WO2013069622A1 - Secondary cell - Google Patents

Secondary cell Download PDF

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Publication number
WO2013069622A1
WO2013069622A1 PCT/JP2012/078693 JP2012078693W WO2013069622A1 WO 2013069622 A1 WO2013069622 A1 WO 2013069622A1 JP 2012078693 W JP2012078693 W JP 2012078693W WO 2013069622 A1 WO2013069622 A1 WO 2013069622A1
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WO
WIPO (PCT)
Prior art keywords
additive
secondary battery
internal pressure
end side
electrolyte
Prior art date
Application number
PCT/JP2012/078693
Other languages
French (fr)
Japanese (ja)
Inventor
晃一 谷山
拓也 宮下
耕嗣 北田
恭平 下山
健治 酒井
Original Assignee
三菱自動車工業株式会社
三菱自動車エンジニアリング株式会社
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Publication date
Application filed by 三菱自動車工業株式会社, 三菱自動車エンジニアリング株式会社 filed Critical 三菱自動車工業株式会社
Priority to KR1020147015103A priority Critical patent/KR101571988B1/en
Priority to CN201280055371.9A priority patent/CN103931041B/en
Publication of WO2013069622A1 publication Critical patent/WO2013069622A1/en

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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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a secondary battery.
  • a rechargeable lithium ion secondary battery is used as a drive battery mounted on such an electric vehicle.
  • VC vinylene carbonate
  • Patent Document 1 VC is added and the film (henceforth a VC film) by VC is formed in an electrode surface, it has suppressed that SEI is formed too much. However, the VC film is gradually peeled off by the expansion and contraction of the electrode body.
  • this VC is put into a capsule so that VC can be gradually added to the electrolyte with the passage of time, and the VC film peeled off by expansion and contraction is continuously regenerated. Control the formation of As a result, deterioration of the battery is suppressed.
  • Patent Document 1 since the capsule is a sustained release capsule and VC is gradually released with the passage of time, it is possible to recover the deterioration in the use state where the battery is deteriorated with the passage of time, which is effective. There is also.
  • an object of the present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a secondary battery capable of effectively suppressing the deterioration of the battery without adding an additive excessively.
  • the secondary battery of the present invention is a secondary battery comprising a battery case, an electrode body housed inside the battery case, and an electrolytic solution filled in the battery case, containing an initial additive.
  • the electrode body is characterized in that an adding means for adding a recovery additive for recovering the deteriorated state according to the deteriorated state of the film formed by the initial additive is provided to the electrolytic solution.
  • recovery of the degradation state refers to recovery of the degradation state of the battery due to peeling off of the film from the electrode due to expansion and contraction.
  • the addition means adds the additive to the electrolytic solution when the internal pressure in the battery case due to the deterioration of the secondary battery rises to a predetermined value or more. That is, the deterioration of the battery can be more effectively suppressed by detecting the deterioration of the battery by the increase in internal pressure and adding the additive to the electrolytic solution.
  • the predetermined value is larger than the internal pressure change due to expansion and contraction during charge and discharge of the electrode body.
  • the addition means has a separation means for separating the additive from the electrolytic solution, and the separation means releases the additive to the electrolytic solution by being deformed according to the internal pressure.
  • the separation means releases the additive to the electrolytic solution by being deformed according to the internal pressure.
  • the addition means is a capsule as the separation means containing the additive, and the wall surface of the capsule is broken when the internal pressure reaches a predetermined value or more, and the additive is added to the electrolytic solution. Is preferred. By using such an addition means, an additive for recovering the deteriorated state can be easily added according to the deteriorated state.
  • the addition means is fitted in a tubular member whose one end side is sealed and the other end side is opened, and a hollow portion of the tubular member, and the hollow portion is moved to the one end side by the increase of the internal pressure And a storage unit in communication with the opening provided at one end side of the initial installation position of the moving unit of the cylindrical member, the storage unit containing the additive, It is preferable that the moving part move by the rising to add the additive to the electrolytic solution.
  • an air reservoir part is formed in the said one end side of the said cylindrical member as the said addition means.
  • the additive can be added according to the deterioration state, and the excellent effect that the deterioration of the battery can be effectively suppressed can be exhibited.
  • FIG. 1 is a perspective view of a secondary battery according to a first embodiment.
  • FIG. 1 is a cross-sectional view of a secondary battery according to Embodiment 1.
  • FIG. 6 is a cross-sectional view of a secondary battery according to a second embodiment.
  • FIG. 7 is a schematic view of an addition device according to Embodiment 3. It is a schematic diagram of the addition apparatus concerning another embodiment.
  • FIG. 1 is a perspective view showing a secondary battery according to the present embodiment
  • FIG. 2 (1) is a cross-sectional view taken along the line AA 'of FIG. 1
  • FIG. 2 (2) is B of FIG. It is sectional drawing in-B 'line.
  • the secondary battery 1 includes a substantially rectangular case 11 and a lid 12 disposed at the opening of the case 11 to seal the case 11.
  • the electrode body 13 is housed in the case 11. Further, the inside of the case 11 is filled with the electrolytic solution 14, and the electrode body 13 is immersed in the electrolytic solution 14.
  • the electrode body 13 is formed by winding a laminate of a positive electrode plate and a negative electrode plate with a separator interposed therebetween, and the lamination direction is the lateral direction in the drawing.
  • the lid 12 is provided with a positive electrode terminal 15 and a negative electrode terminal 16.
  • the positive electrode current collector 17 is connected to the positive electrode terminal 15.
  • a negative electrode current collector 18 is connected to the negative electrode terminal 16.
  • the positive electrode current collecting unit 17 and the negative electrode current collecting unit 18 are connected to the positive electrode plate and the negative electrode plate of the electrode body 13 respectively. That is, the positive electrode plate, the positive electrode current collecting portion 17 and the positive electrode terminal 15 are electrically connected to each other. Further, the negative electrode plate, the negative electrode current collector portion 18 and the negative electrode terminal 16 are electrically connected to each other.
  • the positive electrode plate is made of a commonly used positive electrode material.
  • Commonly used positive electrode materials include, for example, metal oxides capable of absorbing and desorbing lithium, such as metal oxides of layered structure type, spinel type metal oxides and metal compounds, metal salts of oxide salt type, etc.
  • the layered structure type metal oxide may, for example, be a lithium nickel composite oxide, a lithium cobalt composite oxide, or a ternary composite oxide (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 ).
  • lithium nickel oxide (LiNiO 2 ) is mentioned as the lithium nickel composite oxide.
  • the lithium cobalt-based composite oxide preferably includes lithium cobaltate (LiCoO 2 ).
  • the spinel-type metal oxides lithium-manganese-based composite oxide such as lithium manganate (LiMn 2 O 4) can be mentioned.
  • the oxide salt type metal oxide include lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium silicon phosphate and the like.
  • the negative electrode plate is made of a commonly used negative electrode active material.
  • the negative electrode active material include commonly used active materials such as metal lithium, lithium alloy, metal oxide, metal sulfide, metal nitride, and carbon materials such as graphite.
  • the metal oxide include those having irreversible capacity such as tin oxide and silicon oxide.
  • the graphite as the carbon-based material may be artificial graphite or natural graphite, and in the present embodiment, graphite is used as the active material of the negative electrode.
  • Each of the positive electrode plate and the negative electrode plate may further contain a binder, and for example, polyvinylidene fluoride can be used.
  • the active material layer may contain a conductivity improver such as acetylene black, an electrolyte (for example, a lithium salt (supporting electrolyte), an ion conductive polymer, etc.).
  • a polymerization initiator for polymerizing the polymer may be included.
  • the electrolyte solution 14 is a mixed solution of a commonly used electrolyte, for example, ethylene carbonate and propylene carbonate which are cyclic carbonates, and linear carbonates, and 1 mol of LiPF 6 in a mixed solution of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • the organic electrolyte solution melt
  • vinylene carbonate (VC) is added to the electrolytic solution 14 as an initial additive.
  • the electrolyte solution 14 contains capsules 3 and 3A in which a recovery additive (hereinafter, also simply referred to as an additive) for recovering the film on the surface of the electrode is enclosed.
  • a recovery additive hereinafter, also simply referred to as an additive
  • the additive sealed therein is released, so that the deterioration of the battery can be suppressed.
