WO2013042419A1 - 非水二次電池 - Google Patents

非水二次電池 Download PDF

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Publication number
WO2013042419A1
WO2013042419A1 PCT/JP2012/066530 JP2012066530W WO2013042419A1 WO 2013042419 A1 WO2013042419 A1 WO 2013042419A1 JP 2012066530 W JP2012066530 W JP 2012066530W WO 2013042419 A1 WO2013042419 A1 WO 2013042419A1
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negative electrode
secondary battery
positive electrode
general formula
aqueous secondary
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PCT/JP2012/066530
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English (en)
French (fr)
Japanese (ja)
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矢野亮
児島克典
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日立マクセルエナジー株式会社
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Priority to JP2013516809A priority Critical patent/JP5658821B2/ja
Priority to CN201280010944.6A priority patent/CN103415951B/zh
Priority to KR1020137016616A priority patent/KR101489335B1/ko
Publication of WO2013042419A1 publication Critical patent/WO2013042419A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous secondary battery that can exhibit excellent charge / discharge cycle characteristics at a high energy density.
  • the negative electrode using SiO x particles has a large initial charge / discharge capacity, but there is a problem that the capacity decreases when charge / discharge is repeated. This is because SiO x particles are gradually pulverized by volume expansion and contraction due to charge and discharge, and active ultrafine Si exposed on the surface reacts with a non-aqueous electrolyte and the like, and the reaction product generated by the reaction causes Si to It is presumed that the internal resistance of the battery is increased by inhibiting the reaction between Li and Li.
  • Patent Document 1 a method has been proposed in which a non-aqueous electrolyte contains a halogen-substituted cyclic carbonate as an additive.
  • Patent Document 1 a film derived from the additive is formed on the new surface generated by grinding the SiO x particles, and this suppresses the reaction between the non-aqueous electrolyte and Si, so that the increase in the internal resistance does not occur, and the battery Capacity reduction due to charge / discharge cycles is improved.
  • a positive electrode active material that can operate at a high potential.
  • a spinel crystal type Li-containing composite oxide represented by the general formula LiNi 0.5 Mn 1.5 O 4 can operate at a high voltage of about 4.7 V based on lithium.
  • the average discharge voltage can be increased by increasing the charge end voltage.
  • a negative electrode containing a high-capacity negative electrode active material such as SiO x and a positive electrode containing a positive electrode active material capable of operating at a high potential as described above.
  • This invention is made
  • An object of the present invention is to provide a nonaqueous secondary battery having a negative electrode and excellent charge / discharge cycle characteristics.
  • the non-aqueous secondary battery of the present invention is a non-aqueous secondary battery including a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte
  • the negative electrode is a negative electrode material containing silicon and oxygen as constituent elements
  • the said positive electrode is the following general formula (1) or the following general formula (2)
  • a non-aqueous electrolyte containing a halogen-substituted cyclic carbonate and a boric acid triester is the following general formula (1) or the following general formula (2)
  • a non-aqueous electrolyte containing a halogen-substituted cyclic carbonate and a boric acid triester.
  • M 1 is at least one element selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li, and y is 0.45 ⁇ y ⁇ 0.55, z is 0 ⁇ z ⁇ 0.1.
  • M 2 includes at least two or more elements including Ni and Co, and the ratio of the number of elements of Ni, Co and Mn to the total number of elements of M 2 is represented by a (Mol%), b (mol%) and c (mol%), 20 ⁇ a ⁇ 65, 15 ⁇ b ⁇ 55, 0 ⁇ c ⁇ 45, 90 ⁇ a + b + c ⁇ 100.
  • a non-aqueous solution having a positive electrode containing a positive electrode active material capable of operating at a high potential and a negative electrode containing a negative electrode active material made of a material containing Si and O and having excellent charge / discharge cycle characteristics.
  • a secondary battery can be provided.
  • FIG. 1A is a plan view showing an example of the non-aqueous secondary battery of the present invention
  • FIG. 1B is a cross-sectional view of FIG. 1A
  • FIG. 2 is a perspective view of the nonaqueous secondary battery of the present invention shown in FIGS. 1A and 1B
  • FIG. 3 is a plan view showing another example of the nonaqueous secondary battery of the present invention.
  • the non-aqueous secondary battery of the present invention is a non-aqueous secondary battery including the following positive electrode, negative electrode, separator and non-aqueous electrolyte. Each will be described below.
