above, and the measurements described in (6-14) above were performed. The results are shown in Table 17.
- the non-aqueous secondary battery of the present invention is, for example, a rechargeable battery for automobiles such as a hybrid vehicle, a plug-in hybrid vehicle, and an electric vehicle, as well as a portable device such as a mobile phone, a portable audio device, a personal computer, and an IC tag Use as a power storage system is also expected.
- SYMBOLS 100 Lithium ion secondary battery, 110 ... Separator, 120 ... Positive electrode active material layer, 130 ... Negative electrode active material layer, 140 ... Positive electrode collector, 150 ... Negative electrode collector, 160 ... Battery exterior.
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Abstract
Description
自動車等の車両及び住宅用蓄電システムに非水系二次電池を搭載する場合、高温環境下におけるサイクル性能及び長期信頼性等の観点から、電池の構成材料には、化学的、電気化学的な安定性、強度、耐腐食性等に優れた材料が求められている。さらに、携帯用電子機器電源とは使用条件が大きく異なり、寒冷地においても作動しなければならないことから、低温環境下における高出力性能及び長寿命性能も必要な物性として求められている。
一方、今後予測される高容量化・高出力化のニーズに応えるためには、材料開発のみだけでなく、各々の材料がその機能を十分に発揮できるよう、電池として最適な状態に組み上げる必要がある。特に、体積エネルギー密度の高い電極活物質層であるほどリチウムイオンの拡散経路が長く、リチウムイオンの挿入・脱離に伴う内部抵抗が増大してしまうため、実用的な出力性能を維持するには、バランスを考えた設計にしなければならない。
一般に、非水系二次電池の高容量化については、電極活物質の性能向上により達成可能であるとされるが、実際には体積エネルギー密度の高い電極活物質層を作製することが最も重要である。例えば、電極集電体に電極合剤を多く塗布すると、電池の単位体積あたりの電極活物質量が電池容量に関係しない他の電池材料、例えば集電箔やセパレータよりも相対的に多くなるため、電池としては高容量化することになる。また、電極を高圧でプレスすると空孔率の低い電極活物質層が得られ、この場合も同様に電池として高容量化が実現する。
充電時間の短縮、大電流での放電、あるいは低温環境下における放電等、非水系二次電池の出力特性を重視する場合には、高容量化を目指す場合とは逆に、リチウムイオンの拡散経路が短くなるように電極活物質層の設計を行う必要がある。具体的には、電極活物質層の目付量を低くする、電極活物質層の空孔率を上げる等の方法が挙げられる。
ところで、出力特性の向上には、イオン伝導度の高い電解液を選択することも有効である。常温作動型のリチウムイオン二次電池の電解液には非水系電解液を使用することが実用性の観点から望ましく、例えば、環状炭酸エステル等の高誘電性溶媒と低級鎖状炭酸エステル等の低粘性溶媒との組み合わせが一般的な溶媒として挙げられる。ところが、通常の高誘電率溶媒は融点が高く、用いる電解質の種類によってはそれらの出力特性、さらには低温特性を劣化させる原因にもなり得る。このような課題を克服する溶媒の1つとして、粘度と比誘電率とのバランスに優れたニトリル系溶媒が提案されている。中でもアセトニトリルは突出した性能を有する溶媒であることが知られているが、ニトリル基を含有するこれらの溶媒は電気化学的に還元分解するといった致命的な欠点があるため、いくつかの改善策が報告されてきた。
例えば、特許文献1においては、エチレンカーボネート等の環状カーボネート類とアセトニトリルなどのニトリル系溶媒とを混合して希釈することにより得られる、還元分解の影響を低減した電解液が報告されている。また、特許文献2~4においては、ニトリル系溶媒の還元電位よりも貴である負極を用いることによって、ニトリル系溶媒の還元分解を抑制した電池が報告されている。さらに、特許文献5においては、負極への保護皮膜形成を目的として、ニトリル系溶媒に、二酸化硫黄と1つ又はそれ以上のその他の非プロトン性極性溶媒を添加した非水系電解液が報告されている。
一方、これらの公知の技術は、共通して、負極におけるニトリル系溶媒の還元分解に焦点が置かれ、幾つかの課題は残しながらも負極の反応さえ解決できれば二次電池として実施可能であると論じている。ところが、例えば、特許文献2及び4に記載の負極を用いた場合、すなわち負極における還元分解が起こり得ない環境で充放電サイクルを繰り返した場合においても、従来のリチウムイオン二次電池と比較して内部抵抗が大きく増加してしまうといった事実については一切触れられていない。このような内部抵抗の増加は負極における還元分解以外にも要因があると考えざるを得ないが、必ずしも電池として最適な状態に組み上げるには至っておらず、高容量化・高出力化の要求に応えるためには、さらなる改良が切望されている。
すなわち、本発明は下記のとおりである。
リチウム塩と非水系溶媒とを含有する電解液と、正極と、負極とを含む非水系二次電池であって、前記正極に含まれる正極活物質層の目付量が8~100mg/cm2、及び/又は、前記負極に含まれる負極活物質層の目付量が3~46mg/cm2であり、かつ、前記電解液の25℃におけるイオン伝導度が15mS/cm以上である非水系二次電池。
[2]
前記電解液の25℃におけるイオン伝導度が50mS/cm以下である、上記[1]記載の非水系二次電池。
[3]
前記正極に含まれる正極活物質層の目付量が24~100mg/cm2、及び/又は、前記負極に含まれる負極活物質層の目付量が10~46mg/cm2である、上記[1]又は[2]記載の非水系二次電池。
[4]
前記正極又は前記負極の少なくとも一方の電極に含まれる電極活物質層の空孔率が20~45%である、上記[1]~[3]のいずれか記載の非水系二次電池。
[5]
前記正極に含まれる正極活物質層の空孔率が20~45%である、上記[1]~[4]のいずれか記載の非水系二次電池。
[6]
前記負極に含まれる負極活物質層の空孔率が20~45%である、上記[1]~[5]のいずれか記載の非水系二次電池。
[7]
前記非水系溶媒はニトリル系溶媒を含む、上記[1]~[6]のいずれか記載の非水系二次電池。
[8]
前記ニトリル系溶媒はアセトニトリルを含む、上記[7]記載の非水系二次電池。
[9]
前記非水系溶媒中のアセトニトリルの含有量が5~97体積%である、上記[8]記載の非水系二次電池。
[10]
前記非水系溶媒中のアセトニトリルの含有量が25~80体積%である、上記[8]記載の非水系二次電池。
[11]
前記電解液は、アセトニトリルと、リチウム塩と、下記一般式(1)で表される化合物からなる群より選ばれる1種以上の化合物とを含有する、上記[8]~[10]のいずれか記載の非水系二次電池。
R1-A-R2 ・・・・・(1)
(式中、R1及びR2は各々独立して、アリール基若しくはハロゲン原子で置換されていてもよいアルキル基、又は、アルキル基若しくはハロゲン原子で置換されていてもよいアリール基を示し、あるいは、R1とR2とは互いに結合してAと共に不飽和結合を有していてもよい環状構造を形成し、Aは下記式(2)~(6)のいずれか一つで表される構造を有する2価の基を示す。)
前記式(1)で表される化合物は、エチレンサルファイト、プロピレンサルファイト、ブチレンサルファイト、ペンテンサルファイト、スルホラン、3-メチルスルホラン、3-スルホレン、1,3-プロパンスルトン、1,4-ブタンスルトン、1,3-プロパンジオール硫酸エステル及びテトラメチレンスルホキシドからなる群より選ばれる1種以上の化合物を含む、上記[11]記載の非水系二次電池。