  • the capsules 3 and 3A are made of a resin insoluble in the electrolyte, and their thicknesses are set so as to break when a predetermined pressure is applied.
  • the capsule 3A is thicker than the capsule 3 and is hard to break.
  • the secondary battery is used, and when lithium ions intercalate in the carbon electrode, lithium ions react with the electrolyte to generate a gas, whereby a solid electrolyte interface layer (SEI) is formed on the surface of the electrode. It is formed. SEI is necessary to stably charge and discharge at the time of initial operation of the secondary battery, but it is a lithium ion that can move between the positive electrode and the negative electrode in a state where SEI continues to be formed thereafter. And the battery capacity is likely to be reduced (deteriorated state).
  • SEI solid electrolyte interface layer
  • VC vinylene carbonate
  • VC vinylene carbonate
  • the use of a secondary battery causes the VC film to peel off from the electrode surface due to expansion and contraction of the electrode.
  • SEI is likely to be formed at the peeled portion, and as a result, lithium ions which can move between the positive electrode and the negative electrode may be reduced to reduce the battery capacity.
  • VC is excessively added in advance in the secondary battery, the VC film may become too thick and internal resistance may increase.
  • the capsules 3 and 3A as an addition means for adding an additive according to the deterioration state of the secondary battery 1, that is, according to the increase in internal pressure, are contained in the electrolyte solution 14 in the secondary battery 1. It is contained.
  • the state in which the internal pressure is rising corresponds to the deterioration state in which the VC film is peeled off and SEI is easily formed due to use as described above. Therefore, if the additive is released according to the increase in internal pressure, Thus, the coating on the electrode surface can be recovered.
  • the VC film can be formed again in the area where the VC film on the electrode surface is peeled off (that is, the VC film can be recovered), and the formation of SEI
  • the deterioration of the battery that is, the capacity decrease due to the reduction of lithium ions which can move between the positive electrode and the negative electrode.
  • the additive is added in a deteriorated state, that is, in a state in which there is a region where the VC film on the electrode surface is peeled off, it is possible to suppress the VC film itself from being thickened and the battery resistance rising.
  • the additive may be released from the capsule even in a state where the number of times of use is low and no deterioration occurs, and this causes the VC film to be thickened. It is not preferable because it is conceivable. Therefore, it is preferable to be able to add an additive in the state which degraded like this embodiment, and, thereby, deterioration of a battery can be effectively suppressed without adding an additive excessively.
  • the internal pressure also changes due to the expansion and contraction of the electrode during charge and discharge, but the internal pressure change due to the expansion and contraction of the electrode is smaller than the internal pressure change due to deterioration. Therefore, the capsule 3 is broken due to the expansion and contraction of the electrode during charge and discharge by setting the predetermined internal pressure value to break the capsule 3 larger than the amount of change in internal pressure due to the expansion and contraction of the electrode during charge and discharge. There is no.
  • the addition of the additive in this way is considered to prevent the internal pressure from turning to decrease, but the formation of the VC film can suppress the increase in internal pressure for a certain period of time. This simultaneously suppresses the deterioration of the battery. Then, when the VC film on the surface of the electrode is peeled off again by the expansion and contraction of the electrode again, the internal pressure gradually increases again. Then, another capsule 3A other than the torn capsule 3 is broken at a low internal pressure to release the additive.
  • each capsules having different thicknesses in the present embodiment, two capsules having different thicknesses are contained, but the invention is not limited thereto), each is broken at a predetermined internal pressure to form a VC film. can do.
  • Examples of the resin insoluble in the electrolyte constituting the capsules 3 and 3A include polyolefins such as polyethylene and polypropylene, polystyrene, nylon, polycaprolactone, polyamide, and cellulose.
  • an additive capable of forming a VC film again is added, but the additive is not limited to the above-described VC.
  • the additive may be any one as long as it can recover the film which has fallen off due to expansion and contraction of the electrode as described above, and examples thereof include vinylene ethylene carbonate, fluoro-ethylene carbonate, succinic anhydride, lactide, caprolactam, Ethylene sulfite, propane sultone (PS), propene sultone, vinyl sulfone, and derivatives thereof and halogen-substituted compounds can be mentioned.
  • an additive for example, ethylenediaminetetraacetic acid, tetramethylethylenediamine, pyridine, dipyridyl, ethylenebis (diphenylphosphine), butyronitrile, succinonitrile, iodine and ammonium halide, such as hexamethyldisiloxane, hexamethoxycyclotriphosphazene , Hexamethylphosphoramide, cyclohexylbenzene, biphenyl, dimethylpyrrole, and their derivatives.
  • these additives may be selected and contained in the capsules 3 and 3A.
  • the initial additive may also be the same as the additive described above.
  • the total amount of additives released in one addition may be about 0.5 to 1.0% by weight based on the amount of the electrolyte.
  • the initial additive and the recovery additive may be the same as in the present embodiment or may be different. Even if the initial additive and the recovery additive are different, it is sufficient if the reduction of lithium ions which can move between the positive electrode and the negative electrode can be suppressed by protecting the electrode and suppressing the formation of SEI.
  • Second Embodiment differs from the first embodiment in that an addition device 4 shown in FIG. 3 is used instead of a capsule as an addition means.
  • the adding device 4 is installed, for example, on the back surface side of the lid 12 of the secondary battery 1 and adds an additive to the electrolyte solution 14 according to a change in internal pressure.
  • the addition device 4 has a cylindrical portion 41 and a large diameter portion 42 provided on one end side of the cylindrical portion 41 and having a diameter larger than that of the cylindrical portion 41. The other end side of the cylindrical portion 41 is open.
  • the cylindrical portion 41 is provided with a plurality of openings 43 along the longitudinal direction. Reservoir parts 44 communicate with the respective openings 43 respectively.
  • the storage unit 44 is cylindrical with a bottom, and the additive 45 is stored therein.
  • the cylindrical portion 41 is provided with a plug portion 46 which is fitted to the inner wall substantially in agreement with the inner diameter of the cylindrical portion 41.
  • the plug portion 46 is made of, for example, a substance such as rubber.
  • the plug portion 46 is configured to be movable in the tubular portion 41.
  • the plug portion 46 is installed on the other end side of the cylindrical portion 41 as an initial state.
  • the plug 46 is installed and fitted to the other end of the cylindrical portion 41 so that the pressure is the same as the external pressure in a state in which the large diameter portion 42 side of the plug 46 in the addition device 4 receives air. Is configured.
  • the plug 46 when the battery is deteriorated, that is, the internal pressure rises, the plug 46 is pressed by the internal pressure and gradually moves in the longitudinal direction of the cylindrical portion 41 toward one end, that is, the large diameter portion 42 side. Then, as shown in FIG. 3 (2), when the plug portion 46 moves and passes the storage portion 44 closest to the opening side of the cylindrical portion 41, the additive 45 stored in the storage portion 44 is opened. It passes through 43 and is released into the electrolyte 14. Therefore, as the internal pressure rises, the plug portion 46 moves in the cylindrical portion 41, whereby the additive 45 in each storage portion 44 is released into the electrolytic solution 14.
  • the additive 45 is discharged into the electrolyte solution 14 when the secondary battery 1 is deteriorated, that is, the VC film is removed and the increase in internal pressure exceeds a predetermined value.
  • the VC film can be formed again in the region where the VC film of the electrode is peeled, and the secondary battery is recovered. It is possible.
  • the large diameter portion 42 since the large diameter portion 42 is provided, the internal pressure change at the time of charge and discharge can be absorbed. That is, even if there is an internal pressure change at the time of charge and discharge, the detection pressure can be lowered by the air contained in the large diameter portion 42 being pressed outward. As a result, the plug 46 moves due to the change in internal pressure due to deterioration rather than the change in internal pressure due to normal charge and discharge. Since the addition device 4 is provided on the back surface side of the lid 12, the addition device 4 is unlikely to be affected by the expansion and contraction of the electrode body 13. This is because the electrode body 13 expands and contracts in the stacking direction.
  • the present embodiment differs from the second embodiment in that the plug portion 46 of the addition device 5 shown in FIG. 4 is pressed to the outside by an elastic body.