  • the negative electrode according to the nonaqueous secondary battery of the present invention has a structure having, for example, a negative electrode mixture layer containing a negative electrode active material and a binder on one side or both sides of a current collector.
  • the negative electrode active material includes a negative electrode material containing silicon (Si) and oxygen (O) as constituent elements, wherein the atomic ratio x of oxygen to silicon is 0.5 ⁇ x ⁇ 1.5 (Hereinafter, this material is referred to as “SiO x ”).
  • the SiO x may contain Si microcrystal or amorphous phase.
  • the atomic ratio of Si and O is a ratio including Si microcrystal or amorphous phase Si. That is, the SiO x includes a structure in which Si (for example, microcrystalline Si) is dispersed in an amorphous SiO 2 matrix, and is dispersed in the amorphous SiO 2 . In combination with Si, it is sufficient that the atomic ratio x satisfies 0.5 ⁇ x ⁇ 1.5.
  • the composition formula is represented by SiO.
  • a peak due to the presence of Si may not be observed, but when observed with a transmission electron microscope, the presence of fine Si Can be confirmed.
  • the surface of SiO x is preferably covered with a conductive material such as a carbon material. Since SiO x has poor electron conductivity, it is effective to supplement the electron conductivity by covering the surface with a conductive material such as a carbon material in order to ensure good battery characteristics.
  • the carbon material for covering the surface of SiO x for example, low crystalline carbon, carbon nanotube, vapor grown carbon fiber, or the like can be used.
  • the hydrocarbon gas is heated in the gas phase, the carbon generated by thermal decomposition of hydrocarbon gas, a method of depositing on the surface of the SiO x particulate [vapor deposition (CVD) method, the surface of the SiO x Is coated with a carbon material, the hydrocarbon-based gas spreads to every corner of the SiO x particle, and a thin and uniform film (carbon coating) containing a carbon material having electron conductivity in the surface of the particle and in the pores of the surface. Layer), it is possible to impart uniform electron conductivity to the SiO x particles with a small amount of carbon material.
  • CVD vapor deposition
  • toluene, benzene, xylene, mesitylene and the like can be used, but toluene that is easy to handle is particularly preferable.
  • a hydrocarbon-based gas can be obtained by vaporizing them (for example, bubbling with nitrogen gas).
  • methane gas, ethylene gas, acetylene gas, etc. can also be used.
  • the processing temperature of the CVD method is preferably 600 to 1200 ° C., for example. Further, SiO x subjected to CVD method is preferably granulated material was granulated by a known method (composite particles).
  • the amount of the carbon material is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to SiO x : 100 parts by mass, Moreover, it is preferable that it is 95 mass parts or less, and it is more preferable that it is 90 mass parts or less.
  • a graphitic carbon material can be used together with SiO x .
  • SiO x is a high capacity, because of the large volume change accompanying the charge and discharge of the battery, for example, there is a fear of lowering the battery characteristics causing expansion and contraction of the negative electrode, during charge and discharge than SiO x
  • a graphitic carbon material with a small volume change in combination with SiO x the effect on the battery capacity is suppressed as much as possible, and the volume change of the negative electrode accompanying charge / discharge is reduced, resulting in a deterioration in battery characteristics. Etc. can be suppressed.
  • Graphite carbon materials that can be used in combination with SiO x include, for example, natural graphite such as scaly graphite; graphitizable carbon such as pyrolytic carbons, mesophase carbon microbeads (MCMB), and carbon fibers at 2800 ° C. or higher. Artificial graphite subjected to chemical treatment; and the like.
  • the negative electrode active material 100 wt% When used in combination with SiO x and graphitic carbon material in the negative electrode active material, containing SiO x from the viewpoint of satisfactorily ensuring the effect of the high energy density of the battery by the use of SiO x, the negative electrode active material 100 wt% The amount is preferably 3% by mass or more, and more preferably 5% by mass or more. Further, when used in combination with SiO x and graphitic carbon material in the negative electrode active material, the content of SiO x from the viewpoint of satisfactorily ensuring the effect of the above by the use of graphitic carbon material, the anode active material 100 wt% Is preferably 90% by mass or less, and more preferably 80% by mass or less.
  • binder relating to the negative electrode mixture layer for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC) and the like are preferably used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • a negative electrode mixture-containing composition is prepared by dispersing a negative electrode active material and a binder, and if necessary, a conductive additive in a solvent such as N-methyl-2-pyrrolidone (NMP) or water. (However, the binder may be dissolved in a solvent.) After this is applied to one or both sides of the current collector and dried, it is manufactured through a step of applying a calender treatment if necessary.
