WO2013088622A1 - Batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion Download PDF

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Publication number
WO2013088622A1
WO2013088622A1 PCT/JP2012/006716 JP2012006716W WO2013088622A1 WO 2013088622 A1 WO2013088622 A1 WO 2013088622A1 JP 2012006716 W JP2012006716 W JP 2012006716W WO 2013088622 A1 WO2013088622 A1 WO 2013088622A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
ion secondary
lithium
lithium ion
active material
Prior art date
Application number
PCT/JP2012/006716
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English (en)
Japanese (ja)
Inventor
昌洋 木下
名倉　健祐
Original Assignee
パナソニック株式会社
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Filing date
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Publication of WO2013088622A1 publication Critical patent/WO2013088622A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 lithium ion secondary battery having a high set voltage for the end-of-charge voltage.
  • Lithium ion secondary batteries are widely used as drive power sources for portable electronic devices and communication devices.
  • a carbon material capable of inserting and extracting lithium is used for a negative electrode, and a composite oxide of a transition metal such as LiMnO 2 and lithium is used as an active material for a positive electrode.
  • High power and high capacity secondary batteries have been realized.
  • a typical lithium ion secondary battery has a configuration in which an electrode group in which a positive electrode and a negative electrode are wound through a separator is housed in a battery case together with a nonaqueous electrolyte.
  • the nonaqueous electrolyte dissolves a solute composed of a lithium salt such as LiPF 6 or LiBF 4 in a nonaqueous solvent composed of a carbonate such as ethylene carbonate (EC), dimethyl carbonate (DMC), or diethyl carbonate (DEC). Is used.
  • a lithium salt such as LiPF 6 or LiBF 4
  • a nonaqueous solvent composed of a carbonate such as ethylene carbonate (EC), dimethyl carbonate (DMC), or diethyl carbonate (DEC).
  • the conventional non-aqueous solvent comprising a carbonate ester has low oxidation resistance, the non-aqueous solvent is decomposed and a film is formed on the positive electrode, thereby increasing internal resistance and reducing cycle characteristics. There is a problem.
  • Patent Document 1 describes that a nonaqueous solvent containing a fluorinated carboxylic acid ester is used as the nonaqueous solvent.
  • the non-aqueous solvent containing the fluorinated carboxylic acid ester is highly resistant to oxidation and thus is not easily decomposed. For this reason, it is possible to suppress a decrease in cycle characteristics due to film formation on the positive electrode.
  • the end-of-charge voltage of a lithium ion secondary battery is set to 4.1 to 4.2V. If the end-of-charge voltage can be increased to 4.2V or more, the capacity of the lithium ion secondary battery is increased. Can be made.
  • the inventors of the present application have evaluated the characteristics of a lithium ion secondary battery produced using a nonaqueous solvent containing a fluorinated carboxylic acid ester by increasing the end-of-charge voltage to 4.2 V or higher. It was found that the cycle characteristics deteriorated.
  • the present invention has been made in view of such a problem, and a main object thereof is to provide a lithium ion secondary battery with little deterioration in cycle characteristics even when the end-of-charge voltage is increased to 4.2 V or higher.
  • a lithium ion secondary battery according to the present invention is a lithium ion secondary battery including a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte
  • the negative electrode is a negative electrode active material made of a carbon material formed on a current collector.
  • the nonaqueous electrolyte includes a solute composed of a lithium salt and fluorine represented by the following formula: And a non-aqueous solvent comprising a carboxylic acid ester.
  • the metal oxide is preferably made of lithium titanate.
  • the present invention it is possible to provide a lithium ion secondary battery with little deterioration in cycle characteristics even when the end-of-charge voltage is increased to 4.2 V or higher.
  • (A), (b) is sectional drawing explaining the state when the metal eluted from the positive electrode active material deposited on the negative electrode surface. It is sectional drawing which showed the structure of the lithium ion secondary battery in one Embodiment of this invention. It is sectional drawing which showed the structure of the negative electrode in one Embodiment of this invention. (A), (b) is sectional drawing explaining the state when the metal eluted from the positive electrode active material deposited on the negative electrode surface in this invention.
  • Table 1 shows a mixed solvent (mass ratio 1: 1) of ethylene carbonate (EC) and dimethyl carbonate (DMC) and a mixed solvent of ethylene carbonate (EC) and a fluorinated carboxylic acid ester (non-aqueous solvent).
