JP2013098064A - Nonaqueous battery and control method thereof - Google Patents

Nonaqueous battery and control method thereof Download PDF

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JP2013098064A
JP2013098064A JP2011240835A JP2011240835A JP2013098064A JP 2013098064 A JP2013098064 A JP 2013098064A JP 2011240835 A JP2011240835 A JP 2011240835A JP 2011240835 A JP2011240835 A JP 2011240835A JP 2013098064 A JP2013098064 A JP 2013098064A
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electrolytic solution
secondary battery
resistance value
wound body
electrolyte
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Yuki Omae
裕輝 大前
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Toyota Motor Corp
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    • 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
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Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous secondary battery and a control method thereof which can effectively improve durability against high rate discharges.SOLUTION: A nonaqueous secondary battery according to the present invention comprises: a wound body 20 with a first electrolyte impregnated therein; resistance measurement means 16 which measures the internal resistance value of the wound body; and a microcapsule 26 which, when the resistance value exceeds a prescribed threshold, supplies a second electrolyte having higher concentration than the first electrode to the inside of the wound body 20. The threshold is a resistance value at such a point that, when a cycle test consisting of repeated charges and discharges is executed in the nonaqueous secondary battery using the first and the second electrolytes respectively as electrolytes, the relative magnitude of resistance values is reversed.

Description

本発明は、非水二次電池及びその制御方法に関する。   The present invention relates to a non-aqueous secondary battery and a control method thereof.

リチウムイオン電池には、ハイレートでの放電を繰り返す態様で使用されることが想定されるものがある。車両の動力源として用いられるリチウムイオン電池は、このような使用態様が想定される代表例である。一般的なリチウムイオン電池は、ハイレートでの放電を繰り返す充放電パターンでは、性能劣化（内部抵抗の上昇等、以下ハイレート劣化とする）を起こしやすいことが知られていた。   Some lithium ion batteries are assumed to be used in a mode in which discharge at a high rate is repeated. A lithium ion battery used as a power source for a vehicle is a typical example in which such a usage mode is assumed. It has been known that a general lithium ion battery is liable to cause performance deterioration (increase in internal resistance, etc., hereinafter referred to as high rate deterioration) in a charge / discharge pattern that repeats discharge at a high rate.

そこで、特許文献１では、捲回体の中央部のリチウム濃度が低下した場合に、電解液にリチウムイオンを供給することで、ハイレート放電の繰り返しに対する耐久性を向上させている。リチウムイオンを供給する手段としては、容器に収容された当初の電解液のリチウムイオン濃度と実質的に同一のリチウムイオン濃度を有するリチウム溶液を内包したマイクロカプセルが用いられている。   Therefore, in Patent Document 1, when lithium concentration in the central portion of the wound body is lowered, durability against repeated high-rate discharge is improved by supplying lithium ions to the electrolytic solution. As a means for supplying lithium ions, a microcapsule enclosing a lithium solution having a lithium ion concentration substantially the same as the lithium ion concentration of the original electrolyte contained in the container is used.

特開２０１０−８６７２８号公報JP 2010-86728 A

この非水二次電池に関して発明者が検討したところ、以下のようなことが分かった。すなわち、非水二次電池の使用環境下の濃度範囲内において、充放電のサイクルの初期段階では電解液の濃度が低いと低抵抗であるが、サイクル回数の増加に伴いハイレート劣化が進行した段階では電解液の濃度が高いと低抵抗を保持できる。   The inventors have studied the non-aqueous secondary battery and found the following. That is, within the concentration range of the non-aqueous secondary battery in the usage environment, the resistance is low when the electrolyte concentration is low at the initial stage of the charge / discharge cycle, but the high rate deterioration has progressed as the number of cycles increases. Then, when the concentration of the electrolytic solution is high, low resistance can be maintained.