[13]
前記電解液が、炭素間不飽和二重結合を有する環状カーボネートからなる群より選ばれる1種以上の化合物を更に含有する、上記[11]又は[12]記載の非水系二次電池。
[14]
前記リチウム塩は、フッ素原子を有する無機リチウム塩である、上記[1]~[13]のいずれか記載の非水系二次電池。
[15]
前記無機リチウム塩は、LiPF6である、上記[14]記載の非水系二次電池。
[16]
前記無機リチウム塩は、LiBF4である、上記[14]記載の非水系二次電池。
[17]
前記無機リチウム塩の含有量は、前記電解液の全量に対して0.1~40質量%である、上記[14]~[16]のいずれか記載の非水系二次電池。
[18]
有機リチウム塩を更に含有し、前記有機リチウム塩と前記無機リチウム塩とが、下記式(7):
0≦X<1 ・・・・・(7)
(式中、Xは前記無機リチウム塩に対する前記有機リチウム塩の含有モル比である。)
で表される条件を満足する、上記[14]~[17]のいずれか記載の非水系二次電池。
[19]
前記有機リチウム塩は、リチウムビス(オキサラト)ボレート及びリチウムオキサラトジフルオロボレートからなる群より選ばれる1種以上の有機リチウム塩である、上記[18]記載の非水系二次電池。
[20]
前記正極は、正極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料からなる群より選ばれる1種以上の材料を含有し、前記負極は、負極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料及び金属リチウムからなる群より選ばれる1種以上の材料を含有する、上記[1]~[19]のいずれか記載の非水系二次電池。
[21]
前記正極は、前記正極活物質として、リチウム含有化合物を含有する、上記[20]記載の非水系二次電池。
[22]
前記リチウム含有化合物は、リチウムを有する金属酸化物及びリチウムを有する金属カルコゲン化物からなる群より選ばれる1種以上の化合物を含む、上記[21]記載の非水系二次電池。
[23]
前記負極は、前記負極活物質として、金属リチウム、炭素材料、及びリチウムと合金形成が可能な元素を含む材料からなる群より選ばれる1種以上の材料を含有する、上記[20]~[22]のいずれか記載の非水系二次電池。
[24]
前記負極は、前記負極活物質として、リチウムイオンを1.4Vvs.Li/Li+よりも卑な電位で吸蔵する材料を含有する、上記[20]~[23]のいずれか記載の非水系二次電池。
[25]
前記正極の正極合剤は、正極活物質、導電助剤、バインダー、有機酸、及び有機酸塩からなる群から選択される少なくとも1種の化合物を含む、上記[1]~[24]のいずれか記載の非水系二次電池。
[26]
前記化合物は2価以上の有機酸又は有機酸塩を含む、上記[25]記載の非水系二次電池。
[27]
前記正極合剤から作製した正極活物質層の厚さが50~300μmである、上記[25]又は[26]記載の非水系二次電池。
[28]
前記正極及び/又は負極は、電極集電体上に導電性材料を含む導電層を塗布した電極基板上に、正極活物質層及び/又は負極活物質層を塗布した電極である、上記[1]~[27]のいずれか記載の非水系二次電池。
[29]
前記導電層が、導電性材料とバインダーを含む、上記[28]記載の非水系二次電池。
[30]
上記[1]~[29]のいずれか記載の非水系二次電池の製造方法であって、0.001~0.3Cの初回充電を行う工程を有する、非水系二次電池の製造方法。
[31]
前記初回充電が定電圧充電を途中に経由して行われる、上記[30]記載の非水系二次電池の製造方法。
非水系二次電池としては、例えば、正極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料からなる群より選ばれる1種以上の材料を含有する正極と、負極活物質としてリチウムイオンを吸蔵及び放出することが可能な負極材料及び金属リチウムからなる群より選ばれる1種以上の材料を含有する負極と、を備えるリチウムイオン二次電池が挙げられる。
本実施形態における電解液は、リチウム塩と非水系溶媒とを含有し、25℃におけるイオン伝導度が15mS/cm以上であれば特に限定されず、リチウム塩と非水系溶媒は公知のものであってもよい。体積エネルギー密度の高い電極活物質層を設計した場合においても、高出力性能を発揮できる観点から、25℃におけるイオン伝導度は、20mS/cm以上であることが好ましく、25mS/cm以上であることがより好ましい。電解液の25℃におけるイオン伝導度が15mS/cm以上であると、電極活物質層内でのリチウムイオン伝導が充分に行われるため、大電流での充放電が可能となる。また、25℃におけるイオン伝導度の上限は特に限定されないが、各種電池部材の溶出劣化や剥離劣化等、予期せぬ電池劣化を抑制する観点から、イオン伝導度は50mS/cm以下であることが好ましく、49mS/cm以下であることが好ましく、48mS/cm以下であることがさらに好ましい。ここで、電解液のイオン伝導度は、例えば、非水系溶媒の粘度及び/又は極性を調整することにより、制御することができ、より具体的には、低粘度の非水系溶媒と高極性の非水系溶媒とを混合することにより、電解液のイオン伝導度を高く制御することができる。また、低粘度で、かつ高極性を有する非水系溶媒を用いることによって、電解液のイオン伝導度を高く制御することも可能である。なお、電解液のイオン伝導度は、後述の実施例における「(1-1)非水系電解液のイオン伝導度測定」に記載された方法に準拠して測定することができる。
非水系溶媒としては、他の成分と組み合わせて所定のイオン伝導度が得られるものであれば特に制限はなく、例えば、メタノール及びエタノール等のアルコール類、並びに、非プロトン性溶媒が挙げられ、中でも、非プロトン性極性溶媒が好ましい。
リチウム塩としては、非水系二次電池の電解液に通常用いられているものであれば、他の成分と組み合わせて所定のイオン伝導度が得られるものである限りにおいて特に制限はなく、いずれのものであってもよい。リチウム塩は、本実施形態における非水系電解液中に0.1~3mol/Lの濃度で含有されることが好ましく、0.5~2mol/Lの濃度で含有されることがより好ましい。リチウム塩の濃度が上記範囲内にある場合、電解液の導電率がより高い状態に保たれると同時に、非水系二次電池の充放電効率もより高い状態に保たれる傾向にある。
0≦X<1 ・・・・・(7)
で表される条件を満足することが好ましい。ここで、上記式(7)中、Xは、非水系電解液に含まれる無機リチウム塩に対する有機リチウム塩のモル比を示す。非水系電解液に含まれる有機リチウム塩の無機リチウム塩に対するモル比が上記範囲にある場合、無機リチウム塩の高いイオン伝導性能を優先的に機能させることができる傾向にある。
LiC(SO2R3)(SO2R4)(SO2R5) (8a)
LiN(SO2OR6)(SO2OR7) (8b)
LiN(SO2R8)(SO2OR9) (8c)
ここで、式中、R3、R4、R5、R6、R7、R8、及びR9は、互いに同一であっても異なっていてもよく、炭素数1~8のパーフルオロアルキル基を示す。
本実施形態における電解液には、電極を保護する添加剤が含まれていてもよい。添加剤としては、本発明による課題解決を阻害しないものであれば特に制限はなく、リチウム塩を溶解する溶媒としての役割を担う物質、すなわち上記の非水系溶媒と実質的に重複してもよい。また、添加剤は、本実施形態における非水系電解液及び非水系二次電池の性能向上に寄与する物質であることが好ましいが、電気化学的な反応には直接関与しない物質をも包含し、1種を単独で又は2種以上を組み合わせて用いられる。
R1-A-R2 ・・・・・(1)
ここで、式(1)中、R1及びR2は各々独立して、アリール基若しくはハロゲン原子で置換されていてもよいアルキル基、又は、アルキル基若しくはハロゲン原子で置換されていてもよいアリール基を示し、あるいは、R1とR2とは互いに結合してAと共に不飽和結合を有していてもよい環状構造を形成し、Aは下記式(2)~(6)のいずれか一つで表される構造を有する2価の基を示す。
本実施形態における非水系電解液は、ジニトリル化合物、すなわち分子内にニトリル基を2つ有する化合物を更に含有してもよい。ジニトリル化合物は、電池缶や電極等、金属部分の腐食を低減する効果がある。その要因としては、ジニトリル化合物を用いることにより、腐食の低減された金属部分の表面に腐食を抑制する保護皮膜が形成されるためと考えられる。ただし、要因はこれに限定されない。