  • the addition device 5 is also provided, for example, on the back surface side of the lid 12 in the same manner as the addition device 4 (see FIG. 3), and adds an additive to the electrolyte according to the change in internal pressure.
  • the addition device 5 is provided with a spring 51, one end of which is connected to a spring seat 52 provided on the large diameter portion 42, and the other end side is connected to the plug portion 46.
  • the plug portion 46 installed near the inlet of the cylindrical portion 41 is pressed outward by the spring 51.
  • the internal pressure in the secondary battery 1 increases due to deterioration, the internal pressure is higher than the elastic force of the spring 51. As it becomes larger, the plug 46 moves inward. With such a configuration, the plug 46 can be more precisely controlled according to the internal pressure.
  • the additive 45 is discharged into the electrolyte solution 14 when the capacity of the secondary battery 1 is decreased, that is, the VC film is peeled off and the increase in internal pressure exceeds a predetermined value.
  • the VC film can be formed again in the area where the VC film of the electrode is peeled, and the secondary battery 1 is recovered. It is possible to
  • the addition means is not limited to the capsules 3 and 3A and the addition devices 4 and 5 described above.
  • the additive 45 may be added according to the deterioration state. If the separator 45 has separation means for separating the additive 45 from the electrolytic solution and the separation means is configured to be deformed according to the internal pressure, the addition is easily performed according to the change in the internal pressure without providing any measurement means etc. The agent 45 can be effectively added.
  • the shapes of the addition devices 4 and 5 are not limited to the above-described embodiments.
  • it may be a shape having no large diameter portion.
  • the thickness of the cylindrical portion 41 is not constant, and the thickness gradually decreases from the other end side (open side) to the one end side (bottom side). May be In this case, as the plug portion 46 moves to one end side, the plug portion 46 is fitted into the inner wall of the cylindrical portion 41.
  • the addition means is disposed in the electrolyte, but is not limited thereto.
  • the plug 46 can be pressed by a change in internal pressure, it is not limited to being disposed in the electrolytic solution.

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  • Engineering & Computer Science (AREA)
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Abstract

A secondary cell (1) provided with a cell case (11), an electrode body (13) accommodated inside the cell case, and an electrolytic solution (14) containing an initial additive and filling the interior of the cell case, the electrode body being provided with adding means (a capsule (3)) for adding to the electrolytic solution a restoring additive for restoring a deteriorated state of a coating film formed by the initial additive, and the additive being added in response to the deteriorated state.

Description

二次電池Secondary battery
　本発明は二次電池に関する。 The present invention relates to a secondary battery.
　近年、電気自動車やプラグインハイブリッド自動車等の電動車両が多数実用化されている。このような電動車両に搭載されている駆動用のバッテリは、充電可能なリチウムイオン二次電池が用いられている。 In recent years, a large number of electrically powered vehicles such as electric vehicles and plug-in hybrid vehicles have been put to practical use. A rechargeable lithium ion secondary battery is used as a drive battery mounted on such an electric vehicle.
　リチウムイオン二次電池は使用により、リチウムイオンと電解液（電解質）とが反応して電極の表面に固体電解質界面（ＳＥＩ）を形成する。このＳＥＩの形成が不十分であると電解質と電極とが過剰に反応して二次電池の作動が不安定となる問題があるが、ＳＥＩの形成が進みすぎると電池内の正極・負極間を移動するリチウムイオンが減少し、電池が劣化するという問題がある。 In lithium ion secondary batteries, lithium ions and an electrolytic solution (electrolyte) react with each other to form a solid electrolyte interface (SEI) on the surface of an electrode. If the formation of this SEI is insufficient, there is a problem that the electrolyte and the electrode react excessively and the operation of the secondary battery becomes unstable. However, if the formation of SEI proceeds too much, between the positive electrode and the negative electrode in the battery There is a problem that the moving lithium ion decreases and the battery is deteriorated.
　従来、このような問題を解決するために、電解液中に添加剤として、例えばビニレンカーボネート（ＶＣ）を添加することが知られている（例えば、特許文献１参照）。特許文献１では、ＶＣを添加し電極表面にＶＣによる被膜（以下、ＶＣ被膜という）を形成することで、ＳＥＩが形成されすぎることを抑制している。ところが、ＶＣ被膜は電極体の膨張収縮により徐々に剥がれてしまう。 Conventionally, in order to solve such a problem, it is known to add, for example, vinylene carbonate (VC) as an additive to an electrolytic solution (see, for example, Patent Document 1). In patent document 1, VC is added and the film (henceforth a VC film) by VC is formed in an electrode surface, it has suppressed that SEI is formed too much. However, the VC film is gradually peeled off by the expansion and contraction of the electrode body.
　このため、特許文献１に記載の発明では、このＶＣをカプセルに入れて、時間経過と共に徐々に電解質中にＶＣを添加できるようにし、膨張収縮により剥がれたＶＣ被膜を連続的に再生し、ＳＥＩの形成を抑制している。その結果、電池の劣化を抑制している。 Therefore, in the invention described in Patent Document 1, this VC is put into a capsule so that VC can be gradually added to the electrolyte with the passage of time, and the VC film peeled off by expansion and contraction is continuously regenerated. Control the formation of As a result, deterioration of the battery is suppressed.
特開２００９－５０１４１９号公報（請求項１等）JP, 2009-501419, A (claim 1 grade)
　特許文献１では、カプセルが徐放性カプセルであり、時間経過により徐々にＶＣが放出されるため、時間経過と共に電池が劣化するような使用状態では劣化を回復することができ、効果的な面もある。 In Patent Document 1, since the capsule is a sustained release capsule and VC is gradually released with the passage of time, it is possible to recover the deterioration in the use state where the battery is deteriorated with the passage of time, which is effective. There is also.
　しかしながら、徐放性カプセルにより連続的に添加剤を添加するとすれば、時間経過と共に電池が劣化していない場合でも添加剤が放出されてしまうことが考えられる。このような場合、添加剤が放出されすぎてもＶＣ被膜が厚くなりすぎて内部抵抗が高くなるという問題がある。なお、このような問題は、ＶＣに限らず劣化状態を回復するための他の添加剤を投入する場合に同様に生じる。 However, if the additive is continuously added by means of a sustained release capsule, it is conceivable that the additive is released even when the battery has not deteriorated with the passage of time. In such a case, there is a problem that even if the additive is released too much, the VC film becomes too thick and the internal resistance becomes high. Such a problem occurs not only in the case of VC but also in the case of adding other additives for recovering the deteriorated state.
　そこで、本発明の課題は、上記従来技術の問題点を解決することにあり、添加剤を添加しすぎることなく電池の劣化を効果的に抑制できる二次電池を提供しようとするものである。 Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a secondary battery capable of effectively suppressing the deterioration of the battery without adding an additive excessively.
　本発明の二次電池は、電池ケースと、前記電池ケース内部に収納された電極体と、初期添加剤を含み、前記電池ケース内に満たされた電解液とを備えた二次電池であって、前記電極体に前記初期添加剤により形成された被膜の劣化状態に応じて劣化状態を回復するための回復用添加剤を電解液に添加する添加手段を設けることを特徴とする。劣化状態に応じて劣化状態を回復するための回復用添加剤を添加することで、電池の劣化を効果的に抑制できる。なお、ここでいう劣化状態を回復とは、添加剤による被膜が膨張収縮により電極から剥がれ落ちることによる電池の劣化状態を回復することをいう。 The secondary battery of the present invention is a secondary battery comprising a battery case, an electrode body housed inside the battery case, and an electrolytic solution filled in the battery case, containing an initial additive. The electrode body is characterized in that an adding means for adding a recovery additive for recovering the deteriorated state according to the deteriorated state of the film formed by the initial additive is provided to the electrolytic solution. By adding a recovery additive for recovering the deteriorated state according to the deteriorated state, the deterioration of the battery can be effectively suppressed. In addition, recovery of the degradation state as used herein refers to recovery of the degradation state of the battery due to peeling off of the film from the electrode due to expansion and contraction.