このように、リチウム濃度によって、充放電のサイクル数と抵抗値の上昇度は変化する。しかし、特許文献１に記載のリチウムイオン電池では、当初の電解液と同じ濃度のリチウム溶液を供給しているに過ぎない。性能劣化をさらに抑制し、耐久性を向上させるためには、単に同じ濃度のリチウム溶液を供給するだけでは不十分であることが分かった。   Thus, the number of charge / discharge cycles and the degree of increase in resistance value vary depending on the lithium concentration. However, the lithium ion battery described in Patent Document 1 merely supplies a lithium solution having the same concentration as the original electrolytic solution. In order to further suppress the performance deterioration and improve the durability, it has been found that it is not sufficient to simply supply a lithium solution having the same concentration.

本発明は、このような事情を背景としてなされたものであり、本発明の目的は、ハイレート放電に対する耐久性をより効果的に改善することが可能な非水二次電池及びその制御方法を提供することである。   The present invention has been made against the background of the above circumstances, and an object of the present invention is to provide a non-aqueous secondary battery capable of more effectively improving durability against high-rate discharge and a control method thereof. It is to be.

本発明の第１の形態に係る非水二次電池は、第１電解液を含浸させた捲回体と、前記捲回体内の抵抗値を測定する抵抗測定手段と、前記抵抗値が所定の閾値を超えた場合に、前記第１電解液より高濃度の第２電解液又は支持塩を前記捲回体内に供給する供給手段とを備える。このように、当初の第１電解液より高濃度の第２電解液を供給することにより、より抵抗値の上昇を抑制することができ、耐久性を効果的に改善することが可能となる。   A non-aqueous secondary battery according to a first aspect of the present invention includes a wound body impregnated with a first electrolyte, resistance measuring means for measuring a resistance value in the wound body, and the resistance value being a predetermined value. Supply means for supplying a second electrolytic solution or a supporting salt having a higher concentration than the first electrolytic solution into the wound body when the threshold value is exceeded. As described above, by supplying the second electrolytic solution having a higher concentration than the initial first electrolytic solution, it is possible to further suppress an increase in the resistance value and to effectively improve the durability.

本発明の第２の形態に係る非水二次電池は、上記の非水二次電池において、前記閾値は、前記第１電解液と前記第２電解液をそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合に抵抗値の大小が逆転する点での抵抗値であるものである。   The non-aqueous secondary battery according to a second aspect of the present invention is the non-aqueous secondary battery described above, wherein the threshold value is a non-aqueous secondary battery using the first electrolytic solution and the second electrolytic solution as electrolytic solutions, respectively. In the secondary battery, the resistance value is the point at which the magnitude of the resistance value is reversed when a cycle test in which charging and discharging are repeated is performed.

本発明の第３の形態に係る非水二次電池は、上記の非水二次電池において、前記第２電解液を供給する供給手段は、前記捲回体内に配置され、所定の温度で溶解する、前記第２電解液又は支持塩を内包したマイクロカプセルと、前記第１電解液の抵抗値が閾値を超えた場合に、前記捲回体が配置されるセル内の温度を前記所定の温度以上に上昇させる手段とをさらに備える。これにより、容易に第２電解液を供給することが可能となる。   The non-aqueous secondary battery according to a third aspect of the present invention is the above non-aqueous secondary battery, wherein the supply means for supplying the second electrolyte is disposed in the wound body and melts at a predetermined temperature. When the resistance value of the microcapsule encapsulating the second electrolytic solution or the supporting salt and the first electrolytic solution exceeds a threshold value, the temperature in the cell in which the wound body is disposed is the predetermined temperature. And further raising means. This makes it possible to easily supply the second electrolytic solution.