NC-(CR10R11)2a-CN ・・・・・(9)
ここで、式(9)中、R10及びR11は各々独立して、水素原子又はアルキル基を示し、aは1~6の整数を示す。アルキル基は、炭素数1~10であることが好ましい。
正極は、非水系二次電池の正極として作用するものであれば特に限定されず、公知のものであってもよい。
正極は、正極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料からなる群より選ばれる1種以上の材料を含有する場合、高電圧及び高エネルギー密度を得ることができる傾向にあるので好ましい。そのような材料としては、例えば、下記一般式(10a)及び(10b)で表されるリチウム含有化合物、並びにトンネル構造及び層状構造の金属酸化物及び金属カルコゲン化物が挙げられる。なお、カルコゲン化物とは、硫化物、セレン化物、及びテルル化物をいう。
LixMO2 (10a)
LiyM2O4 (10b)
ここで、式中、Mは少なくとも1種の遷移金属元素を含む1種以上の金属元素を示し、xは0~1.1の数、yは0~2の数を示す。
LivMID2 (11a)
LiwMIIPO4 (11b)
ここで、式中、Dは酸素またはカルコゲン元素を示し、MI及びMIIはそれぞれ1種以上の遷移金属元素を示し、v及びwの値は電池の充放電状態によって異なるが、通常vは0.05~1.10、wは0.05~1.10の数を示す。
目付量[mg/cm2]=(電極質量[mg]-電極集電体質量[mg])÷電極面積[cm2] ・・・・・(12)
空孔率[%]=(1-実電極密度[g/cm3]/理論電極密度[g/cm3])×100 ・・・・・(13)
実電極密度は、電極活物質層質量を電極活物質層体積で割ることにより求めることができる。ここで、電極活物質層質量とは、打ち抜きポンチ等の打抜機で所定面積を打ち抜いた電極の質量から電極集電体の質量を引いて算出した値であり、電極活物質層体積とは、マイクロメータにより測定した電極の厚さから電極集電体の厚さを引いた電極活物質層厚さに面積をかけて算出した値である。
理論電極密度は、電極活物質、導電助剤およびバインダー等、電極を構成する材料それぞれの密度と組成比率をかけて足し合わせることにより求めることができる。なお、粒子の密度とは、粒子の内部にある閉じた空洞を含む粒子の体積で粒子の質量を割った値であり、粒子表面の凹みや割れ目、開いた空洞は粒子の体積に含めない。
負極は、非水系二次電池の負極として作用するものであれば特に限定されず、公知のものであってもよい。
負極は、負極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料及び金属リチウムからなる群より選ばれる1種以上の材料を含有することが好ましい。そのような材料としては金属リチウムの他、例えば、アモルファスカーボン(ハードカーボン)、人造黒鉛、天然黒鉛、熱分解炭素、コークス、ガラス状炭素、有機高分子化合物の焼成体、メソカーボンマイクロビーズ、炭素繊維、活性炭、グラファイト、炭素コロイド、カーボンブラックに代表される炭素材料が挙げられる。コークスとしては、例えば、ピッチコークス、ニードルコークス及び石油コークスが挙げられる。有機高分子化合物の焼成体とは、フェノール樹脂やフラン樹脂などの高分子材料を適当な温度で焼成して炭素化したものである。炭素材料には、炭素以外にも、O、B、P、N、S、Si、SiC、SiO、SiO2、B4C等の異種元素または異種化合物が含まれていてよい。異種元素または異種化合物の含有量としては、炭素材料に対して0~10質量%であることが好ましい。
本実施形態における非水系二次電池に含まれる正極及び負極は、電極集電体上に導電性材料を含む導電層を塗布し、その上に正極活物質層又は負極活物質層を形成した電極であることも好ましい態様の一つである。
本実施形態における非水系二次電池は、正負極の短絡防止、シャットダウン等の安全性付与の観点から、正極と負極との間にセパレータを備えることが好ましい。セパレータとしては、公知の非水系二次電池に備えられるものと同様のものを用いてもよく、イオン透過性が大きく、機械的強度に優れる絶縁性の薄膜が好ましい。セパレータとしては、例えば、織布、不織布、合成樹脂製微多孔膜が挙げられ、これらの中でも、合成樹脂製微多孔膜が好ましい。合成樹脂製微多孔膜としては、例えば、ポリエチレン又はポリプロピレンを主成分として含有する微多孔膜、あるいは、これらのポリオレフィンを共に含有する微多孔膜等のポリオレフィン系微多孔膜が好適に用いられる。不織布としては、セラミック製、ポリオレフィン製、ポリエステル製、ポリアミド製、液晶ポリエステル製、アラミド製など、耐熱樹脂製の多孔膜が挙げられる。
本実施形態における非水系二次電池の電池外装は特に限定されないが、電池缶及びラミネートフィルム外装体のいずれかの電池外装を用いることができる。電池缶としては、例えば、スチール又はアルミニウムからなる金属缶を用いることができる。ラミネートフィルム外装体としては、例えば、熱溶融樹脂/金属フィルム/樹脂の3層構成からなるラミネートフィルムを、熱溶融樹脂側を内側に向けた状態で2枚重ねて端部をヒートシールにて封止したものを用いることができる。なお、ラミネートフィルム外装体を用いる場合、正極集電体及び負極集電体にそれぞれ正極端子(又は正極端子と接続するリードタブ)及び負極端子(又は負極端子と接続するリードタブ)を接続し、両端子(又はリードタブ)の端部が外装体の外部に引き出された状態でラミネートフィルム外装体を封止してもよい。
本実施形態における非水系二次電池は、上述の電解液、正極と正極集電体とからなる正極体、負極と負極集電体とからなる負極体、及び必要に応じてセパレータを用いて、公知の方法により作製される。例えば、長尺の正極体と負極体とを、その間に長尺のセパレータを介在させた積層状態で巻回して巻回構造の積層体に成形することができる。また、それらを一定の面積と形状とを有する複数枚のシートに切断して、交互に積層した複数の正極体シートと負極体シートとの間にセパレータシートが介在する積層構造の積層体に成形することができる。また、長尺のセパレータをつづら折にして、つづら折になったセパレータ同士の間に交互に正極体シートと負極体シートとを挿入して積層構造の積層体に成形することができる。
(1)測定
(1-1)非水系電解液のイオン伝導度測定
非水系電解液をポリプロピレン製容器内で調製し、東亜ディーケーケー(株)製のイオン伝導度計「CM-30R」(商品名)に接続した東亜ディーケーケー(株)製のイオン伝導度測定用セル「CT-57101B」(商品名)を、非水系電解液が収容された上記容器に挿入し、25℃での非水系電解液のイオン伝導度を測定した。
電極活物質層の目付量は、以下の式(12)により算出した。
目付量[mg/cm2]=(電極質量[mg]-電極集電体質量[mg])÷電極面積[cm2] ・・・・・(12)
電極活物質層の空孔率は、以下の式(13)により求めた。
空孔率[%]=(1-実電極密度[g/cm3]/理論電極密度[g/cm3])×100 ・・・・・(13)
実電極密度は、電極活物質層質量を電極活物質層体積で割ることにより求めた。ここで、電極活物質層質量は、面積が2cm2になるよう打ち抜きポンチで打ち抜いた電極の質量から同じ面積で別途打ち抜いた電極集電体の質量を引いて算出した値を用い、電極活物質層体積は、マイクロメータにより測定した電極の厚さから別途測定した電極集電体の厚さを引いた電極活物質層厚さに面積をかけて算出した。理論電極密度は、電極を構成する電極活物質、導電助剤およびバインダーの密度と組成比率をそれぞれかけて足し合わせることにより求めた。
電極活物質層の厚さは、マイクロメータにより測定した電極の厚さから別途測定した電極集電体の厚さを引くことにより求めた。
正極はそれぞれ以下のようにして作製した。
(2-1)正極(P1)の作製
正極活物質として数平均粒子径7.4μmのコバルト酸リチウム(LiCoO2;密度4.95g/cm3)と、導電助剤として数平均粒子径48nmのアセチレンブラック(密度1.95g/cm3)と、バインダーとしてポリフッ化ビニリデン(PVdF;密度1.75g/cm3)とを、89.3:5.2:5.5の質量比で混合し、正極合剤を得た。得られた正極合剤に溶剤としてN-メチル-2-ピロリドンを固形分68質量%となるように投入して更に混合して、正極合剤含有スラリーを調製した。正極集電体となる厚さ20μm、幅200mmのアルミニウム箔の片面に、この正極合剤含有スラリーを目付量が6.1mg/cm2になるよう調節しながらドクターブレード法で塗布し、溶剤を乾燥除去した。その後、ロールプレスで実電極密度が2.77g/cm3になるよう圧延して、正極活物質層と正極集電体からなる正極(P1)を得た。なお、理論電極密度は4.62g/cm3と算出された。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