　前記添加手段は、前記二次電池の劣化による前記電池ケース内の内圧が上昇して所定値以上となった場合に、前記添加剤を前記電解液に添加することが好ましい。即ち、電池の劣化を内圧上昇により検知して、これにより添加剤を前記電解液に添加することで、より効果的に電池の劣化を抑制できる。 It is preferable that the addition means adds the additive to the electrolytic solution when the internal pressure in the battery case due to the deterioration of the secondary battery rises to a predetermined value or more. That is, the deterioration of the battery can be more effectively suppressed by detecting the deterioration of the battery by the increase in internal pressure and adding the additive to the electrolytic solution.
　本発明の好ましい実施形態としては、前記所定値は、前記電極体の充放電時の膨張収縮による内圧変化よりも大きいことが挙げられる。 In a preferred embodiment of the present invention, the predetermined value is larger than the internal pressure change due to expansion and contraction during charge and discharge of the electrode body.
　前記添加手段は、前記添加剤を前記電解液から隔離する隔離手段を有し、該隔離手段が前記内圧に応じて変形することで前記添加剤を前記電解液へ放出することが好ましい。このように特に内圧を測定する測定手段を持たずに直接的に内圧により変形する部材から構成されることで、より簡易に添加剤を添加することが可能である。 It is preferable that the addition means has a separation means for separating the additive from the electrolytic solution, and the separation means releases the additive to the electrolytic solution by being deformed according to the internal pressure. Thus, it is possible to add an additive more simply by comprising from the member which deform | transforms by an internal pressure directly, without having a measurement means which measures an internal pressure especially.
　前記添加手段は、前記添加剤を内包した前記隔離手段としてのカプセルであり、前記内圧が所定値以上となると該カプセルの壁面が破れて前記添加剤を前記電解液に添加するように構成されていることが好ましい。このような添加手段を用いれば、簡易に劣化状態に応じて劣化状態を回復するための添加剤を添加することができる。 The addition means is a capsule as the separation means containing the additive, and the wall surface of the capsule is broken when the internal pressure reaches a predetermined value or more, and the additive is added to the electrolytic solution. Is preferred. By using such an addition means, an additive for recovering the deteriorated state can be easily added according to the deteriorated state.
　前記添加手段は、その一端側が封止され、他端側が開放された筒状部材、及び該筒状部材の中空部に嵌合し、該中空部を前記内圧の上昇により前記一端側に移動する移動部からなる前記隔離手段と、前記筒状部材の前記移動部の初期設置位置よりも一端側に設けられた開口に連通し、前記添加剤が貯留された貯留部とを備え、前記内圧の上昇により前記移動部が移動して、前記添加剤を前記電解液に添加するように構成されていることが好ましい。このような添加手段を用いれば、簡易に劣化状態に応じて劣化状態を回復するための添加剤を添加することができる。 The addition means is fitted in a tubular member whose one end side is sealed and the other end side is opened, and a hollow portion of the tubular member, and the hollow portion is moved to the one end side by the increase of the internal pressure And a storage unit in communication with the opening provided at one end side of the initial installation position of the moving unit of the cylindrical member, the storage unit containing the additive, It is preferable that the moving part move by the rising to add the additive to the electrolytic solution. By using such an addition means, an additive for recovering the deteriorated state can be easily added according to the deteriorated state.
　前記添加手段は、前記筒状部材の前記一端側に空気溜まり部が形成されていることが好ましい。このように構成されていることで、前記電極体の充放電時の膨張収縮による内圧変化を吸収することができる。 It is preferable that an air reservoir part is formed in the said one end side of the said cylindrical member as the said addition means. By being comprised in this way, the internal pressure change by the expansion-contraction at the time of charge / discharge of the said electrode body can be absorbed.
　本発明の二次電池によれば、劣化状態に応じて添加剤を添加することができ電池の劣化を効果的に抑制できるという優れた効果を奏し得る。 According to the secondary battery of the present invention, the additive can be added according to the deterioration state, and the excellent effect that the deterioration of the battery can be effectively suppressed can be exhibited.
実施形態１にかかる二次電池の斜視図である。FIG. 1 is a perspective view of a secondary battery according to a first embodiment. 実施形態１にかかる二次電池の断面図である。FIG. 1 is a cross-sectional view of a secondary battery according to Embodiment 1. 実施形態２にかかる二次電池の断面図である。FIG. 6 is a cross-sectional view of a secondary battery according to a second embodiment. 実施形態３にかかる添加装置の模式図である。FIG. 7 is a schematic view of an addition device according to Embodiment 3. 別の実施形態にかかる添加装置の模式図である。It is a schematic diagram of the addition apparatus concerning another embodiment.
（実施形態１）
　本発明の第１の実施形態について、図１、２を用いて説明する。図１は、本実施形態にかかる二次電池を示す斜視図であり、図２（１）は図１のＡ－Ａ’線での断面図であり、図２（２）は図１のＢ－Ｂ’線での断面図である。 (Embodiment 1)
A first embodiment of the present invention will be described using FIGS. FIG. 1 is a perspective view showing a secondary battery according to the present embodiment, FIG. 2 (1) is a cross-sectional view taken along the line AA 'of FIG. 1, and FIG. 2 (2) is B of FIG. It is sectional drawing in-B 'line.
　二次電池１は、略直方体形状のケース１１と、ケース１１の開口部に配されてケース１１を封止する蓋部１２とを備える。図２に示すように、ケース１１内には電極体１３が収納されている。また、ケース１１内部は電解液１４によって満たされており、電極体１３は電解液１４中に浸漬されている。電極体１３は、セパレータを介して正極板及び負極板が積層されたものを巻回して形成されたものであり、積層方向は、図中横方向となっている。 The secondary battery 1 includes a substantially rectangular case 11 and a lid 12 disposed at the opening of the case 11 to seal the case 11. As shown in FIG. 2, the electrode body 13 is housed in the case 11. Further, the inside of the case 11 is filled with the electrolytic solution 14, and the electrode body 13 is immersed in the electrolytic solution 14. The electrode body 13 is formed by winding a laminate of a positive electrode plate and a negative electrode plate with a separator interposed therebetween, and the lamination direction is the lateral direction in the drawing.
　蓋部１２には正極端子１５と、負極端子１６とが設けられている。この正極端子１５には、正極集電部１７が接続する。また、負極端子１６には負極集電部１８が接続する。正極集電部１７及び負極集電部１８は、それぞれ電極体１３の正極板及び負極板に接続する。即ち、正極板と正極集電部１７と正極端子１５とは互いに電気的に接続されている。また、負極板と負極集電部１８と負極端子１６とは互いに電気的に接続されている。 The lid 12 is provided with a positive electrode terminal 15 and a negative electrode terminal 16. The positive electrode current collector 17 is connected to the positive electrode terminal 15. Further, a negative electrode current collector 18 is connected to the negative electrode terminal 16. The positive electrode current collecting unit 17 and the negative electrode current collecting unit 18 are connected to the positive electrode plate and the negative electrode plate of the electrode body 13 respectively. That is, the positive electrode plate, the positive electrode current collecting portion 17 and the positive electrode terminal 15 are electrically connected to each other. Further, the negative electrode plate, the negative electrode current collector portion 18 and the negative electrode terminal 16 are electrically connected to each other.
　正極板は、通常用いられる正極材料からなる。通常用いられる正極材料としては、例えばリチウムを吸蔵および放出可能な金属酸化物、例えば層状構造型の金属酸化物、スピネル型の金属酸化物及び金属化合物、酸化酸塩型の金属酸化物などが挙げられる。層状構造型の金属酸化物としては、リチウムニッケル系複合酸化物、リチウムコバルト系複合酸化物、三元系複合酸化物（ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２）が挙げられる。リチウムニッケル系複合酸化物としては、好ましくはニッケル酸リチウム（ＬｉＮｉＯ２）が挙げられる。リチウムコバルト系複合酸化物としては、好ましくはコバルト酸リチウム（ＬｉＣｏＯ２）が挙げられる。スピネル型の金属酸化物としては、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）等のリチウムマンガン系複合酸化物が挙げられる。酸化酸塩型の金属酸化物としては、リン酸鉄リチウム（ＬｉＦｅＰＯ４）、リン酸マンガンリチウム（ＬｉＭｎＰＯ４）、リン酸シリコンリチウム等が挙げられる。 The positive electrode plate is made of a commonly used positive electrode material. Commonly used positive electrode materials include, for example, metal oxides capable of absorbing and desorbing lithium, such as metal oxides of layered structure type, spinel type metal oxides and metal compounds, metal salts of oxide salt type, etc. Be The layered structure type metal oxide may, for example, be a lithium nickel composite oxide, a lithium cobalt composite oxide, or a ternary composite oxide (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 ). Preferably, lithium nickel oxide (LiNiO 2 ) is mentioned as the lithium nickel composite oxide. The lithium cobalt-based composite oxide preferably includes lithium cobaltate (LiCoO 2 ). The spinel-type metal oxides, lithium-manganese-based composite oxide such as lithium manganate (LiMn 2 O 4) can be mentioned. Examples of the oxide salt type metal oxide include lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium silicon phosphate and the like.