本発明の第４の形態に係る非水二次電池は、上記の非水二次電池において、前記第２電解液を供給した後の電解液の濃度は、前記第１電解液の濃度よりも高いことを特徴とする。これにより、さらに抵抗値を抑制することができ、長寿命化を実現できる。   In the non-aqueous secondary battery according to the fourth aspect of the present invention, in the non-aqueous secondary battery, the concentration of the electrolytic solution after supplying the second electrolytic solution is higher than the concentration of the first electrolytic solution. It is characterized by being expensive. As a result, the resistance value can be further suppressed, and a longer life can be realized.

本発明の第５の形態に係る非水二次電池は、上記の非水二次電池において、前記供給手段は、前記捲回体内に前記第２電解液又は支持塩を供給するための注液栓を有し、前記注液栓から、シリンジを介して前記第２電解液又は支持塩を注入するものである。   The non-aqueous secondary battery according to a fifth aspect of the present invention is the non-aqueous secondary battery described above, wherein the supply means is an injection for supplying the second electrolytic solution or supporting salt into the wound body. A stopper is provided, and the second electrolytic solution or supporting salt is injected from the injection stopper through a syringe.

本発明の第６の形態に係る非水二次電池の制御方法は、第１電解液を含浸させた捲回体内の抵抗値を測定し、前記抵抗値が所定の閾値を超えた場合に、当該第１電解液より高濃度の第２電解液又は支持塩を前記捲回体内に供給する。このように、当初の第１電解液より高濃度の第２電解液を供給することにより、より抵抗値の上昇を低減させることができ、耐久性を効果的に改善することが可能となる。   The control method of the non-aqueous secondary battery according to the sixth aspect of the present invention measures the resistance value in the wound body impregnated with the first electrolytic solution, and when the resistance value exceeds a predetermined threshold value, A second electrolytic solution or a supporting salt having a higher concentration than the first electrolytic solution is supplied into the wound body. As described above, by supplying the second electrolytic solution having a higher concentration than the initial first electrolytic solution, the increase in the resistance value can be further reduced, and the durability can be effectively improved.

本発明の第７の形態に係る非水二次電池の制御方法は、上記の方法において、前記閾値は、前記第１電解液と前記第２電解液をそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合に抵抗値の大小が逆転する点での抵抗値である。   A control method for a non-aqueous secondary battery according to a seventh aspect of the present invention is the above-described method, wherein the threshold value is a non-aqueous secondary using the first electrolyte solution and the second electrolyte solution as electrolyte solutions, respectively. In the battery, the resistance value is the point at which the magnitude of the resistance value is reversed when a cycle test that repeats charging and discharging is performed.

本発明の第８の形態に係る非水二次電池の制御方法は、上記の方法において、前記第１電解液の抵抗値が閾値を超えた場合に、前記捲回体が配置されるセル内の温度を上昇させ、前記第２電解液又は支持塩を内包したマイクロカプセルを溶解させ、前記第２電解液を前記捲回体内に流出させることを特徴とする。これにより、容易に第２電解液を供給することが可能となる。   The method for controlling a non-aqueous secondary battery according to an eighth aspect of the present invention is the method described above, wherein in the above method, when the resistance value of the first electrolyte exceeds a threshold value, the inside of the cell in which the wound body is disposed And the microcapsule containing the second electrolyte solution or the supporting salt is dissolved, and the second electrolyte solution is allowed to flow into the wound body. This makes it possible to easily supply the second electrolytic solution.

本発明の第９の形態に係る非水二次電池の制御方法は、上記の方法において、前記第２電解液を供給した後の電解液の濃度が、前記第１電解液の濃度よりも高くなるように、前記第２電解液を供給することを特徴とする。これにより、さらに抵抗値を低減させることができ、長寿命化を実現できる。   In the method for controlling a non-aqueous secondary battery according to a ninth aspect of the present invention, in the above method, the concentration of the electrolytic solution after supplying the second electrolytic solution is higher than the concentration of the first electrolytic solution. As described above, the second electrolytic solution is supplied. As a result, the resistance value can be further reduced, and a longer life can be realized.