正極合剤含有スラリーを目付量が10.3mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が2.58g/cm3になるよう圧延したこと以外は、(2-1)と同様にして正極(P2)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
正極合剤含有スラリーを目付量が26.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が3.17g/cm3になるよう圧延したこと以外は、(2-1)と同様にして正極(P3)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
正極合剤含有スラリーを目付量が39.3mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が3.20g/cm3になるよう圧延したこと以外は、(2-1)と同様にして正極(P4)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
導電性材料として数平均粒子径3μmのグラファイト炭素粉末と、バインダーとしてポリフッ化ビニリデン(PVdF)とを90:10の質量比で混合した。得られた混合物にN-メチル-2-ピロリドンを固形分60質量%となるように投入して更に混合して、導電合剤スラリーを調製した。この導電合剤スラリーを厚さ20μm、幅200mmのアルミニウム箔の片面に塗布し、溶剤を乾燥除去した後、ロールプレスで圧延した。導電層の厚みは5μmであった。
この導電層の上に、正極合剤含有スラリーを目付量が10.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が2.50g/cm3になるよう圧延したこと以外は、(2-1)と同様にして正極(P5)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
正極集電体として厚さ30μmのアルミニウム箔を用い、正極合剤含有スラリーを目付量が24.6mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が3.00g/cm3になるよう圧延したこと以外は、(2-1)と同様にして正極(P6)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
正極合剤含有スラリーを目付量が24.6mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が3.00g/cm3になるよう圧延したこと以外は、(2-5)と同様にして正極(P7)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表1に示す。
正極活物質として数平均粒子径11μmのリチウムとニッケル、マンガン及びコバルトとの複合酸化物(Ni/Mn/Co=1/1/1(元素比);密度4.70g/cm3)と、導電助剤として数平均粒子径6.5μmのグラファイト炭素粉末(密度2.26g/cm3)及び数平均粒子径48nmのアセチレンブラック粉末(密度1.95g/cm3)と、バインダーとしてポリフッ化ビニリデン(PVdF;密度1.75g/cm3)とを、90.4:3.8:1.6:4.2の質量比で混合し、正極合剤を得た。得られた正極合剤に溶剤としてN-メチル-2-ピロリドンを固形分68質量%となるように投入して更に混合して、正極合剤含有スラリーを調製した。正極集電体となる厚さ20μm、幅200mmのアルミニウム箔の片面に、この正極合剤含有スラリーを目付量が12.0mg/cm2になるように調節しながらドクターブレード法で塗布し、溶剤を乾燥除去した。その後、ロールプレスで実電極密度が3.24g/cm3になるよう圧延して、正極活物質層と正極集電体からなる正極(P8)を得た。なお、理論電極密度は4.44g/cm3と算出された。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
ロールプレスを調整して実電極密度が3.02g/cm3になるよう圧延したこと以外は、(2-8)と同様にして正極(P9)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
ロールプレスを調整して実電極密度が2.66g/cm3になるよう圧延したこと以外は、(2-8)と同様にして正極(P10)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
ロールプレスで圧延しなかったこと以外は、(2-8)と同様にして正極(P11)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
導電性材料として数平均粒子径3μmのグラファイト炭素粉末と、バインダーとしてポリフッ化ビニリデン(PVdF)とを90:10の質量比で混合した。得られた混合物にN-メチル-2-ピロリドンを固形分60質量%となるように投入して更に混合して、導電合剤スラリーを調製した。この導電合剤スラリーを厚さ20μm、幅200mmのアルミニウム箔の片面に塗布し、溶剤を乾燥除去した後、ロールプレスで圧延した。導電層の厚みは5μmであった。
この導電層の上に、正極合剤含有スラリーを目付量が12.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が3.02g/cm3になるよう圧延したこと以外は、(2-8)と同様にして正極(P12)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
正極合剤含有スラリーを目付量が24.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が2.90g/cm3になるよう圧延したこと以外は、(2-8)と同様にして正極(P13)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
正極合剤含有スラリーを目付量が36.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が3.00g/cm3になるよう圧延したこと以外は、(2-8)と同様にして正極(P14)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表2に示す。
正極活物質として数平均粒子径11μmのリチウムとニッケル、マンガン及びコバルトとの複合酸化物(Ni/Mn/Co=1/1/1(元素比);密度4.70g/cm3)と、導電助剤として数平均粒子径6.5μmのグラファイト炭素粉末(密度2.26g/cm3)及び数平均粒子径48nmのアセチレンブラック粉末(密度1.95g/cm3)と、バインダーとしてポリフッ化ビニリデン(PVdF;密度1.75g/cm3)とを、100:4.2:1.8:4.5の質量比で準備した。次に、正極活物質と、導電助剤と、2価以上の有機酸としてシュウ酸を正極活物質100質量部に対して0.1質量部となるように調整した後、ドライの状態で均一に混合した。得られた混合物に、バインダーと、溶剤としてN-メチル-2-ピロリドンを固形分68質量%となるように投入して更に混合して、正極合剤含有スラリーを調製した。正極集電体となる厚さ20μm、幅200mmのアルミニウム箔の片面に、この正極合剤含有スラリーを目付量が24.9mg/cm2になるように調節しながらドクターブレード法で塗布し、溶剤を乾燥除去した。その後、ロールプレスで実電極密度が2.77g/cm3になるよう圧延して、正極活物質層と正極集電体からなる正極(P15)を得た。なお、理論電極密度は4.44g/cm3と算出された。目付量、電極活物質層厚さ、実電極密度、空孔率を表3に示す。
有機酸としてマロン酸を使用したこと以外は、(2-15)と同様にして正極(P16)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表3に示す。