　負極板は、通常用いられる負極活物質からなる。負極活物質としては、通常用いられる活物質、例えば金属リチウム、リチウム合金、金属酸化物、金属硫化物、金属窒化物、および黒鉛等の炭素材料等を挙げることができる。金属酸化物としては、例えばスズ酸化物やケイ素酸化物などの不可逆性容量をもつものが挙げられる。炭素系材料としての黒鉛としては、人造黒鉛であっても天然黒鉛であっても良く、本実施形態では、負極の活物質としてはグラファイトを用いている。 The negative electrode plate is made of a commonly used negative electrode active material. Examples of the negative electrode active material include commonly used active materials such as metal lithium, lithium alloy, metal oxide, metal sulfide, metal nitride, and carbon materials such as graphite. Examples of the metal oxide include those having irreversible capacity such as tin oxide and silicon oxide. The graphite as the carbon-based material may be artificial graphite or natural graphite, and in the present embodiment, graphite is used as the active material of the negative electrode.
　正極板及び負極板にはそれぞれさらにバインダーが含有されていてもよく、例えばポリフッ化ビニリデンを用いることができる。なお、活物質層にはアセチレンブラック等の導電性向上剤、電解質（例えば、リチウム塩（支持電解質）、イオン伝導性ポリマー等）が含まれていてもよい。また、イオン伝導性ポリマーが含まれる場合には、前記ポリマーを重合させるための重合開始剤が含まれてもよい。 Each of the positive electrode plate and the negative electrode plate may further contain a binder, and for example, polyvinylidene fluoride can be used. The active material layer may contain a conductivity improver such as acetylene black, an electrolyte (for example, a lithium salt (supporting electrolyte), an ion conductive polymer, etc.). In addition, when an ion conductive polymer is included, a polymerization initiator for polymerizing the polymer may be included.
　電解液１４は、通常用いられる電解質、例えば環状炭酸エステルであるエチレンカーボネートやプロピレンカーボネートと、また、鎖状炭酸エステルでありジメチルカーボネートやエチルメチルカーボネート、ジエチルカーボネートとの混合溶液にＬｉＰＦ６を１モル濃度程度溶解した有機電解液が挙げられる。また、この電解液１４には初期添加剤としてビニレンカーボネート（ＶＣ）が添加されている。 The electrolyte solution 14 is a mixed solution of a commonly used electrolyte, for example, ethylene carbonate and propylene carbonate which are cyclic carbonates, and linear carbonates, and 1 mol of LiPF 6 in a mixed solution of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate. The organic electrolyte solution melt | dissolved to a density | concentration extent is mentioned. Further, vinylene carbonate (VC) is added to the electrolytic solution 14 as an initial additive.
　また、本実施形態では、電解液１４には電極表面の被膜を回復するための回復用添加剤（以下、単に添加剤ともいう）が封入されたカプセル３、３Ａが含有されている。本実施形態では、このカプセル３、３Ａからそれぞれ所定の内圧以上となると内部に封入された添加剤が放出されることで、電池の劣化を抑制することができる。 Further, in the present embodiment, the electrolyte solution 14 contains capsules 3 and 3A in which a recovery additive (hereinafter, also simply referred to as an additive) for recovering the film on the surface of the electrode is enclosed. In the present embodiment, when the internal pressure is equal to or higher than the predetermined internal pressure from the capsules 3 and 3A, the additive sealed therein is released, so that the deterioration of the battery can be suppressed.
　カプセル３、３Ａは、電解質に不溶である樹脂から構成され、所定の圧力が印加された場合に破れるようにそれぞれその厚みが設定されて構成されている。本実施形態では、カプセル３よりもカプセル３Ａの方が厚みが厚く、破れにくく構成されている。二次電池が使用により劣化すると、ケース１１の内圧が上昇するので、このケース１１の内圧によりカプセル３、３Ａが破けて封入された添加剤が放出されることにより、劣化状態に応じて必要量の添加剤を電解質に投入することができ、これにより劣化を抑制しているのである。 The capsules 3 and 3A are made of a resin insoluble in the electrolyte, and their thicknesses are set so as to break when a predetermined pressure is applied. In the present embodiment, the capsule 3A is thicker than the capsule 3 and is hard to break. When the secondary battery is deteriorated by use, the internal pressure of the case 11 is increased. Therefore, the internal pressure of the case 11 is broken to release the encapsulated additive and the required amount according to the deterioration state. Additives can be added to the electrolyte, thereby suppressing the deterioration.
　以下、この内圧と劣化状態との関係について具体的に説明する。二次電池は使用されることで、リチウムイオンが炭素電極にインターカレートする際にリチウムイオンと電解質とが反応してガスが発生し、これにより電極の表面に固体電解質界面層（ＳＥＩ）が形成される。ＳＥＩは二次電池の初期作動時において安定的に充放電するためには必要であるが、それ以降もＳＥＩが形成され続けてしまうような状態であると、正極―負極間を移動できるリチウムイオンが不足して電池容量が減少した状態（劣化状態）となりやすい。即ち、ＳＥＩが形成されてしまう状態では、ＳＥＩ形成による正極―負極間を移動できるリチウムイオンの減少による電池容量の減少という二次電池の劣化が引き起こされやすく、この劣化と同時にＳＥＩ形成時のガスの放出による内圧の上昇により電池の外形が変化するという問題が進行する。 Hereinafter, the relationship between the internal pressure and the deterioration state will be specifically described. The secondary battery is used, and when lithium ions intercalate in the carbon electrode, lithium ions react with the electrolyte to generate a gas, whereby a solid electrolyte interface layer (SEI) is formed on the surface of the electrode. It is formed. SEI is necessary to stably charge and discharge at the time of initial operation of the secondary battery, but it is a lithium ion that can move between the positive electrode and the negative electrode in a state where SEI continues to be formed thereafter. And the battery capacity is likely to be reduced (deteriorated state). That is, in the state where SEI is formed, deterioration of the secondary battery is easily caused by reduction of battery capacity due to decrease of lithium ions which can move between the positive electrode and the negative electrode due to SEI formation. The problem is that the battery's external shape changes due to the rise in internal pressure due to the release of
　他方で、通常は二次電池内にＳＥＩの形成を抑制するための初期添加剤としてビニレンカーボネート（ＶＣ）を予め電解液中に添加している。これにより、電極表面にＶＣ被膜を形成してＳＥＩの形成を抑制し、その結果電池容量の減少を抑制し、同時に内圧の上昇を抑制している。しかしながら、二次電池を使用することにより電極が膨張・収縮することでＶＣ被膜は電極表面から剥がれてしまう。そうすると、この剥がれた部分でＳＥＩが形成されやすく、その結果、正極―負極間を移動できるリチウムイオンが減少して電池容量を減少させることがあった。この場合に、二次電池内に予め過剰にＶＣを添加しておくと、ＶＣ被膜が厚くなりすぎて内部抵抗が増大することがあった。 On the other hand, vinylene carbonate (VC) is usually added in advance to the electrolyte as an initial additive for suppressing the formation of SEI in the secondary battery. As a result, a VC film is formed on the electrode surface to suppress the formation of SEI, and as a result, a decrease in battery capacity is suppressed, and at the same time, an increase in internal pressure is suppressed. However, the use of a secondary battery causes the VC film to peel off from the electrode surface due to expansion and contraction of the electrode. Then, SEI is likely to be formed at the peeled portion, and as a result, lithium ions which can move between the positive electrode and the negative electrode may be reduced to reduce the battery capacity. In this case, if VC is excessively added in advance in the secondary battery, the VC film may become too thick and internal resistance may increase.