  • Cycle characteristics (capacity retention rate) when lithium ion secondary batteries (battery 1 to battery 6) were prepared using mass ratios 1: 1) and the end-of-charge voltage was changed to 4.1 to 4.4V. ) Shows the measurement results.
  • fluoromethyl propionate methyl 3,3,3-trifluoropropionate CAS: 18830-44-9; FMP
  • FMP fluorinated carboxylic acid ester.
  • LiNi 0.5 Mn 0.5 O 2 was used as the positive electrode active material
  • artificial graphite as the carbon material was used as the negative electrode active material
  • LiPF 6 was used as the nonaqueous electrolyte.
  • the cycle characteristics were evaluated as follows. First, in an environment of 25 ° C., after constant current charging at 0.2 C to the end-of-charge voltage (4.1 to 4.4 V), constant-voltage charging to the end current of 0.05 C, and then at 2 C at 2 C . Constant current discharge to 5V. This charging / discharging was performed 100 cycles, and the ratio of the discharge capacity after 100 cycles to the discharge capacity at the first cycle (capacity maintenance ratio) was determined to evaluate the cycle characteristics.
  • the capacity retention ratio is about 3 even when the end-of-charge voltage is increased from 4.1 V to 4.4 V.
  • the end-of-charge voltage is increased from 4.1 V to 4.4 V. It can be seen that the capacity retention rate has decreased by about 24%.
  • the fluorinated carboxylic acid ester used in the batteries 4 to 6 has a structure represented by the following formula (1).
  • H 2 (proton) bonded to C ( ⁇ O) is adjacent to C having an F group with high electronegativity, and the charge is attracted, while the opposite carbonyl group is conjugated. Since it becomes a structure and electrons are delocalized, it is stabilized in a state where protons are desorbed. Therefore, when the end-of-charge voltage is set to 4.1 V or more, protons are easily released from the nonaqueous solvent.
  • Protons released from the nonaqueous solvent react with the positive electrode active material (LiNi 0.5 Mn 0.5 O 2 ), and the elution of metal (for example, Mn 2+ ) from the positive electrode active material is accelerated.
  • the metal (Mn 2+ ) eluted from the positive electrode active material is deposited on the surface of the active material layer 11 formed on the current collector 10 of the negative electrode, and FIG. As shown in FIG. 2, a film 20 is formed on the surface of the active material layer 11.
  • the metal in the coating 20 (Mn 2+) by binding with lithium occluded in the active material layer 11 (Li +), lithium in the active material layer 11 (Li +) is decreased.
  • the battery whose cycle characteristics were evaluated was disassembled, and the amount of Li present in the coating 20 on the negative electrode surface was measured.
  • the amount of Li was measured by the following method. First, the battery was disassembled in a state where the battery was discharged to 2.5 V, and a cell in which the extracted negative electrode and Li metal were combined was produced. After this cell was charged to 1.5 V at 0.01 C, the cell was again disassembled and the negative electrode was taken out. An acid was added to the extracted negative electrode to dissolve it, and the amount of remaining Li was measured using an ICP-MS (inductively coupled plasma mass spectrometry) method. The results are shown in Table 2.
  • ICP-MS inductively coupled plasma mass spectrometry
  • the present inventors have been able to suppress the reaction between the metal (Mn 2+ ) eluted from the positive electrode active material and the lithium (Li + ) occluded in the negative electrode active material. Even if the voltage is increased to 4.2 V or higher, it is considered that the decrease in cycle characteristics (capacity maintenance ratio) can be suppressed, and the present invention has been conceived.
  • FIG. 2 is a cross-sectional view showing the configuration of the lithium ion secondary battery 100 in one embodiment of the present invention.
  • an electrode group 4 in which a positive electrode 1 and a negative electrode 2 are wound through a separator 3 is accommodated in a cylindrical battery case 7 together with a nonaqueous electrolyte (not shown).
  • the positive electrode 1 is joined to a sealing body 8 that also serves as a positive electrode terminal via a positive electrode lead 5
  • the negative electrode 2 is joined to the bottom of a battery case 7 that also serves as a negative electrode terminal via a negative electrode lead 6.
  • the opening of the battery case 7 is sealed with a sealing body 8 via a gasket 9.