  • NMP N-methyl-2-pyrrolidone
  • the manufacturing method of the negative electrode is not limited to the above method, and may be manufactured by other manufacturing methods.
  • the amount of the negative electrode active material is preferably 80 to 95% by mass
  • the amount of the binder is preferably 1 to 20% by mass
  • a conductive assistant is used.
  • the amount is preferably 1 to 10% by mass.
  • the thickness of the negative electrode mixture layer is preferably 10 to 100 ⁇ m per one side of the current collector.
  • a foil made of copper, stainless steel, nickel, titanium, or an alloy thereof, a punched metal, an expanded metal, a net, or the like can be used.
  • a copper having a thickness of 5 to 30 ⁇ m is used.
  • a foil is preferably used.
  • the positive electrode according to the nonaqueous secondary battery of the present invention has, for example, a structure having a positive electrode mixture layer containing a positive electrode active material, a conductive additive and a binder on one side or both sides of a current collector.
  • Li-containing composite oxide represented by the following general formula (1) or the following general formula (2) is used.
  • M 1 is at least one element selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li, and y is 0.45 ⁇ y ⁇ 0.55, z is 0 ⁇ z ⁇ 0.1.
  • M 2 includes at least two or more elements including Ni and Co, and the ratio of the number of elements of Ni, Co and Mn to the total number of elements of M 2 is represented by a (Mol%), b (mol%) and c (mol%), 20 ⁇ a ⁇ 65, 15 ⁇ b ⁇ 55, 0 ⁇ c ⁇ 45, 90 ⁇ a + b + c ⁇ 100.
  • the Li-containing composite oxide represented by the general formula (1) is obtained by substituting a part of Mn of the spinel-type positive electrode active material LiMn 2 O 4 with Ni, and is about 4.7 V based on Li. A high discharge voltage can be obtained.
  • the Li-containing composite oxide represented by the general formula (1) it is mainly oxidation / reduction of Ni 2+ / Ni 4+ that compensates for charges by desorption / insertion of Li ions. Since the discharge voltage decreases when the Ni substitution amount y deviates significantly from 0.5, it is necessary that 0.45 ⁇ y ⁇ 0.55.
  • the Li-containing composite oxide represented by the general formula (1) contains at least one additive element M 1 selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li. May be. However, if the amount of these additive elements M 1 is too large, the discharge capacity decreases, so the amount z of the additive elements M 1 is set to 0.1 or less.
  • the Li-containing composite oxide represented by the general formula (2) is a positive electrode active material having the same layered crystal as LiCoO 2 or the like, but by increasing the charging voltage to 4.4 V or more on the basis of Li, a high voltage and High capacity discharge characteristics can be obtained.
  • this active material each of Ni, Co, and Mn changes in valence due to desorption / insertion of Li ions, contributing to charge / discharge characteristics.
  • M 2 related to the Li-containing composite oxide represented by the general formula (2) includes at least two or more elements including Ni and Co.
  • the Ni ratio a is 20 mol% or more. Further, in the Li-containing composite oxide represented by the general formula (2), if the amount of Ni is too large, for example, the amount of Co or Mn is decreased, and the effect of these may be reduced. Therefore, in the general composition formula (2), when the total number of elements of M 2 is 100 mol%, the Ni ratio a is 65 mol% or less.
  • the Co ratio b is 15 mol% or more.
  • the Co ratio b is 55 mol% or less.
  • the Li-containing composite oxide represented by the general formula (2) may contain Mn. However, if the amount of Mn in the Li-containing composite oxide represented by the general formula (2) is too large, the discharge capacity decreases. Therefore, in the general formula (2), when the total number of elements of M 2 is 100 mol%, the ratio c of Mn is 0 mol% or more and 45 mol% or less.
  • M 2 according to the Li-containing complex oxide represented by the general formula (2) is, Ni, may contain additive elements other than Co and Mn.
  • additive elements include Al, Mg, Zn, Ca, Ti, Cr, Zr, and Li.
  • the Li-containing composite oxide represented by the general formula (2) if the amount of these additive elements is too large, the discharge capacity may be reduced. Therefore, in the general formula (2), when the total number of elements of M 2 is 100 mol%, the ratio of additive elements other than Ni, Co, and Mn is preferably 10 mol% or less.