　そこで、本実施形態では、二次電池１には、二次電池１の劣化状態に応じて、即ち内圧上昇に応じて添加剤を添加する添加手段としてのカプセル３、３Ａが電解液１４内に含有されているのである。内圧が上昇している状態とは、上述のように使用によりＶＣ被膜が剥がれ落ちてＳＥＩが形成されやすい劣化状態に一致するので、内圧上昇に応じて添加剤を放出すれば、劣化状態に応じて電極表面の被膜を回復することができるのである。 Therefore, in the present embodiment, the capsules 3 and 3A as an addition means for adding an additive according to the deterioration state of the secondary battery 1, that is, according to the increase in internal pressure, are contained in the electrolyte solution 14 in the secondary battery 1. It is contained. The state in which the internal pressure is rising corresponds to the deterioration state in which the VC film is peeled off and SEI is easily formed due to use as described above. Therefore, if the additive is released according to the increase in internal pressure, Thus, the coating on the electrode surface can be recovered.
　カプセル３が破れて添加剤が放出されることで、電極表面のＶＣ被膜が剥がれてしまった領域に再度ＶＣ被膜を形成することができ（即ちＶＣ被膜を回復することができ）、ＳＥＩの生成を抑制、即ち正極―負極間を移動できるリチウムイオンの減少による容量低下という電池の劣化を抑制することができる。さらに、劣化した状態、即ち電極表面のＶＣ被膜が剥がれてしまった領域がある状態で添加剤を添加することから、ＶＣ被膜自体が厚くなって電池の抵抗が上昇することも抑制できる。例えば、一定の時間を経過した後にカプセルが溶解するように形成するとすれば、使用回数が少なく劣化が生じていない状態でも添加剤をカプセルから放出してしまい、これによりＶＣ被膜が厚くなってしまうことが考えられるので好ましくない。従って、本実施形態のように劣化した状態で添加剤を添加できるように構成することが好ましく、これによって添加剤を添加しすぎることなく電池の劣化を効果的に抑制できる。 By breaking the capsule 3 and releasing the additive, the VC film can be formed again in the area where the VC film on the electrode surface is peeled off (that is, the VC film can be recovered), and the formation of SEI Thus, it is possible to suppress the deterioration of the battery, that is, the capacity decrease due to the reduction of lithium ions which can move between the positive electrode and the negative electrode. Furthermore, since the additive is added in a deteriorated state, that is, in a state in which there is a region where the VC film on the electrode surface is peeled off, it is possible to suppress the VC film itself from being thickened and the battery resistance rising. For example, if the capsule is formed so as to dissolve after a certain period of time, the additive may be released from the capsule even in a state where the number of times of use is low and no deterioration occurs, and this causes the VC film to be thickened. It is not preferable because it is conceivable. Therefore, it is preferable to be able to add an additive in the state which degraded like this embodiment, and, thereby, deterioration of a battery can be effectively suppressed without adding an additive excessively.
　なお、内圧は充放電時の電極の膨張・収縮によっても変化するが、この電極の膨張・収縮による内圧変化は劣化による内圧変化と比較すると小さい。従って、カプセル３が破れる所定の内圧値をこれらの充放電時の電極の膨張・収縮による内圧変化量よりも大きく設定することとで、カプセル３が充放電時の電極の膨張・収縮により破れることはない。 The internal pressure also changes due to the expansion and contraction of the electrode during charge and discharge, but the internal pressure change due to the expansion and contraction of the electrode is smaller than the internal pressure change due to deterioration. Therefore, the capsule 3 is broken due to the expansion and contraction of the electrode during charge and discharge by setting the predetermined internal pressure value to break the capsule 3 larger than the amount of change in internal pressure due to the expansion and contraction of the electrode during charge and discharge. There is no.
　このように添加剤が添加されることで、内圧が減少に転じることはないと考えられるが、ＶＣ被膜が再度形成されることで、内圧の上昇は一定期間抑制できる。これは同時に電池の劣化を抑制している。そして、その後再度電極が膨張収縮を繰り返すことより電極表面のＶＣ被膜が剥がれてしまうと、再度、徐々に内圧が上昇する。そうすると、低い内圧で破れたカプセル３とは別のカプセル３Ａが破れて添加剤を放出する。このように、複数の厚さの異なるカプセルを含有させることで（本実施形態では二つの厚みの異なるカプセルを含有させているがこれに限定されない）、それぞれ所定の内圧で破れてＶＣ被膜を形成することができる。 The addition of the additive in this way is considered to prevent the internal pressure from turning to decrease, but the formation of the VC film can suppress the increase in internal pressure for a certain period of time. This simultaneously suppresses the deterioration of the battery. Then, when the VC film on the surface of the electrode is peeled off again by the expansion and contraction of the electrode again, the internal pressure gradually increases again. Then, another capsule 3A other than the torn capsule 3 is broken at a low internal pressure to release the additive. Thus, by containing a plurality of capsules having different thicknesses (in the present embodiment, two capsules having different thicknesses are contained, but the invention is not limited thereto), each is broken at a predetermined internal pressure to form a VC film. can do.
　なお、カプセルは添加剤の添加量に応じて複数含有させていてもよい。即ち、カプセル３、３Ａをそれぞれ複数含有させていてもよいし、添加量に応じてそれぞれ異なる個数を含有させていてもよい。もちろん厚みの異なるカプセルを３個以上含有させてもよい。 In addition, you may be made to contain two or more capsules according to the addition amount of an additive. That is, a plurality of capsules 3 and 3A may be contained, or different numbers may be contained according to the addition amount. Of course, three or more capsules having different thicknesses may be contained.
　カプセル３、３Ａを構成する電解質に不溶である樹脂としては、ポリエチレン、ポリプロピレンなどのポリオレフィン、ポリスチレン、ナイロン、ポリカプロラクトン、ポリアミド、セルロース等が挙げられる。 Examples of the resin insoluble in the electrolyte constituting the capsules 3 and 3A include polyolefins such as polyethylene and polypropylene, polystyrene, nylon, polycaprolactone, polyamide, and cellulose.
　本実施形態では、ＶＣ被膜を再度形成することができる添加剤を添加したが、添加剤は上述したＶＣに限定されない。添加剤としては、上述したように電極の膨張収縮により剥がれ落ちてしまった被膜を回復することができるものであればよく、例えばビニレンエチレンカーボネート、フルオロ－エチレンカーボネート、無水コハク酸、ラクチド、カプロラクタム、エチレンサルファイト、プロパンスルトン（ＰＳ）、プロペンスルトン、ビニルスルホン、及びそれらの誘導体及びハロゲン置換された化合物、が挙げられる。さらに、添加剤としては、例えばエチレンジアミンテトラ酢酸、テトラメチルエチレンジアミン、ピリジン、ジピリジル、エチレンビス（ジフェニルホスフィン）、ブチロニトリル、スクシノニトリル、ヨウ素及びアンモニウムハロゲン化物、例えばヘキサメチルジシロキサン、ヘキサメトキシシクロトリホスファゼン、ヘキサメチルホスホルアミド、シクロヘキシルベンゼン、ビフェニル、ジメチルピロール、およびそれらの誘導体を含んでいてもよい。これらの添加剤から、一種又は複数を選択してカプセル３、３Ａ内に含有させればよい。初期添加剤も、上述した添加剤と同一のものを用いてもよい。 In the present embodiment, an additive capable of forming a VC film again is added, but the additive is not limited to the above-described VC. The additive may be any one as long as it can recover the film which has fallen off due to expansion and contraction of the electrode as described above, and examples thereof include vinylene ethylene carbonate, fluoro-ethylene carbonate, succinic anhydride, lactide, caprolactam, Ethylene sulfite, propane sultone (PS), propene sultone, vinyl sulfone, and derivatives thereof and halogen-substituted compounds can be mentioned. Furthermore, as an additive, for example, ethylenediaminetetraacetic acid, tetramethylethylenediamine, pyridine, dipyridyl, ethylenebis (diphenylphosphine), butyronitrile, succinonitrile, iodine and ammonium halide, such as hexamethyldisiloxane, hexamethoxycyclotriphosphazene , Hexamethylphosphoramide, cyclohexylbenzene, biphenyl, dimethylpyrrole, and their derivatives. One or more of these additives may be selected and contained in the capsules 3 and 3A. The initial additive may also be the same as the additive described above.