  • the lithium ion secondary battery 100 according to the present invention is not particularly limited with respect to the other components constituting the lithium ion secondary battery, except for the non-aqueous electrolyte material described later and the configuration of the negative electrode 2.
  • the member used etc. can be used.
  • the lithium ion secondary battery 100 in the present invention is not limited to a cylindrical secondary battery, and may be, for example, a square secondary battery.
  • the electrode group 4 may be one in which the positive electrode 1 and the negative electrode 2 are laminated via the separator 3.
  • the non-aqueous electrolyte in the present invention is formed by dissolving a solute composed of a lithium salt such as LiPF 6 or LiBF 4 in a non-aqueous solvent containing a fluorinated carboxylic acid ester.
  • the fluorinated carboxylic acid ester has a structure represented by the above formula (1).
  • the non-aqueous solvent may be a mixed solvent containing other solvents such as ethylene carbonate (EC). In that case, the mixing ratio of the fluorinated carboxylic acid ester and the other solvent in the mixed solvent can be appropriately determined within the range where the effects of the present invention are exhibited.
  • FIG. 3 is a cross-sectional view showing the configuration of the negative electrode 2 in the present embodiment.
  • the negative electrode 2 includes a current collector 10, an active material layer 11 containing an active material formed on the current collector 10, and lithium ions formed on the active material layer 11. And a protective layer 12 containing a metal oxide capable of occluding and releasing.
  • the active material contained in the active material layer 11 is made of a carbon material, and examples thereof include graphite, carbon black, acetylene black, and carbon fiber.
  • the metal oxide contained in the protective layer 12 include molybdenum oxide in addition to lithium titanate (LixTiyOz: LTO).
  • the active material layer 11 may contain a predetermined amount of a binder.
  • the binder include polyvinylidene fluoride (PVDF), fluorine-based rubber, styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), acrylic rubber (ACM), and the like.
  • the protective layer 12 may contain a predetermined amount of a conductive agent and a binder.
  • a conductive agent include carbon materials such as graphite.
  • the binder include polyvinylidene fluoride (PVDF), fluorine rubber, styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), and acrylic rubber (ACM).
  • the current collector 10 can be made of, for example, a copper foil or a copper alloy foil.
  • the protective layer 12 since the protective layer 12 includes a metal oxide capable of inserting and extracting lithium ions, it also functions as an active material layer. However, since the metal oxide contained in the protective layer 12 is generally made of a material having lower conductivity and smaller capacity than the carbon material contained in the active material layer 11, The protective layer 12 is distinguished from the layer 11.
  • Table 3 shows a lithium non-aqueous solvent using a mixed solvent of ethylene carbonate (EC) and fluorinated carboxylic acid ester (FMP) (mass ratio 1: 1) and having the negative electrode 2 having the structure shown in FIG. Results of measurement of cycle characteristics (capacity retention ratio) and the amount of Li on the negative electrode surface when an ion secondary battery (batteries 7 and 8) was prepared and the end-of-charge voltage was changed to 4.2 to 4.3 V Is shown.
  • the batteries 5 and 6 shown in Table 2 are listed for comparison.
  • the negative electrode 2 used for the batteries 5 and 6 has a structure in which an active material layer 11 made of artificial graphite (C) is formed on the current collector 10, and the positive electrode active material used for the batteries 7 and 8 is Same as batteries 5 and 6.
  • the protective layer 12 made of LTO formed on the surface of the active material layer 11 contains the metal (Mn 2+ ) eluted from the positive electrode active material and the active material layer 11. This is thought to be because the reaction with the occluded lithium (Li + ) was suppressed.
  • FIG. 4B the decrease in lithium (Li + ) occluded in the active material layer 11 is suppressed, and even when the end-of-charge voltage is increased to 4.2 V or more, the capacity retention rate is reduced. It is thought that the decrease could be suppressed.
  • LTO has the property of occluding and releasing lithium, like the carbon material (C), and therefore, lithium (Li + ) is also occluded in the protective layer 12.
  • the crystal structure of LTO has a spinel structure, and the activation energy of lithium is lower than that of the layered crystal carbon material (C). Therefore, even if metal (Mn 2+ ) is deposited on the surface of the protective layer 12, it is difficult to bond with lithium (Li + ) occluded in the protective layer 12, so that the metal (Mn 2+ ) and lithium (Li + ) It is thought that the reaction with was able to be suppressed.