本発明の第１０の形態に係る非水二次電池の制御方法は、上記の方法において、前記捲回体内に前記第２電解液又は支持塩を供給するための注液栓を開け、前記注液栓から前記第２電解液又は支持塩を注入することを特徴とする。   The method for controlling a non-aqueous secondary battery according to a tenth aspect of the present invention is the method described above, wherein the injection plug for supplying the second electrolyte or supporting salt into the wound body is opened, and the injection The second electrolytic solution or the supporting salt is injected from a liquid stopper.

本発明により、ハイレート放電に対する耐久性をより効果的に改善することが可能な非水二次電池及びその制御方法を提供するができる。   According to the present invention, it is possible to provide a non-aqueous secondary battery and a control method thereof that can more effectively improve durability against high-rate discharge.

実施の形態に係る非水二次電池の構成を示す模式図である。It is a schematic diagram which shows the structure of the non-aqueous secondary battery which concerns on embodiment. 図１のＩＩ−ＩＩ断面図である。It is II-II sectional drawing of FIG. 実施の形態に係る非水二次電池の捲回体の構成を示す模式図である。It is a schematic diagram which shows the structure of the winding body of the non-aqueous secondary battery which concerns on embodiment. 実施の形態に係る非水二次電池における第２電解液の供給タイミングを決定するための閾値について説明する図である。It is a figure explaining the threshold value for determining the supply timing of the 2nd electrolyte solution in the non-aqueous secondary battery which concerns on embodiment. 実施の形態に係る非水二次電池における、第２電解液の供給タイミングを説明するための図である。It is a figure for demonstrating the supply timing of the 2nd electrolyte solution in the non-aqueous secondary battery which concerns on embodiment. 第２電解液の濃度の最適値を説明するための図である。It is a figure for demonstrating the optimal value of the density | concentration of a 2nd electrolyte solution.

以下、本発明の実施の形態について図面を参照しながら説明する。以下の説明は、本発明の実施の形態を説明するものであり、本発明が以下の実施形態に限定されるものではない。説明の明確化のため、以下の記載は、適宜、省略及び簡略化がなされている。又、当業者であれば、以下の実施形態の各要素を、本発明の範囲において容易に変更、追加、変換することが可能である。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following description explains the embodiment of the present invention, and the present invention is not limited to the following embodiment. For clarity of explanation, the following description is omitted and simplified as appropriate. Moreover, those skilled in the art can easily change, add, and convert each element of the following embodiments within the scope of the present invention.

実施の形態．
本発明の実施の形態に係る非水二次電池について、図１を参照して説明する。図１は、実施の形態に係る非水二次電池１０の構成の一例を示す模式図である。ここでは、非水二次電池１０の一例として、扁平に捲回された電極体と電解液とが、直方体形状のセルに収容された形態のリチウムイオン電池について説明する。なお、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付し、重複する説明は省略または簡略化することがある。 Embodiment.
A nonaqueous secondary battery according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic diagram illustrating an example of a configuration of a nonaqueous secondary battery 10 according to an embodiment. Here, as an example of the non-aqueous secondary battery 10, a lithium ion battery in a form in which a flatly wound electrode body and an electrolytic solution are accommodated in a rectangular parallelepiped cell will be described. In addition, in the following drawings, the same code | symbol is attached | subjected to the member and site | part which show | plays the same effect | action, and the overlapping description may be abbreviate | omitted or simplified.

図１に示すように、非水二次電池１０は、セル１１、蓋体１２、正極端子１３、負極端子１４、加熱手段１５、抵抗測定手段１６を備えている。本発明に係る非水二次電池１０は、特に自動車等の車両に搭載されるモータ（電動機）用電源として好適に使用し得る。   As shown in FIG. 1, the nonaqueous secondary battery 10 includes a cell 11, a lid body 12, a positive electrode terminal 13, a negative electrode terminal 14, a heating unit 15, and a resistance measurement unit 16. The non-aqueous secondary battery 10 according to the present invention can be suitably used as a power source for a motor (electric motor) mounted on a vehicle such as an automobile.