  • the total number of elements in the element group M 2 is taken as 100 mol%, and the ratio a of Ni, the ratio of Co b, the ratio of Mn
  • the total (a + b + c) with c is 90 mol% or more and 100 mol% or less.
  • the positive electrode active material according to the non-aqueous secondary battery of the present invention includes any one of the Li-containing composite oxide represented by the general formula (1) and the Li-containing composite oxide represented by the general formula (2). Only one of them may be used, or both of them may be used together. Either of the Li-containing composite oxide represented by the general formula (1) and the Li-containing composite oxide represented by the general formula (2) Either one or both may be used in combination with another positive electrode active material.
  • Examples of other positive electrode active materials that can be used in combination with the Li-containing composite oxide represented by the general formula (1) and the Li-containing composite oxide represented by the general formula (2) include LiCoO 2 ; LiCoO 2. Li-containing composite oxides in which a part of Co is substituted with other metal elements such as Ti, Zr, Mg, and Al [however, those that do not satisfy the general formula (2)]; and the like.
  • the amount of the Li composite oxide represented by the above general formula (1) and the Li-containing composite oxide represented by the above general formula (2) in all the positive electrode active materials [represented by the above general formula (1) When only one of Li composite oxide and Li-containing composite oxide represented by the above general formula (2) is used, it is the amount thereof, and when both are used, the total amount thereof. ] Is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • the conductive additive for the positive electrode is non-crystalline such as graphite; carbon black (acetylene black, ketjen black, etc.) or a carbon material with amorphous carbon formed on the surface.
  • Carbonaceous materials far-grown carbon fibers, carbon fibers obtained by carbonizing after spinning a pitch
  • carbon nanotubes variant multi-layer or single-wall carbon nanotubes
  • the conductive additive for the positive electrode those exemplified above may be used alone or in combination of two or more.
  • Fluorine resin such as PVDF and polytetrafluoroethylene; polyacrylic acid; SBR; and the like can be used for the positive electrode binder.
  • a paste-like or slurry-like positive electrode mixture-containing composition in which a positive electrode active material, a binder, and a conductive additive are dispersed in a solvent such as NMP is prepared (however, the binder is dissolved in the solvent). It may be manufactured through a step of applying a calender treatment if necessary after applying it to one or both sides of the current collector and drying it.
  • the manufacturing method of a positive electrode is not necessarily restricted to said method, You may manufacture with another manufacturing method.
  • the positive electrode active material is preferably 70 to 99% by mass
  • the conductive auxiliary agent is preferably 1 to 20% by mass
  • the binder is 1 to 30% by mass. It is preferable.
  • the thickness of the positive electrode mixture layer is preferably 1 to 100 ⁇ m per side of the current collector.
  • a foil made of aluminum, stainless steel, nickel, titanium or an alloy thereof, a punched metal, an expanded metal, a net, or the like can be used.
  • an aluminum foil having a thickness of 10 to 30 ⁇ m is used.
  • the negative electrode and the positive electrode are used, for example, in the form of a laminated electrode body laminated with a separator interposed therebetween, or a wound electrode body obtained by winding the separator in a spiral shape. .
  • the separator it is preferable that the separator has sufficient strength and can retain a large amount of nonaqueous electrolyte. From such a viewpoint, polyethylene, polypropylene, or ethylene having a thickness of 10 to 50 ⁇ m and an aperture ratio of 30 to 70% is used. A microporous film or a nonwoven fabric containing a propylene copolymer is preferred.
  • Non-aqueous electrolyte For the nonaqueous electrolyte according to the nonaqueous secondary battery of the present invention, a nonaqueous liquid electrolyte (nonaqueous electrolyte) in which an electrolyte salt such as a lithium salt is dissolved in an organic solvent is usually used.
  • the nonaqueous electrolyte according to the present invention contains a halogen-substituted cyclic carbonate and a boric acid triester.
  • the charging / discharging cycle deterioration suppressing mechanism according to the present invention is considered as follows.
  • Charge / discharge cycle deterioration in the negative electrode using SiO x as the negative electrode active material is caused by gradual pulverization of the SiO x particles due to volume expansion / contraction due to charge / discharge, and active ultrafine Si exposed on the surface is non-aqueous electrolyte. This is considered to be caused by increasing the internal resistance of the battery by inhibiting the reaction between Si and Li by the reaction product produced by the reaction with the above solvent.