有機酸を使用しなかったこと以外は、(2-15)と同様にして正極(P17)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表3に示す。
有機酸として酢酸を使用したこと以外は、(2-15)と同様にして正極(P18)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表3に示す。
正極合剤含有スラリーを目付量が35.6mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が2.94g/cm3になるよう圧延したこと以外は、(2-15)と同様にして正極(P19)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表3に示す。
正極活物質として数平均粒子径11μmのリチウムとニッケル、マンガン及びコバルトとの複合酸化物(Ni/Mn/Co=1/1/1(元素比);密度4.70g/cm3)と、導電助剤として数平均粒子径6.5μmのグラファイト炭素粉末(密度2.26g/cm3)及び数平均粒子径48nmのアセチレンブラック粉末(密度1.95g/cm3)と、バインダーとしてポリフッ化ビニリデン(PVdF;密度1.75g/cm3)とを、90.4:3.8:1.6:4.2の質量比で混合し、正極合剤を得た。得られた正極合剤に溶剤としてN-メチル-2-ピロリドンを固形分70質量%となるように投入して更に混合して、正極合剤含有スラリーを調製した。正極合剤含有スラリーを目付量が48.2mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が2.47g/cm3になるよう圧延したこと以外は、(2-8)と同様にして正極(P20)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表3に示す。
負極はそれぞれ以下のようにして作製した。
(3-1)負極(N1)の作製
負極活物質として数平均粒子径25μmのグラファイト炭素粉末(商品名「MCMB25-28」、大阪ガスケミカル(株)製;密度2.25g/cm3)と、導電助剤として数平均粒子径48nmのアセチレンブラック(密度1.95g/cm3)と、バインダーとしてポリフッ化ビニリデン(PVdF;密度1.75g/cm3)とを、93.0:2.0:5.0の質量比で混合し、負極合剤を得た。得られた負極合剤に溶剤としてN-メチル-2-ピロリドンを固形分45質量%となるように投入して更に混合して、負極合剤含有スラリーを調製した。負極集電体となる厚さ18μm、幅200mmの銅箔の片面に、この負極合剤含有スラリーを目付量が2.3mg/cm2になるよう調節しながらドクターブレード法で塗布し、溶剤を乾燥除去した。その後、ロールプレスで実電極密度が1.15g/cm3になるよう圧延して、負極活物質層と負極集電体からなる負極(N1)を得た。なお、理論電極密度は2.22g/cm3と算出された。目付量、電極活物質層厚さ、実電極密度、空孔率を表4に示す。
負極合剤含有スラリーを目付量が4.1mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.41g/cm3になるよう圧延したこと以外は、(3-1)と同様にして負極(N2)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表4に示す。
負極合剤含有スラリーを目付量が12.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.45g/cm3になるよう圧延したこと以外は、(3-1)と同様にして負極(N3)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表4に示す。
負極合剤含有スラリーを目付量が18.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.18g/cm3になるよう圧延したこと以外は、(3-1)と同様にして負極(N4)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表4に示す。
負極合剤含有スラリーを目付量が11.8mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.42g/cm3になるよう圧延したこと以外は、(3-1)と同様にして負極(N5)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表4に示す。
負極活物質として数平均粒子径7.4μmのLi4Ti5O12(密度3.30g/cm3)と、導電助剤として数平均粒子径48nmのアセチレンブラック(密度1.95g/cm3)と、バインダーとしてポリフッ化ビニリデン(PVdF;密度1.75g/cm3)とを、82.0:8.0:10.0の質量比で混合し、負極合剤を得た。得られた負極合剤に溶剤としてN-メチル-2-ピロリドンを固形分45質量%となるように投入して更に混合して、負極合剤含有スラリーを調製した。負極集電体となる厚さ18μm、幅200mmの銅箔の片面に、この負極合剤含有スラリーを目付量が29.4mg/cm2になるよう調節しながらドクターブレード法で塗布し、溶剤を乾燥除去した。その後、ロールプレスで実電極密度が1.86g/cm3になるよう圧延して、負極活物質層と負極集電体からなる負極(N6)を得た。なお、理論電極密度は3.04g/cm3と算出された。目付量、電極活物質層厚さ、実電極密度、空孔率を表4に示す。
負極活物質として数平均粒子径12.7μmのグラファイト炭素粉末(密度2.23g/cm3)及び数平均粒子径6.5μmのグラファイト炭素粉末(密度2.27g/cm3)と、バインダーとしてカルボキシメチルセルロース(密度1.60g/cm3)溶液(固形分濃度1.83質量%)と、ジエン系ゴム(ガラス転移温度:-5℃、乾燥時の数平均粒子径:120nm、密度1.00g/cm3、分散媒:水、固形分濃度40質量%)とを、87.2:9.7:1.4:1.7の固形分質量比で混合し、負極合剤を得た。得られた負極合剤に溶剤として水を固形分45質量%となるように投入して更に混合して、負極合剤含有スラリーを調製した。負極集電体となる厚さ10μm、幅200mmの銅箔の片面に、この負極合剤含有スラリーを目付量が5.5mg/cm2になるよう調節しながらドクターブレード法で塗布し、溶剤を乾燥除去した。その後、ロールプレスで実電極密度が1.62g/cm3になるよう圧延して、負極活物質層と負極集電体からなる負極(N7)を得た。なお、理論電極密度は2.20g/cm3と算出された。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
ロールプレスを調整して実電極密度が1.50g/cm3になるよう圧延したこと以外は、(3-7)と同様にして負極(N8)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
ロールプレスを調整して実電極密度が1.32g/cm3になるよう圧延したこと以外は、(3-7)と同様にして負極(N9)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
ロールプレスで圧延しなかったこと以外は、(3-7)と同様にして負極(N10)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
負極合剤含有スラリーを目付量が10.6mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.50g/cm3になるよう圧延したこと以外は、(3-7)と同様にして負極(N11)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
負極合剤含有スラリーを目付量が10.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.35g/cm3になるよう圧延したこと以外は、(3-7)と同様にして負極(N12)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