　一回の添加で放出される添加剤の総量は、電解液量に対して０．５～１．０重量％程度とされていればよい。 The total amount of additives released in one addition may be about 0.5 to 1.0% by weight based on the amount of the electrolyte.
　初期添加剤と回復用添加剤とは、本実施形態のように同一のものであってもよく、異なるものであってもよい。初期添加剤と回復用添加剤とが異なったとしても、電極を保護しＳＥＩの形成を抑制することで正極―負極間を移動できるリチウムイオンの減少を抑制することができればよい。 The initial additive and the recovery additive may be the same as in the present embodiment or may be different. Even if the initial additive and the recovery additive are different, it is sufficient if the reduction of lithium ions which can move between the positive electrode and the negative electrode can be suppressed by protecting the electrode and suppressing the formation of SEI.
　（実施形態２）
　本実施形態では、添加手段としてカプセルの代わりに図３に示す添加装置４を用いている点が実施形態１とは異なる。 Second Embodiment
The present embodiment differs from the first embodiment in that an addition device 4 shown in FIG. 3 is used instead of a capsule as an addition means.
　添加装置４は、例えば二次電池１の蓋部１２の裏面側に設置され、内圧の変化に応じて添加剤を電解液１４中に添加するものである。添加装置４は、筒状部４１と、筒状部４１の一端側に設けられ、筒状部４１よりも径が大きい大径部４２とを有する。筒状部４１の他端側は開放されている。筒状部４１には、その長手方向に沿って開口４３が複数列設されている。各開口４３にはそれぞれに貯留部４４が連通している。貯留部４４は有底筒状であり、それぞれ添加剤４５が貯留されている。また、筒状部４１には、筒状部４１の内径に略一致して内壁に嵌合する栓部４６が設けられている。栓部４６は、例えばゴム等の物質から構成されている。栓部４６は、筒状部４１内を移動可能であるように構成されている。栓部４６は、初期状態としては筒状部４１の他端側に設置されている。栓部４６が筒状部４１の他端側に設置され嵌合することで、添加装置４において栓部４６よりも大径部４２側は空気が入った状態で圧力が外圧と同一であるように構成されている。 The adding device 4 is installed, for example, on the back surface side of the lid 12 of the secondary battery 1 and adds an additive to the electrolyte solution 14 according to a change in internal pressure. The addition device 4 has a cylindrical portion 41 and a large diameter portion 42 provided on one end side of the cylindrical portion 41 and having a diameter larger than that of the cylindrical portion 41. The other end side of the cylindrical portion 41 is open. The cylindrical portion 41 is provided with a plurality of openings 43 along the longitudinal direction. Reservoir parts 44 communicate with the respective openings 43 respectively. The storage unit 44 is cylindrical with a bottom, and the additive 45 is stored therein. In addition, the cylindrical portion 41 is provided with a plug portion 46 which is fitted to the inner wall substantially in agreement with the inner diameter of the cylindrical portion 41. The plug portion 46 is made of, for example, a substance such as rubber. The plug portion 46 is configured to be movable in the tubular portion 41. The plug portion 46 is installed on the other end side of the cylindrical portion 41 as an initial state. The plug 46 is installed and fitted to the other end of the cylindrical portion 41 so that the pressure is the same as the external pressure in a state in which the large diameter portion 42 side of the plug 46 in the addition device 4 receives air. Is configured.
　かかる添加装置４では、電池の劣化、即ち内圧の上昇が生じると、栓部４６が内圧により押圧されて筒状部４１の長手方向を一端側、即ち大径部４２側へ徐々に移動する。そして、図３（２）に示すように栓部４６が移動していき、筒状部４１の最も開口側に近い貯留部４４を越えると、貯留部４４に貯留されていた添加剤４５が開口４３を通過して電解液１４内に放出される。従って、内圧上昇が生じるにつれて栓部４６が筒状部４１を移動して、これにより各貯留部４４内の添加剤４５が電解液１４内に放出される。 In the addition device 4, when the battery is deteriorated, that is, the internal pressure rises, the plug 46 is pressed by the internal pressure and gradually moves in the longitudinal direction of the cylindrical portion 41 toward one end, that is, the large diameter portion 42 side. Then, as shown in FIG. 3 (2), when the plug portion 46 moves and passes the storage portion 44 closest to the opening side of the cylindrical portion 41, the additive 45 stored in the storage portion 44 is opened. It passes through 43 and is released into the electrolyte 14. Therefore, as the internal pressure rises, the plug portion 46 moves in the cylindrical portion 41, whereby the additive 45 in each storage portion 44 is released into the electrolytic solution 14.
　即ち、本実施形態においても二次電池１の劣化、即ちＶＣ被膜が除去されて内圧の上昇が所定値以上となると添加剤４５が電解液１４内に放出するように構成されている。これにより、電極でのＶＣ被膜が剥がれた状態になったときにＶＣが添加されることから、電極のＶＣ被膜が剥がれた領域に再度ＶＣ被膜を形成することができ、二次電池を回復させることが可能である。 That is, also in the present embodiment, the additive 45 is discharged into the electrolyte solution 14 when the secondary battery 1 is deteriorated, that is, the VC film is removed and the increase in internal pressure exceeds a predetermined value. Thus, since VC is added when the VC film at the electrode is in a peeled state, the VC film can be formed again in the region where the VC film of the electrode is peeled, and the secondary battery is recovered. It is possible.
　この場合において、大径部４２を設けていることから、充放電時における内圧変化を吸収できる。即ち、充放電時における内圧変化があったとしても、大径部４２内に含まれた空気が外側へ押圧することで、検知圧を下げることができる。これにより、通常の充放電による内圧変化ではなく劣化による内圧変化により栓部４６が移動する。なお、かかる添加装置４は、蓋部１２の裏面側に設けられていることから、電極体１３の膨張収縮の影響を受けにくい。電極体１３は、その積層方向に膨張収縮するからである。 In this case, since the large diameter portion 42 is provided, the internal pressure change at the time of charge and discharge can be absorbed. That is, even if there is an internal pressure change at the time of charge and discharge, the detection pressure can be lowered by the air contained in the large diameter portion 42 being pressed outward. As a result, the plug 46 moves due to the change in internal pressure due to deterioration rather than the change in internal pressure due to normal charge and discharge. Since the addition device 4 is provided on the back surface side of the lid 12, the addition device 4 is unlikely to be affected by the expansion and contraction of the electrode body 13. This is because the electrode body 13 expands and contracts in the stacking direction.
　（実施形態３）
　本実施形態では、図４に示す添加装置５の栓部４６が弾性体により外部へ押圧されている点が実施形態２とは異なる。 (Embodiment 3)
The present embodiment differs from the second embodiment in that the plug portion 46 of the addition device 5 shown in FIG. 4 is pressed to the outside by an elastic body.
　本実施形態にかかる添加装置５も、添加装置４（図３参照）と同様に例えば蓋部１２の裏面側に設置され、内圧の変化に応じて添加剤を電解質中に添加するものである。添加装置５にはバネ５１が設けられ、バネ５１はその一端が大径部４２に設けられたバネ座５２に接続され、他端側が栓部４６に接続されている。筒状部４１の入口付近に設置された栓部４６は、バネ５１により外部側へ押圧されているが、劣化により二次電池１内の内圧が大きくなるにつれてバネ５１の弾性力よりも内圧が大きくなり、栓部４６が内側に移動する。このように構成されていることで、より栓部４６を内圧に応じて精密に制御することができる。 The addition device 5 according to the present embodiment is also provided, for example, on the back surface side of the lid 12 in the same manner as the addition device 4 (see FIG. 3), and adds an additive to the electrolyte according to the change in internal pressure. The addition device 5 is provided with a spring 51, one end of which is connected to a spring seat 52 provided on the large diameter portion 42, and the other end side is connected to the plug portion 46. The plug portion 46 installed near the inlet of the cylindrical portion 41 is pressed outward by the spring 51. However, as the internal pressure in the secondary battery 1 increases due to deterioration, the internal pressure is higher than the elastic force of the spring 51. As it becomes larger, the plug 46 moves inward. With such a configuration, the plug 46 can be more precisely controlled according to the internal pressure.