  • the halogen-substituted cyclic carbonate contained in the non-aqueous electrolyte has a property that it is more easily reduced than the carbonate generally used as a non-aqueous electrolyte solvent for non-aqueous secondary batteries. It is considered that the film is reduced and decomposed to form a film on a new surface produced by grinding by expansion and contraction of SiO x , and this film suppresses the reaction between the nonaqueous electrolyte and Si.
  • the halogen-substituted cyclic carbonate in the non-aqueous electrolyte is highly resistant to oxidation, and is therefore difficult to decompose on the positive electrode side.
  • it has a positive electrode using the Li-containing composite oxide represented by the general formula (1) or the Li-containing composite oxide represented by the general formula (2) as a positive electrode active material, and is charged at a high potential.
  • the halogen-substituted cyclic carbonate is exposed to a higher potential than the conventional one on the positive electrode side and is therefore oxidatively decomposed.
  • the boric acid triester contained in the nonaqueous electrolyte according to the present invention is more easily oxidized than, for example, carbonates commonly used in nonaqueous electrolyte solvents. It is expected to form a film on the surface.
  • This boric acid triester-derived film exhibits a protective action to suppress decomposition of the halogen-substituted cyclic carbonate on the positive electrode side, and the halogen-substituted cyclic carbonate can form a film on the negative electrode surface.
  • deterioration of charge / discharge cycle characteristics is improved. Since boric acid triester has high reduction resistance, it is difficult to reduce and decompose on the negative electrode side, and it is presumed that the protective action on the positive electrode side is well exhibited.
  • halogen-substituted cyclic carbonate to be contained in the nonaqueous electrolyte, a compound represented by the following general formula (3) can be used.
  • R 1 , R 2 , R 3 and R 4 represent hydrogen, a halogen element or an alkyl group having 1 to 10 carbon atoms, and a part or all of the hydrogen in the alkyl group is halogen. may be substituted with an element, at least one of R 1, R 2, R 3 and R 4 are halogen, R 1, R 2, R 3 and R 4 have different respective Two or more may be the same.
  • R 1 , R 2 , R 3 and R 4 are alkyl groups, the smaller the number of carbon atoms, the better.
  • the halogen element fluorine is particularly preferable.
  • FEC 4-fluoro-1,3-dioxolan-2-one
  • the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used in the non-aqueous secondary battery is 0.5% by mass from the viewpoint of better ensuring the reaction suppressing effect on the new surface of the SiO x particles in the negative electrode.
  • the above is preferable, and the content is more preferably 1% by mass or more.
  • the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used in the non-aqueous secondary battery is preferably 20% by mass or less, and more preferably 10% by mass or less.
  • a trialkyl ester of boric acid is preferable.
  • the alkyl moiety in the trialkyl ester of boric acid preferably has 1 to 4 carbon atoms, and part or all of the hydrogen in the alkyl moiety may be substituted with fluorine.
  • the three alkyl moieties in the trialkyl ester of boric acid may all be the same structure, two may be the same structure and the other one may be different, or all may be different from each other. .
  • boric acid triesters include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, dimethylethyl boric acid, and the like.
  • boric acid triester for example, those exemplified above may be used alone or in combination of two or more.
  • triethyl borate (TEB) is particularly preferred.
  • the content of boric acid triester in the non-aqueous electrolyte used for the non-aqueous secondary battery is 0.1% from the viewpoint of allowing the positive electrode surface to form a good film and exhibiting the above-described protective action well.
  • the content is preferably at least mass%, more preferably at least 0.2 mass%.
  • the content of boric acid triester in the non-aqueous electrolyte used in the non-aqueous secondary battery is preferably 1% by mass or less, and more preferably 0.8% by mass or less.
  • the organic solvent related to the non-aqueous electrolyte is not particularly limited.
  • chain esters such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methyl propyl carbonate; ethylene carbonate, propylene carbonate, butylene carbonate, vinylene
  • a cyclic ester having a high dielectric constant such as carbonate; a mixed solvent of a chain ester and a cyclic ester; and the like.
  • a mixed solvent with a cyclic ester having a chain ester as a main solvent is suitable.
  • non-aqueous electrolyte electrolyte salt to be dissolved in the organic solvent
  • Li 2 C 2 F 4 (SO 3 ) 2 LiC n F 2n + 1 SO 3 (2 ⁇ n ⁇ 7)
  • LiN (RfSO 2 ) (Rf′SO 2 ) LiC (RfSO 2 ) 3
  • LiN (RfOSO 2 ) 2 [Wherein Rf and Rf ′ each represents a fluoroalkyl group. ] Are used alone or in admixture of two or more.