負極合剤含有スラリーを目付量が16.0mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.51g/cm3になるよう圧延したこと以外は、(3-7)と同様にして負極(N13)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
負極活物質として数平均粒子径12.7μmのグラファイト炭素粉末(密度2.23g/cm3)及び数平均粒子径6.5μmのグラファイト炭素粉末(密度2.27g/cm3)と、バインダーとしてカルボキシメチルセルロース(密度1.60g/cm3)溶液(固形分濃度1.83質量%)と、ジエン系ゴム(ガラス転移温度:-5℃、乾燥時の数平均粒子径:120nm、密度1.00g/cm3、分散媒:水、固形分濃度40質量%)とを、87.2:9.7:1.4:1.7の固形分質量比で混合し、負極合剤を得た。得られた負極合剤に溶剤として水を固形分48質量%となるように投入して更に混合して、負極合剤含有スラリーを調製した。負極合剤含有スラリーを目付量が21.4mg/cm2になるように調節しながらドクターブレード法で塗布し、ロールプレスを調整して実電極密度が1.24g/cm3になるよう圧延したこと以外は、(3-7)と同様にして負極(N14)を得た。目付量、電極活物質層厚さ、実電極密度、空孔率を表5に示す。
(4-1)溶媒の調製
各種有機溶媒を所定の体積比になるよう混合して、溶媒(L1)~(L22)を調製した。各溶媒の組成を表6に示す。なお、表6において、「AN」はアセトニトリル、「ADN」はアジポニトリル、「DMC」はジメチルカーボネート、「EC」はエチレンカーボネート、「EMC」はエチルメチルカーボネート、「GBL」はγ-ブチロラクトン、「PC」はプロピレンカーボネート、をそれぞれ示す。
上述の(4-1)で調製した溶媒と各種添加剤とをそれぞれが所定の濃度になるよう混合し、更に、リチウム塩を所定の濃度になるよう添加して、電解液(α)として(S1)~(S27)を調製した。また、これらの電解液(α)について上記(1-1)に記載の測定を行った。結果を表7に示す。なお、表7において、「VC」はビニレンカーボネート、「FEC」は4-フルオロ-1,3-ジオキソラン-2-オン、「ES」はエチレンサルファイト、「1,3-PS」は1,3-プロパンスルトン、「TMSO」はテトラメチレンスルホキシド、「SL」はスルホラン、「3-SLE」は3-スルホレン、「LiPF6」はヘキサフルオロリン酸リチウム、「LiBF4」はテトラフルオロホウ酸リチウム、「LiBOB」はリチウムビスオキサレートボレート、をそれぞれ示す。
溶媒にリチウム塩を所定の濃度になるよう添加して、電解液(β)を調製した(以下、添加剤を添加する前の電解液(β)を「母電解液(β)」という)。その母電解液(β)に各種添加剤並びにジニトリル化合物を所定の濃度となるよう混合して、電解液(γ)を得た。この調製方法により得られた電解液(γ)を表8の(S28)~(S48)に示す。なお、表8において、「SN」はスクシノニトリルを示す。
上述の方法により得られた電極と電解液とを組み合わせることにより、各種電池を作製した。具体的な作製方法を以下に示す。
(5-1)小型非水系二次電池の作製
上述のようにして得られた正極を直径16mmの円盤状に打ち抜いたものと、上述のようにして得られた負極を直径16mmの円盤状に打ち抜いたものとをポリエチレンからなるセパレータ(膜厚25μm、空孔率50%、孔径0.1μm~1μm)の両側に重ね合わせて積層体を得た。その積層体をSUS製の円盤型電池ケースに挿入した。次いで、その電池ケース内に電解液を0.5mL注入し、積層体を電解液に浸漬した後、電池ケースを密閉して25℃で24時間保持し、積層体に電解液を十分馴染ませて小型非水系二次電池を得た。
CR2032タイプの電池ケース(SUS304/Alクラッド)にポリプロピレン製ガスケットをセットし、その中央に上述のようにして得られた正極を直径16mmの円盤状に打ち抜いたものを、正極活物質層を上向きにしてセットした。その上からガラス繊維濾紙(アドバンテック社製ガラス繊維濾紙 GA-100)を直径16mmの円盤状に打ち抜いたものをセットして、電解液を150μL注入した後、上述のようにして得られた負極を直径16mmの円盤状に打ち抜いたものを、負極活物質層を下向きにしてセットした。さらにスペーサーとスプリングをセットした後に電池キャップをはめ込み、カシメ機でかしめた。あふれた電解液はウエスできれいにふきとった。25℃で24時間保持し、積層体に電解液を十分馴染ませてコイン型非水系二次電池を得た。
上述のようにして得られた評価用電池について、まず、下記(6-1)~(6-4)の手順に従って、初回充放電処理及び初回充放電容量測定を行った。次に、下記(6-5)~(6-14)に従って、それぞれの電池を評価した。なお、充放電はアスカ電子(株)製の充放電装置ACD-01(商品名)及び二葉科学社製の恒温槽PLM-63S(商品名)を用いて行った。
ここで、1Cとは満充電状態の電池を定電流で放電して1時間で放電終了となることが期待される電流値を意味する。負極(N6)以外を用いた場合には4.2Vの満充電状態から定電流で3.0Vまで放電して1時間で放電終了となることが期待される電流値を意味し、負極(N6)を用いた場合には2.7Vの満充電状態から定電流で1.5Vまで放電して1時間で放電終了となることが期待される電流値を意味する。正極(P1)~(P20)について1Cに相当する電流値を表9に示す。
0.005Cに相当する定電流で充電して3.0Vに到達した後、3.0Vで合計30時間充電を行った。さらに、0.2Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計8時間充電を行った。その後、0.3Cに相当する定電流で3.0Vまで放電した。このときの電池の周囲温度は25℃に設定した。
0.3Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計8時間充電を行った。その後、0.3Cに相当する定電流で3.0Vまで放電した。このときの電池の周囲温度は25℃に設定した。
0.3Cに相当する定電流で充電して2.7Vに到達した後、2.7Vの定電圧で合計8時間充電を行った。その後、0.3Cに相当する定電流で1.5Vまで放電した。このときの電池の周囲温度は25℃に設定した。
0.1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計15時間充電を行った。その後、0.3Cに相当する定電流で3.0Vまで放電した。このときの電池の周囲温度は25℃に設定した。
上記(6-1)に記載の方法で初回充放電処理を行った電池を用い、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、10Cに相当する定電流で3.0Vまで放電した。このときの放電容量を10C放電容量とし、上記(6-1)の放電容量を0.3C放電容量とした。
上記(6-1)に記載の方法で初回充放電処理を行った電池を用い、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、1Cに相当する定電流で3.0Vまで放電した。このときの放電容量を1C放電容量とした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、10Cに相当する定電流で3.0Vまで放電した。このときの放電容量を10C放電容量とした。上記(6-1)の放電容量を0.3C放電容量とし、0.3C放電容量を100%としたときの1C又は10C放電容量が75%以上である場合をそれぞれ◎、65%以上75%未満である場合をそれぞれ○、55%以上65%未満である場合をそれぞれ△、55%未満である場合をそれぞれ×と判定した。
上記(6-1)に記載の方法で初回充放電処理を行った電池を用い、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、1Cに相当する定電流で3.0Vまで放電した。このときの放電容量を1C放電容量とした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、3Cに相当する定電流で3.0Vまで放電した。このときの放電容量を3C放電容量とした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、5Cに相当する定電流で3.0Vまで放電した。このときの放電容量を5C放電容量とした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、10Cに相当する定電流で3.0Vまで放電した。このときの放電容量を10C放電容量とした。上記(6-1)の放電容量を0.3C放電容量とし、0.3C放電容量を100%としたときの1C、3C、5C又は10C放電容量が40%以上である場合をそれぞれ◎、20%以上40%未満である場合をそれぞれ○、20%未満である場合をそれぞれ×と判定した。