　即ち、本実施形態においても二次電池１の容量の低下、即ちＶＣ被膜が剥がれ落ちて内圧の上昇が所定値以上となると添加剤４５が電解液１４内に放出するように構成されている。これにより、電極でのＶＣ被膜が剥がれた状態になったときにＶＣが添加されることから、電極のＶＣ被膜が剥がれた領域に再度ＶＣ被膜を形成することができ、二次電池１を回復させることが可能である。 That is, also in the present embodiment, the additive 45 is discharged into the electrolyte solution 14 when the capacity of the secondary battery 1 is decreased, that is, the VC film is peeled off and the increase in internal pressure exceeds a predetermined value. Thus, since VC is added when the VC film at the electrode is in a peeled state, the VC film can be formed again in the area where the VC film of the electrode is peeled, and the secondary battery 1 is recovered. It is possible to
　添加手段は、上述したカプセル３、３Ａ及び添加装置４、５に限定されない。劣化状態に応じて添加剤４５を添加できればよい。添加剤４５を電解液から隔離する隔離手段を有し、該隔離手段が前記内圧に応じて変形するように構成されていれば、特に測定手段等を設けることなく内圧変化に応じて簡易に添加剤４５を効果的に添加することができる。 The addition means is not limited to the capsules 3 and 3A and the addition devices 4 and 5 described above. The additive 45 may be added according to the deterioration state. If the separator 45 has separation means for separating the additive 45 from the electrolytic solution and the separation means is configured to be deformed according to the internal pressure, the addition is easily performed according to the change in the internal pressure without providing any measurement means etc. The agent 45 can be effectively added.
　添加装置４、５の形状は上述した各実施形態に限定されない。例えば、図５に示すように、大径部を持たない形状であってもよい。さらに、図５に示すように、筒状部４１の太さが一定でなく、他端側（開放側）から一端側（底側）へいくにつれて徐々にその太さが細くなるように構成してもよい。この場合には、栓部４６が一端側に移動するにつれて、筒状部４１の内壁によりはまっていく形態となる。 The shapes of the addition devices 4 and 5 are not limited to the above-described embodiments. For example, as shown in FIG. 5, it may be a shape having no large diameter portion. Furthermore, as shown in FIG. 5, the thickness of the cylindrical portion 41 is not constant, and the thickness gradually decreases from the other end side (open side) to the one end side (bottom side). May be In this case, as the plug portion 46 moves to one end side, the plug portion 46 is fitted into the inner wall of the cylindrical portion 41.
　各実施形態では、添加手段は電解液内に配されたが、これに限定されない。例えば、内圧の変化により栓部４６が押圧されることができれば、電解液中に配されることに限定されない。 In each embodiment, the addition means is disposed in the electrolyte, but is not limited thereto. For example, as long as the plug 46 can be pressed by a change in internal pressure, it is not limited to being disposed in the electrolytic solution.
１     二次電池
３、３Ａ　カプセル
４、５　　添加装置（添加手段）
５     添加手段
１１   ケース
１２   蓋部
１３   電極体
１４   電解液
１５   正極端子
１６   負極端子
１７   正極集電部
１８   負極集電部
４１   筒状部
４２   大径部
４３   開口
４４   貯留部
４５   添加剤
４６   栓部 1 Secondary battery 3, 3A capsule 4, 5 Addition device (addition means)
DESCRIPTION OF SYMBOLS 5 Addition means 11 Case 12 Lid 13 Electrode body 14 Electrolyte 15 Positive electrode terminal 16 Negative electrode terminal 17 Positive electrode current collection part 18 Negative electrode current collection part 41 Tubular part 42 Large diameter part 43 Opening 44 Reservoir part 45 Additive 46 Plug part

Claims (7)

  1. 　電池ケースと、前記電池ケース内部に収納された電極体と、初期添加剤を含み、前記電池ケース内に満たされた電解液とを備えた二次電池であって、
    　前記電極体に前記初期添加剤により形成された被膜の劣化状態に応じて劣化状態を回復するための回復用添加剤を電解液に添加する添加手段を設けることを特徴とする二次電池。     A secondary battery comprising: a battery case; an electrode body housed inside the battery case; and an electrolyte solution containing an initial additive and filled in the battery case,
    A secondary battery comprising an addition means for adding to the electrolytic solution a recovery additive for recovering the deteriorated state according to the deteriorated state of the film formed by the initial additive on the electrode body.
  2. 　前記添加手段は、前記二次電池の劣化による前記電池ケース内の内圧が上昇して所定値以上となった場合に、前記添加剤を前記電解液に添加することを特徴とする請求項１記載の二次電池。 The said addition means adds the said additive to the said electrolyte solution, when the internal pressure in the said battery case by deterioration of the said secondary battery rises and it becomes more than predetermined value. Secondary battery.
  3. 　前記所定値は、前記電極体の充放電時の膨張収縮による内圧変化よりも大きいことを特徴とする請求項２記載の二次電池。 The secondary battery according to claim 2, wherein the predetermined value is larger than a change in internal pressure due to expansion and contraction at the time of charge and discharge of the electrode body.
  4. 　前記添加手段は、前記添加剤を前記電解液から隔離する隔離手段を有し、該隔離手段が前記内圧に応じて変形することで前記添加剤を前記電解液へ放出することを特徴とする請求項２又は３記載の二次電池。 The addition means includes separation means for separating the additive from the electrolyte, and the separation means is deformed according to the internal pressure to release the additive to the electrolyte. Item 4. A secondary battery according to item 2 or 3.
  5. 　前記添加手段は、前記添加剤を内包した前記隔離手段としてのカプセルであり、前記内圧が所定値以上となると該カプセルの壁面が破れて前記添加剤を前記電解液に添加するように構成されていることを特徴とする請求項４に記載の二次電池。 The addition means is a capsule as the separation means containing the additive, and the wall surface of the capsule is broken when the internal pressure reaches a predetermined value or more, and the additive is added to the electrolytic solution. The secondary battery according to claim 4, characterized in that:
  6. 　前記添加手段は、その一端側が封止され、他端側が開放された筒状部材、及び該筒状部材の中空部に嵌合し、該中空部を前記内圧の上昇により前記一端側に移動する移動部からなる前記隔離手段と、前記筒状部材の前記移動部の初期設置位置よりも一端側に設けられた開口に連通し、前記添加剤が貯留された貯留部とを備え、前記内圧の上昇により前記移動部が移動して、前記添加剤を前記電解液に添加するように構成されていることを特徴とする請求項４に記載の二次電池。 The addition means is fitted in a tubular member whose one end side is sealed and the other end side is opened, and a hollow portion of the tubular member, and the hollow portion is moved to the one end side by the increase of the internal pressure And a storage unit in communication with the opening provided at one end side of the initial installation position of the moving unit of the cylindrical member, the storage unit containing the additive, The secondary battery according to claim 4, wherein the moving part is moved by the rising to add the additive to the electrolytic solution.
  7. 　前記添加手段は、前記筒状部材の前記一端側に空気溜まり部が形成されていることを特徴とする請求項６記載の二次電池。 The secondary battery according to claim 6, wherein the addition means has an air reservoir formed on the one end side of the cylindrical member.
PCT/JP2012/078693 2011-11-10 2012-11-06 Secondary cell WO2013069622A1 (en)

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CN103811711A (en) * 2014-02-27 2014-05-21 深圳市格瑞普电池有限公司 Lithium ion battery with capsule
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CN104425844A (en) * 2013-09-09 2015-03-18 浙江万向亿能动力电池有限公司 Method for improving safety of power battery by isolation type inflame-retardant liquid
CN103682241A (en) * 2013-12-17 2014-03-26 深圳市格瑞普电池有限公司 Lithium ion battery provided with non-dust cloths
WO2015089749A1 (en) * 2013-12-17 2015-06-25 深圳市格瑞普电池有限公司 Lithium-ion battery provided with non-dust cloth
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EP4170768A4 (en) * 2021-08-26 2023-10-18 Contemporary Amperex Technology Co., Limited Battery cell, battery, and power consuming device

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JP2013105544A (en) 2013-05-30
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KR101571988B1 (en) 2015-11-25
KR20140105454A (en) 2014-09-01
CN103931041A (en) 2014-07-16

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