  • the concentration of the electrolyte salt in the nonaqueous electrolyte is not particularly limited, but is preferably 0.3 mol / L or more, more preferably 0.4 mol / L or more, and 1.7 mol. / L or less is preferable, and 1.5 mol / L or less is more preferable.
  • non-aqueous secondary battery of the present invention in addition to the liquid electrolyte (non-aqueous electrolyte), a gel electrolyte obtained by gelling the non-aqueous electrolyte with a gelling agent composed of a polymer or the like is also included. Can be used.
  • Non-aqueous secondary battery of the present invention for example, a tubular shape (such as a square tubular shape or a cylindrical shape) using a steel can, an aluminum can, or the like as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
  • FIG. 1A is a plan view showing an example of the non-aqueous secondary battery of the present invention
  • FIG. 1B is a cross-sectional view of FIG. 1A
  • 2 is a perspective view of the nonaqueous secondary battery of the present invention shown in FIGS. 1A and 1B.
  • the positive electrode 1 and the negative electrode 2 are wound in a spiral shape via a separator 3 and then pressed so as to become a flat shape to form a flat wound electrode body 6 as a rectangular tube-shaped exterior.
  • the can 4 is accommodated together with a non-aqueous electrolyte.
  • the metal foil, the non-aqueous electrolyte, and the like as the current collector used in the production of the positive electrode 1 and the negative electrode 2 are not illustrated, and the winding electrode body 6
  • the inner peripheral portion is not cross-sectional.
  • the outer can 4 is made of an aluminum alloy and constitutes an outer casing of the battery.
  • the outer can 4 also serves as a positive electrode terminal.
  • the insulator 5 which consists of a polyethylene sheet is arrange
  • the positive electrode lead body 7 and the negative electrode lead body 8 are drawn out.
  • a stainless steel terminal 11 is attached to a sealing lid plate 9 made of aluminum alloy for sealing the opening of the outer can 4 via a polypropylene insulating packing 10, and an insulator 12 is attached to the terminal 11.
  • a stainless steel lead plate 13 is attached via
  • the cover plate 9 is inserted into the opening of the outer can 4 and welded to join the opening of the outer can 4 to seal the inside of the battery.
  • a non-aqueous electrolyte inlet 14 is provided in the lid plate 9, and a sealing member is inserted into the non-aqueous electrolyte inlet 14, for example, a laser.
  • the battery is hermetically sealed by welding or the like, so that the battery is sealed. Therefore, in the batteries of FIGS. 1A, 1B and 2, the non-aqueous electrolyte inlet 14 is actually a non-aqueous electrolyte inlet and a sealing member. An electrolyte inlet 14 is shown.
  • the lid plate 9 is provided with a cleavage vent 15 as a mechanism for discharging the internal gas to the outside when the temperature of the battery rises.
  • the outer can 4 and the lid plate 9 function as a positive electrode terminal, and the negative electrode lead body 8 is welded to the lead plate 13.
  • the terminal 11 functions as a negative electrode terminal by connecting the negative electrode lead body 8 and the terminal 11 to each other.
  • the sign may be reversed depending on the material of the outer can 4, the sign may be reversed.
  • FIG. 3 is a plan view showing another example of the nonaqueous secondary battery of the present invention.
  • the positive electrode, the negative electrode, and the nonaqueous electrolyte are accommodated in an outer package 21 made of an aluminum laminate film that is rectangular in plan view.
  • the positive external terminal 22 and the negative external terminal 23 are drawn from the same side of the exterior body 21.
  • the non-aqueous secondary battery of the present invention can exhibit excellent charge / discharge cycle characteristics even when high voltage charging is performed.
  • the battery of the present invention makes use of such characteristics, and power sources for various devices such as electronic devices (especially portable electronic devices such as mobile phones and notebook personal computers), power supply systems, vehicles (electric cars, electric bicycles, etc.). It can be preferably used for applications.
  • Example 1 ⁇ Preparation of positive electrode> LiNi 0.5 Mn 1.5 O 4 which is a positive electrode active material [corresponding to the Li-containing composite oxide represented by the above general formula (1), average particle size: 15 ⁇ m]: 85 parts by mass, a conductive additive Acetylene black (average particle size: 50 nm): 10 parts by mass and PVDF: 5 parts by mass as a binder were mixed to prepare a positive electrode mixture, and this was dispersed in NMP to prepare a positive electrode mixture-containing paste. .