上記(6-3)に記載の方法で初回充放電処理を行った電池を用い、1Cに相当する定電流で充電して2.7Vに到達した後、2.7Vの定電圧で合計3時間充電を行った。その後、1Cに相当する定電流で1.5Vまで放電した。このときの放電容量を1C放電容量とした。次に、1Cに相当する定電流で充電して2.7Vに到達した後、2.7Vの定電圧で合計3時間充電を行った。その後、3Cに相当する定電流で1.5Vまで放電した。このときの放電容量を3C放電容量とした。次に、1Cに相当する定電流で充電して2.7Vに到達した後、2.7Vの定電圧で合計3時間充電を行った。その後、5Cに相当する定電流で1.5Vまで放電した。このときの放電容量を5C放電容量とした。次に、1Cに相当する定電流で充電して2.7Vに到達した後、2.7Vの定電圧で合計3時間充電を行った。その後、10Cに相当する定電流で1.5Vまで放電した。このときの放電容量を10C放電容量とした。上記(6-3)の放電容量を0.3C放電容量とし、0.3C放電容量を100%としたときの1C、3C、5C又は10C放電容量が40%以上である場合をそれぞれ◎、20%以上40%未満である場合をそれぞれ○、20%未満である場合をそれぞれ×と判定した。
上記(6-1)又は(6-2)に記載の方法で初回充放電処理を行った電池を用い、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、1Cに相当する定電流で3.0Vまで放電した。このときの放電容量をAとした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vの定電圧で合計3時間充電を行った。その後、5Cに相当する定電流で3.0Vまで放電した。このときの放電容量をBとした。出力試験測定値として、100×B/A[%]を求めた。
上記(6-9)に記載の方法で出力試験を行った後の電池について、50℃における充放電サイクル特性を評価した。まず、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vで合計3時間充電を行い、1Cに相当する定電流で3.0Vまで放電した。充電と放電とを各々1回ずつ行うこの工程を1サイクルとし、25サイクルの充放電を行った。なお、1回目及び25回目の放電は1Cに代えて0.3Cに相当する定電流で行った。25サイクル終了後も充分な放電容量が維持できている場合、更にこれと同じサイクル評価を繰り返し行った。2サイクル目の放電容量を100%としたときの各サイクルの放電容量の比率を放電容量維持率とした。なお、放電容量維持率が10%未満となった時点で測定を終了した。これらの測定に際しての電池の周囲温度は50℃に設定した。
上記(6-4)に記載の方法で初回充放電処理を行った電池について、50℃における充放電サイクル特性を評価した。まず、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vで合計3時間充電を行い、1Cに相当する定電流で3.0Vまで放電した。充電と放電とを各々1回ずつ行うこの工程を1サイクルとし、50サイクル目の充電まで繰り返し充放電を行った。1サイクル目の放電容量を100%としたときの49サイクル目の放電容量の比率を放電容量維持率とした。これらの測定に際しての電池の周囲温度は50℃に設定した。
交流インピーダンスの測定は、ソーラトロン社製の周波数応答アナライザ1400(商品名)とソーラトロン社製のポテンショ-ガルバノスタット1470E(商品名)とを用いて行った。測定する非水系二次電池は、上記(6-10)に記載のように充放電を繰り返し、初回充放電処理後、並びに、25サイクル及び100サイクル後の電池を、1Cに相当する定電流で充電して4.0Vに到達した後、4.0Vで合計3時間充電を行った状態のものを用いた。測定条件は、振幅を±5mV、周波数を0.1~20kHzに設定した。0.1kHz及び20kHzにおける交流インピーダンス値を求めた。交流インピーダンスを測定する際の電池の周囲温度は25℃であった。
上記(6-11)に記載の方法で50サイクル目の充電まで行った電池について、上記(6-12)に記載の装置を用い交流インピーダンスの測定を行った。測定条件は、振幅を±5mV、周波数を0.1~20kHzに設定した。0.1kHz及び20kHzにおける交流インピーダンス値を求めた。交流インピーダンスを測定する際の電池の周囲温度は25℃であった。
上記(6-4)に記載の方法で初回充放電処理を行った電池について、85℃満充電保存時の耐久性能を評価した。まず、電池の周囲温度を25℃に設定し、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vで合計3時間充電を行った。次に、この非水系二次電池を85℃の恒温槽に4時間保存した。その後、電池の周囲温度を25℃に戻し、0.3Cに相当する定電流で3.0Vまで放電した。このときの放電容量を残存容量とした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vで合計3時間充電を行い、0.3Cに相当する定電流で3.0Vまで放電した。このときの放電容量を0.3C回復容量とした。次に、1Cに相当する定電流で充電して4.2Vに到達した後、4.2Vで合計3時間充電を行い、1.5Cに相当する定電流で3.0Vまで放電した。このときの放電容量を1.5C回復容量とした。
正極(P1)~(P5)、(P20)、負極(N1)~(N4)、(N14)、及び電解液(S1)~(S4)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-1)に記載の方法で初回充放電処理を行い、上記(6-5)に記載の測定を行った。結果を表10に示す。
正極(P8)~(P12)、負極(N7)~(N10)、及び電解液(S1)、(S5)~(S7)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-1)に記載の方法で初回充放電処理を行い、上記(6-6)に記載の測定を行った。結果を表11に示す。
正極(P6)~(P7)、負極(N5)、及び電解液(S1)、(S8)~(S9)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-1)に記載の方法で初回充放電処理を行い、上記(6-7)に記載の測定を行った。結果を表12に示す。
正極(P6)、負極(N6)、及び電解液(S1)、(S8)~(S9)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-3)に記載の方法で初回充放電処理を行い、上記(6-8)に記載の測定を行った。結果を表12に示す。
なお、炭素材料と比較して導電性の低いLi4Ti5O12等の合金を負極活物質として用いた非水系二次電池は、負極活物質層の導電ネットワークを確保するため比表面積を大きくすることや粒径を小さくすること等の工夫が必要であるが、一般に、目付量の低い電極と既存のカーボネート系電解液を組み合わせた場合には問題なく作動することが知られている。一方、本実施形態における非水系二次電池のように、目付量の高い電極と高イオン伝導度の非水系電解液とを組み合わせた場合には、実用性能としては十分であるものの、炭素材料とは異なる粒子性状に起因して出力性能が炭素材料には及ばなかったと推測される。
正極(P13)、負極(N11)、及び電解液(S28)~(S36)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-1)に記載の方法で初回充放電処理を行い、上記(6-9)に記載の測定を行った。結果を表13に示す。
正極(P13)、負極(N11)、及び電解液(S41)、(S42)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-2)に記載の方法で初回充放電処理を行い、上記(6-9)に記載の測定を行ったが、放電容量維持率が低く、その他の測定は行わなかった。結果を表14に示す。