図２は、図１のＩＩ−ＩＩ断面図である。図２に示すように、非水二次電池１０では、扁平に捲回された電極体である捲回体２０と図示しない第１電解液とが、予め、一端に開口部を有する直方体形状のセル１１に収容されている。セル１１は、蓋体１２により封止されている。   2 is a cross-sectional view taken along the line II-II in FIG. As shown in FIG. 2, in the nonaqueous secondary battery 10, the wound body 20, which is a flatly wound electrode body, and a first electrolyte solution (not shown) have a rectangular parallelepiped shape having an opening at one end in advance. It is accommodated in the cell 11. The cell 11 is sealed with a lid 12.

第１電解液としては、従来からリチウムイオン電池に用いられる非水電解液と同様のものを特に限定なく使用することができる。このような第１電解液は、典型的には、適当な非水溶媒に支持塩を含有させた組成を有する。また、非水二次電池１０は、セル１１の温度を上昇させる加熱手段１５を有する。加熱手段１５としては、例えば、車両用の暖機装置等を用いることができる。さらに、非水二次電池１０には、捲回体２０内の抵抗値を測定する抵抗測定手段１６が設けられている。抵抗測定手段１６は、例えば、非水二次電池１０の電圧変化値を車両のエンジン始動時に流す電流値で除算することにより抵抗値を算出する。   As a 1st electrolyte solution, the thing similar to the nonaqueous electrolyte solution conventionally used for a lithium ion battery can be used without limitation. Such a first electrolytic solution typically has a composition in which a supporting salt is contained in a suitable nonaqueous solvent. In addition, the nonaqueous secondary battery 10 includes a heating unit 15 that raises the temperature of the cell 11. As the heating means 15, for example, a warming-up device for vehicles can be used. Further, the non-aqueous secondary battery 10 is provided with a resistance measuring means 16 that measures the resistance value in the wound body 20. For example, the resistance measuring unit 16 calculates the resistance value by dividing the voltage change value of the non-aqueous secondary battery 10 by the current value that flows when the engine of the vehicle is started.

図３は、捲回体２０の構成を示す模式図である。図３に示すように、捲回体２０は、正極シート２１、負極シート２２、正極活物質層２３、負極活物質層２４、セパレータ２５、マイクロカプセル２６を備える。セパレータ２５には、マイクロカプセル２６が保持されている。   FIG. 3 is a schematic diagram showing the configuration of the wound body 20. As shown in FIG. 3, the wound body 20 includes a positive electrode sheet 21, a negative electrode sheet 22, a positive electrode active material layer 23, a negative electrode active material layer 24, a separator 25, and a microcapsule 26. The separator 25 holds the microcapsule 26.

捲回体２０は、セパレータ２５にマイクロカプセル２６が保持されている点を除いて、通常のリチウムイオン電池の捲回体と同様である。正極活物質層２３、セパレータ２５、負極活物質層２４がこの順で、長尺状の正極シート２１と負極シート２２との間に配置されている。この長尺状の積層体が、扁平に捲回されて捲回体２０が構成される。   The wound body 20 is the same as the wound body of a normal lithium ion battery except that the microcapsules 26 are held by the separator 25. The positive electrode active material layer 23, the separator 25, and the negative electrode active material layer 24 are disposed in this order between the long positive electrode sheet 21 and the negative electrode sheet 22. The elongated laminate is wound flatly to form a wound body 20.