  • This positive electrode mixture-containing paste is applied to one side of a current collector made of an aluminum foil having a thickness of 15 ⁇ m, dried to form a positive electrode mixture layer, pressed, and then dried at 120 ° C.
  • the positive electrode sheet material was punched into a circle having a diameter of 13 mm to obtain a positive electrode.
  • the positive electrode mixture layer had a thickness of 60 ⁇ m, and the amount of the positive electrode active material excluding the conductive additive and binder in the positive electrode mixture layer was 15 mg / cm 2 .
  • SiO particles having a structure in which Si was dispersed in an amorphous SiO 2 matrix and having a molar ratio of SiO 2 to Si of 1: 1 were coated with a carbon material by a CVD method to obtain a negative electrode active material.
  • Carbon coated SiO (average particle size: 5 ⁇ m): 82 parts by mass, Ketjen black (average particle size 40 nm) as a conductive auxiliary agent: 10 parts by mass, PVDF as a binder: 8 parts by mass
  • a negative electrode mixture-containing paste was prepared by dispersing it in NMP as a negative electrode mixture.
  • the ratio (mass ratio) between SiO and the carbon material determined from the mass change before and after the CVD method was 80:20.
  • the negative electrode mixture-containing paste is applied to one side of a current collector made of a copper foil having a thickness of 15 ⁇ m, dried to form a negative electrode mixture layer, pressed, and dried at 120 ° C. to obtain a negative electrode sheet material. It was. This negative electrode sheet material was punched into a circle having a diameter of 14 mm to form a negative electrode.
  • the thickness of the negative electrode mixture layer was 25 ⁇ m, and the amount of the negative electrode active material excluding the conductive additive and the binder in the negative electrode mixture layer was 3 mg / cm 2 .
  • ⁇ Battery assembly> The battery was assembled in an argon glove box.
  • a porous polyethylene film (thickness: 16 ⁇ m) was used.
  • the above-mentioned non-aqueous electrolyte in which a “HS flat cell” manufactured by Hosen Co., Ltd. is used as the battery outer package, and a laminate in which the positive electrode, the separator, and the negative electrode are stacked in this order is accommodated in the outer package, and then FEC and TEB are added. was injected at 100 ⁇ L. Then, the exterior body was sealed and the non-aqueous secondary battery was produced.
  • the initial characteristics and charge / discharge cycle characteristics were evaluated as charge / discharge characteristics of the non-aqueous secondary battery by the following method.
  • the non-aqueous secondary battery is charged at a constant current of 0.2 mA / cm 2 in a 25 ° C. environment until the battery voltage reaches 5 V, and then the battery voltage is adjusted at a constant current of 0.2 mA / cm 2. It discharged until it became 3.0V. This series of operations was repeated 5 cycles, and the discharge capacity at the 5th cycle was defined as the initial discharge capacity.
  • the non-aqueous secondary battery whose initial characteristics have been measured is charged at a constant current of 1 mA / cm 2 in a 25 ° C. environment until the battery voltage reaches 4.85 V (charge end voltage), and then 1 mA / cm.
  • the battery was discharged at a constant current of 2 until the battery voltage reached 3.0 V (discharge end voltage). This series of operations was repeated as 100 cycles for 100 cycles.
  • the battery charged and discharged for 100 cycles was charged with a constant current of 0.2 mA / cm 2 until the battery voltage reached 5 V, and then the battery voltage was 3.0 V with a constant current of 0.2 mA / cm 2.
  • the discharge capacity was taken as the discharge capacity after the charge / discharge cycle.
  • the initial discharge capacity measured as the initial characteristic is defined as the discharge capacity before the charge / discharge cycle, and the ratio of the discharge capacity after the charge / discharge cycle to the discharge capacity before the charge / discharge cycle is expressed as a percentage. Asked.
  • Example 2 Except for changing the positive electrode active material to LiNi 0.5 Co 0.2 Mn 0.3 O 2 [corresponding to the Li-containing composite oxide represented by the above general formula (2), average particle size: 10 ⁇ m]
  • a positive electrode was produced in the same manner as in Example 1.
  • the amount of the positive electrode active material excluding the conductive additive and binder in the positive electrode mixture layer of this positive electrode was 10 mg / cm 2 .