正極(P13)、負極(N11)、及び電解液(S14)、(S18)、(S19)、(S40)、(S43)~(S48)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-1)に記載の方法で初回充放電処理を行い、上記(6-9)、(6-10)及び(6-12)に記載の測定を行った。結果を表15に示す。
正極(P15)~(P20)、負極(N12)~(N14)、及び電解液(S1)、(S10)~(S12)、(S25)~(S27)を組み合わせ、上述の(5-1)に記載の方法に従って小型非水系二次電池を作製した。これらの電池について上記(6-4)に記載の方法で初回充放電処理を行い、上記(6-7)、(6-11)及び(6-13)に記載の測定を行った。結果を表16に示す。
正極(P14)、(P19)、負極(N13)、及び電解液(S20)~(S24)を組み合わせ、上述の(5-2)に記載の方法に従ってコイン型非水系二次電池を作製した。これらの電池について上記(6-4)に記載の方法で初回充放電処理を行い、上記(6-14)に記載の測定を行った。結果を表17に示す。
Claims (31)
- リチウム塩と非水系溶媒とを含有する電解液と、正極と、負極とを含む非水系二次電池であって、前記正極に含まれる正極活物質層の目付量が8~100mg/cm2、及び/又は、前記負極に含まれる負極活物質層の目付量が3~46mg/cm2であり、かつ、前記電解液の25℃におけるイオン伝導度が15mS/cm以上である非水系二次電池。
- 前記電解液の25℃におけるイオン伝導度が50mS/cm以下である、請求項1記載の非水系二次電池。
- 前記正極に含まれる正極活物質層の目付量が24~100mg/cm2、及び/又は、前記負極に含まれる負極活物質層の目付量が10~46mg/cm2である、請求項1又は2記載の非水系二次電池。
- 前記正極又は前記負極の少なくとも一方の電極に含まれる電極活物質層の空孔率が20~45%である、請求項1~3のいずれか1項記載の非水系二次電池。
- 前記正極に含まれる正極活物質層の空孔率が20~45%である、請求項1~4のいずれか1項記載の非水系二次電池。
- 前記負極に含まれる負極活物質層の空孔率が20~45%である、請求項1~5のいずれか1項記載の非水系二次電池。
- 前記非水系溶媒はニトリル系溶媒を含む、請求項1~6のいずれか1項記載の非水系二次電池。
- 前記ニトリル系溶媒はアセトニトリルを含む、請求項7記載の非水系二次電池。
- 前記非水系溶媒中のアセトニトリルの含有量が5~97体積%である、請求項8記載の非水系二次電池。
- 前記非水系溶媒中のアセトニトリルの含有量が25~80体積%である、請求項8記載の非水系二次電池。
- 前記式(1)で表される化合物は、エチレンサルファイト、プロピレンサルファイト、ブチレンサルファイト、ペンテンサルファイト、スルホラン、3-メチルスルホラン、3-スルホレン、1,3-プロパンスルトン、1,4-ブタンスルトン、1,3-プロパンジオール硫酸エステル及びテトラメチレンスルホキシドからなる群より選ばれる1種以上の化合物を含む、請求項11記載の非水系二次電池。
- 前記電解液が、炭素間不飽和二重結合を有する環状カーボネートからなる群より選ばれる1種以上の化合物を更に含有する、請求項11又は12記載の非水系二次電池。
- 前記リチウム塩は、フッ素原子を有する無機リチウム塩である、請求項1~13のいずれか1項記載の非水系二次電池。
- 前記無機リチウム塩は、LiPF6である、請求項14記載の非水系二次電池。
- 前記無機リチウム塩は、LiBF4である、請求項14記載の非水系二次電池。
- 前記無機リチウム塩の含有量は、前記電解液の全量に対して0.1~40質量%である、請求項14~16のいずれか1項記載の非水系二次電池。
- 有機リチウム塩を更に含有し、前記有機リチウム塩と前記無機リチウム塩とが、下記式(7):
0≦X<1 ・・・・・(7)
(式中、Xは前記無機リチウム塩に対する前記有機リチウム塩の含有モル比である。)
で表される条件を満足する、請求項14~17のいずれか1項記載の非水系二次電池。 - 前記有機リチウム塩は、リチウムビス(オキサラト)ボレート及びリチウムオキサラトジフルオロボレートからなる群より選ばれる1種以上の有機リチウム塩である、請求項18記載の非水系二次電池。
- 前記正極は、正極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料からなる群より選ばれる1種以上の材料を含有し、前記負極は、負極活物質としてリチウムイオンを吸蔵及び放出することが可能な材料及び金属リチウムからなる群より選ばれる1種以上の材料を含有する、請求項1~19のいずれか1項記載の非水系二次電池。
- 前記正極は、前記正極活物質として、リチウム含有化合物を含有する、請求項20記載の非水系二次電池。
- 前記リチウム含有化合物は、リチウムを有する金属酸化物及びリチウムを有する金属カルコゲン化物からなる群より選ばれる1種以上の化合物を含む、請求項21記載の非水系二次電池。
- 前記負極は、前記負極活物質として、金属リチウム、炭素材料、及びリチウムと合金形成が可能な元素を含む材料からなる群より選ばれる1種以上の材料を含有する、請求項20~22のいずれか1項記載の非水系二次電池。
- 前記負極は、前記負極活物質として、リチウムイオンを1.4Vvs.Li/Li+よりも卑な電位で吸蔵する材料を含有する、請求項20~23のいずれか1項記載の非水系二次電池。
- 前記正極の正極合剤は、正極活物質、導電助剤、バインダー、有機酸、及び有機酸塩からなる群から選択される少なくとも1種の化合物を含む、請求項1~24のいずれか1項記載の非水系二次電池。
- 前記化合物は2価以上の有機酸又は有機酸塩を含む、請求項25記載の非水系二次電池。
- 前記正極合剤から作製した正極活物質層の厚さが50~300μmである、請求項25又は26記載の非水系二次電池。
- 前記正極及び/又は負極は、電極集電体上に導電性材料を含む導電層を塗布した電極基板上に、正極活物質層及び/又は負極活物質層を塗布した電極である、請求項1~27のいずれか1項記載の非水系二次電池。
- 前記導電層が、導電性材料とバインダーを含む、請求項28記載の非水系二次電池。
- 請求項1~29のいずれか1項記載の非水系二次電池の製造方法であって、0.001~0.3Cの初回充電を行う工程を有する、非水系二次電池の製造方法。
- 前記初回充電が定電圧充電を途中に経由して行われる、請求項30記載の非水系二次電池の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12843297.8A EP2772981B1 (en) | 2011-10-28 | 2012-10-25 | Non-aqueous secondary battery |
CN201280051508.3A CN103891028B (zh) | 2011-10-28 | 2012-10-25 | 非水系二次电池 |
US14/352,864 US10644353B2 (en) | 2011-10-28 | 2012-10-25 | Non-aqueous secondary battery |
KR1020147010256A KR101551135B1 (ko) | 2011-10-28 | 2012-10-25 | 비수계 이차 전지 |
JP2013540829A JP6120772B2 (ja) | 2011-10-28 | 2012-10-25 | 非水系二次電池 |
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EP2772981B1 (en) | 2020-10-21 |
EP2772981A1 (en) | 2014-09-03 |
EP2772981A4 (en) | 2015-04-08 |
CN103891028B (zh) | 2016-04-13 |
KR20140072105A (ko) | 2014-06-12 |
TWI472083B (zh) | 2015-02-01 |
CN103891028A (zh) | 2014-06-25 |
JP2017054822A (ja) | 2017-03-16 |
US20140255796A1 (en) | 2014-09-11 |
JP6427544B2 (ja) | 2018-11-21 |
KR101551135B1 (ko) | 2015-09-07 |
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