正極シート２１、負極シート２２には、これらの両電極シートと活物質層、セパレータ２５が捲回されたコア部分から外側にはみ出した部分がある。正極シート２１のコア部分から外側にはみ出した部分には、正極端子１３の一端が接続される。負極シート２２のコア部分から外側にはみ出した部分には、負極端子１４の一端が接続される。正極端子１３、負極端子１４の他端は、蓋体１２から外部に引き出されている。   The positive electrode sheet 21 and the negative electrode sheet 22 have a portion that protrudes outward from the core portion around which both the electrode sheet, the active material layer, and the separator 25 are wound. One end of the positive electrode terminal 13 is connected to a portion of the positive electrode sheet 21 that protrudes outward from the core portion. One end of the negative electrode terminal 14 is connected to a portion of the negative electrode sheet 22 that protrudes outward from the core portion. The other ends of the positive electrode terminal 13 and the negative electrode terminal 14 are drawn out from the lid body 12.

なお、正極シート２１、負極シート２２、正極活物質層２３、負極活物質層２４、セパレータ２５としては、従来のリチウムイオン電池に備えられる電極体と同様のものを用いることができる。   In addition, as the positive electrode sheet 21, the negative electrode sheet 22, the positive electrode active material layer 23, the negative electrode active material layer 24, and the separator 25, the thing similar to the electrode body with which the conventional lithium ion battery is equipped can be used.

正極シート２１と負極シート２２との間に配置されるセパレータ２５としては、捲回体を備える従来のリチウムイオン電池のセパレータと同様の各種多孔質シートを用いることができる。本実施の形態に係る非水二次電池１０では、セパレータ２５には、第２電解液を内包するマイクロカプセル２６が保持されている。   As the separator 25 disposed between the positive electrode sheet 21 and the negative electrode sheet 22, various porous sheets similar to the separators of a conventional lithium ion battery including a wound body can be used. In the nonaqueous secondary battery 10 according to the present embodiment, the separator 25 holds the microcapsule 26 that contains the second electrolytic solution.

非水二次電池１０は、捲回体２０内の抵抗値が所定の閾値を超えた場合に、第１電解液より高濃度の第２電解液を捲回体２０内に供給することを特徴としている。本実施の形態に示す例では、マイクロカプセル２６が第２電解液の供給手段となる。   The nonaqueous secondary battery 10 supplies a second electrolytic solution having a higher concentration than the first electrolytic solution into the wound body 20 when the resistance value in the wound body 20 exceeds a predetermined threshold value. It is said. In the example shown in the present embodiment, the microcapsule 26 serves as the second electrolytic solution supply means.

マイクロカプセル２６の外殻は、６０〜８０℃の所定の温度で溶解、分解するものが用いられる。このような外殻を構成し得る材料としては、例えば、高分子材料、脂肪族炭化水素化合物、アルコール、エステル、脂肪酸等があげられる。非水二次電池１０が車両に適用される場合において、通常の車両の使用時には、非水二次電池１０が６０℃以上となることはないため、マイクロカプセル２６は溶解しない。   As the outer shell of the microcapsule 26, one that dissolves and decomposes at a predetermined temperature of 60 to 80 ° C. is used. Examples of materials that can constitute such an outer shell include polymer materials, aliphatic hydrocarbon compounds, alcohols, esters, fatty acids, and the like. When the nonaqueous secondary battery 10 is applied to a vehicle, the microcapsule 26 does not dissolve when the normal vehicle is used because the nonaqueous secondary battery 10 does not reach 60 ° C. or higher.

マイクロカプセル２６には、第１電解液のリチウム濃度よりも濃度が高い第２電解液が内包されている。第２電解液として、捲回体２０に予め含浸された第１電解液と実質的に同組成のものを用いることができる。また、第２電解液の溶媒としては、例えば、第１電解液の構成成分として用いられる各種の非水溶媒のうちの一種以上を採用することができる。第２電解液を構成する支持塩としては、電解液の支持塩として例示した各種の支持塩が挙げられる。   The microcapsule 26 contains a second electrolytic solution having a higher concentration than the lithium concentration of the first electrolytic solution. As the second electrolytic solution, one having substantially the same composition as that of the first electrolytic solution previously impregnated in the wound body 20 can be used. Moreover, as a solvent of 2nd electrolyte solution, 1 or more types of the various nonaqueous solvents used as a structural component of 1st electrolyte solution are employable, for example. Examples of the supporting salt constituting the second electrolytic solution include various supporting salts exemplified as the supporting salt for the electrolytic solution.