  • the non-aqueous secondary battery was produced like Example 1 except having used this positive electrode.
  • charge / discharge cycle characteristics were performed in the same manner as the non-aqueous secondary battery of Example 1 except that the charge end voltage was 4.6 V and the discharge end voltage was 2.5 V. Rate).
  • Example 1 A nonaqueous electrolyte was prepared in the same manner as in Example 1 except that TEB was not added, and a nonaqueous secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used. And about this non-aqueous secondary battery, the charge / discharge cycle characteristic (capacity maintenance factor) was evaluated by the same method as the non-aqueous secondary battery of Example 1.
  • Example 2 A nonaqueous electrolyte was prepared in the same manner as in Example 1 except that FEC was not added, and a nonaqueous secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used. And about this non-aqueous secondary battery, the charge / discharge cycle characteristic (capacity maintenance factor) was evaluated by the same method as the non-aqueous secondary battery of Example 1.
  • Table 1 shows the measurement results of the capacity retention ratio before and after the charge / discharge cycle in the nonaqueous secondary batteries of Examples 1 and 2 and Comparative Examples 1 and 2.
  • the non-aqueous secondary batteries of Examples 1 and 2 using a non-aqueous electrolyte containing a halogen-substituted cyclic carbonate and a boric acid triester include a negative electrode using SiO x as a negative electrode active material, A positive electrode having a Li-containing composite oxide represented by the general formula (1) or a Li-containing composite oxide represented by the general formula (2) as a positive electrode active material, and having a high potential. It can be seen that the capacity retention rate before and after the charging / discharging cycle is high even when charging / discharging is performed, and good charging / discharging cycle characteristics can be secured.

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JP2013131486A (ja) * 2011-11-24 2013-07-04 Toyota Industries Corp リチウムイオン二次電池
CN103311571A (zh) * 2013-05-21 2013-09-18 东莞新能源科技有限公司 锂离子二次电池及其电解液
JP2016186854A (ja) * 2015-03-27 2016-10-27 日本電気株式会社 リチウムイオン二次電池用正極およびその製造方法、並びにリチウムイオン二次電池
JP2019040701A (ja) * 2017-08-23 2019-03-14 三洋電機株式会社 非水電解質二次電池
JP2019160789A (ja) * 2018-03-08 2019-09-19 三洋化成工業株式会社 リチウムイオン電池用負極及びリチウムイオン電池

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CN104051784A (zh) * 2014-07-02 2014-09-17 东莞市凯欣电池材料有限公司 锂二次电池电解液及其制备方法以及锂二次电池
JP6396136B2 (ja) * 2014-09-18 2018-09-26 マクセルホールディングス株式会社 リチウム二次電池
CN105244540A (zh) * 2015-11-13 2016-01-13 华南师范大学 一种含硼酸三乙酯添加剂的电解液及其制备方法与应用
CN105390747A (zh) * 2015-11-13 2016-03-09 华南师范大学 一种含硼酸三甲酯添加剂的电解液及其制备方法与应用
CN105633464A (zh) * 2016-03-09 2016-06-01 华南师范大学 一种含硼酸三甲酯添加剂的高压功能电解液及其制备与应用
CN106207122A (zh) * 2016-08-12 2016-12-07 联想(北京)有限公司 聚合物锂离子电池负极材料以及聚合物锂离子电池和电子设备
WO2018139065A1 (ja) * 2017-01-30 2018-08-02 パナソニック株式会社 非水電解質二次電池

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JP2013131486A (ja) * 2011-11-24 2013-07-04 Toyota Industries Corp リチウムイオン二次電池
CN103311571A (zh) * 2013-05-21 2013-09-18 东莞新能源科技有限公司 锂离子二次电池及其电解液
JP2016186854A (ja) * 2015-03-27 2016-10-27 日本電気株式会社 リチウムイオン二次電池用正極およびその製造方法、並びにリチウムイオン二次電池
JP2019040701A (ja) * 2017-08-23 2019-03-14 三洋電機株式会社 非水電解質二次電池
JP2019160789A (ja) * 2018-03-08 2019-09-19 三洋化成工業株式会社 リチウムイオン電池用負極及びリチウムイオン電池
JP7356232B2 (ja) 2018-03-08 2023-10-04 三洋化成工業株式会社 リチウムイオン電池用負極及びリチウムイオン電池

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