  • the negative electrode 2 As described above, in the lithium ion secondary battery including the nonaqueous electrolyte including the solute composed of the lithium salt and the nonaqueous solvent composed of the fluorinated carboxylic acid ester represented by the above formula (1), the negative electrode 2
  • the active material layer 11 made of a carbon material formed on the current collector 10 and the protective layer 12 formed on the active material layer 11 and containing a metal oxide capable of inserting and extracting lithium ions.
  • the metal oxide is made of a material whose activation energy of lithium is lower than that of the carbon material constituting the active material layer 11, and typically, lithium titanate is preferably used.
  • the present invention is particularly effective when the positive electrode 1 having a positive electrode active material layer made of a lithium-containing metal oxide containing Mn or Fe is used. This is because the lithium-containing metal oxide containing Mn or Fe is likely to react with protons that are released from the non-aqueous solvent.
  • the thickness of the protective layer 12 is preferably in the range of 1 to 20 ⁇ m. If it is thinner than 1 ⁇ m, the effect of suppressing the reaction between the metal (Mn 2+ ) and lithium (Li + ) is not sufficiently exhibited. On the other hand, when it is thicker than 20 ⁇ m, LTO has a lower conductivity and a smaller capacity than a carbon material, leading to a decrease in discharge performance of the lithium ion battery.
  • the active material layer 11 and the protective layer 12 are formed on one surface of the current collector 10 in the above embodiment, the negative electrode 2 may be formed on both surfaces of the current collector 10.
  • the present invention is useful as a power source for driving automobiles, electric motorcycles, electric playground equipment and the like.

Abstract

La présente invention vise à proposer une batterie secondaire au lithium-ion qui présente une faible diminution dans les propriétés de cycle même lorsqu'une tension finale de charge est augmentée à 4,2 V ou plus. La présente invention est une batterie secondaire au lithium-ion équipée d'une électrode positive (1), d'une électrode négative (2), d'un séparateur (3) et d'un électrolyte non aqueux, dans laquelle : l'électrode négative (2) contient une couche de matériau active (11) comprenant un matériau carboné et formée sur un collecteur de courant (10), et une couche de protection (12) contenant un oxyde métallique apte à absorber et de décharger des ions de lithium, et formée sur la couche de matériau active (11) ; et l'électrolyte non aqueux contient un soluté contenant un sel de lithium, et un solvant non aqueux contenant un ester d'acide carboxylique fluoré représenté par cette formule. CFxH3-x-CH2-C(=O)-OR (1 ≤ x ≤ 3 ; R représentant un groupe alkyle)
PCT/JP2012/006716 2011-12-14 2012-10-19 Batterie secondaire au lithium-ion WO2013088622A1 (fr)

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JP2011-273415 2011-12-14
JP2011273415 2011-12-14

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103762335A (zh) * 2013-12-30 2014-04-30 曙鹏科技（深圳）有限公司 钛酸锂电极片及锂离子电池
WO2015004841A1 (fr) * 2013-07-08 2015-01-15 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
WO2023025067A1 (fr) * 2021-08-27 2023-03-02 深圳市原速光电科技有限公司 Couche de protection d'électrode, son procédé de préparation et son utilisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11120992A (ja) * 1997-10-08 1999-04-30 Ricoh Co Ltd 非水電解質二次電池
JP2006294469A (ja) * 2005-04-12 2006-10-26 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP2009289414A (ja) * 2007-02-20 2009-12-10 Sanyo Electric Co Ltd 二次電池用非水電解液及び非水電解液二次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11120992A (ja) * 1997-10-08 1999-04-30 Ricoh Co Ltd 非水電解質二次電池
JP2006294469A (ja) * 2005-04-12 2006-10-26 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP2009289414A (ja) * 2007-02-20 2009-12-10 Sanyo Electric Co Ltd 二次電池用非水電解液及び非水電解液二次電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015004841A1 (fr) * 2013-07-08 2015-01-15 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
CN105122533A (zh) * 2013-07-08 2015-12-02 松下电器产业株式会社 非水电解质二次电池
CN103762335A (zh) * 2013-12-30 2014-04-30 曙鹏科技（深圳）有限公司 钛酸锂电极片及锂离子电池
WO2023025067A1 (fr) * 2021-08-27 2023-03-02 深圳市原速光电科技有限公司 Couche de protection d'électrode, son procédé de préparation et son utilisation

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