ここで、図４を参照して、第２電解液の供給タイミングを決定する閾値について説明する。図４は、非水二次電池１０における第２電解液の供給タイミングを決定するための閾値について説明する図である。図４は、異なるリチウム濃度の電解液Ａ、Ｂをそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合の抵抗値の変化を示している。   Here, with reference to FIG. 4, the threshold value which determines the supply timing of 2nd electrolyte solution is demonstrated. FIG. 4 is a diagram illustrating threshold values for determining the supply timing of the second electrolyte solution in the nonaqueous secondary battery 10. FIG. 4 shows a change in resistance value when a cycle test in which charge and discharge are repeated in a non-aqueous secondary battery using electrolytic solutions A and B having different lithium concentrations as electrolytic solutions, respectively.

図４において、横軸はハイレートでの充放電のサイクル数（ｃｙｃ）を示しており、縦軸は捲回体２０内の抵抗値を示している。電解液Ｂのほうが電解液Ａよりもリチウム濃度が高いものとする。   In FIG. 4, the horizontal axis indicates the number of cycles of charge / discharge (cyc) at a high rate, and the vertical axis indicates the resistance value in the wound body 20. It is assumed that the electrolytic solution B has a higher lithium concentration than the electrolytic solution A.

図４の鎖線円中に示すように、初期の段階では、低濃度の電解液Ａを用いた場合のほうが高濃度の電解液Ｂを用いた場合よりも抵抗値が小さい。しかし、サイクル試験を繰り返し行うと、図４中矢印で示すように、電解液Ａと電解液Ｂの抵抗値の大小が逆転する点が存在する。   As shown in the chain line circle in FIG. 4, at the initial stage, the resistance value is smaller when the low concentration electrolytic solution A is used than when the high concentration electrolytic solution B is used. However, when the cycle test is repeatedly performed, there is a point where the resistance values of the electrolytic solution A and the electrolytic solution B are reversed as indicated by arrows in FIG.

さらにサイクル試験を繰り返した場合、低濃度の電解液Ａと比較すると、高濃度の電解液Ｂでは抵抗値の上昇が緩やかになる。このことから、高濃度の電解液のほうがハイレート耐性に優れているということが分かる。   Further, when the cycle test is repeated, the resistance value increases more slowly in the high concentration electrolytic solution B than in the low concentration electrolytic solution A. From this, it can be seen that a high concentration electrolytic solution is superior in high-rate resistance.

そこで、本実施の形態では、濃度の異なる電解液をそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合に捲回体内の抵抗値の大小が逆転する点での抵抗値を閾値とする。   Therefore, in this embodiment, in a non-aqueous secondary battery using electrolytes with different concentrations as electrolytes, the resistance value in the wound body is reversed when a cycle test that repeats charging and discharging is performed. The resistance value at is a threshold value.

ここで、図５を参照して、第２電解液の供給タイミングについて説明する。図５は、非水二次電池１０における、第２電解液の供給タイミングを説明するための図である。図５において、横軸はハイレートでの充放電のサイクル数（ｃｙｃ）を示しており、縦軸は捲回体２０内の抵抗値を示している。   Here, the supply timing of the second electrolytic solution will be described with reference to FIG. FIG. 5 is a diagram for explaining the supply timing of the second electrolyte solution in the nonaqueous secondary battery 10. In FIG. 5, the horizontal axis represents the number of cycles of charge / discharge at a high rate (cyc), and the vertical axis represents the resistance value in the wound body 20.

図５中、破線は第２電解液を注入しなかった場合の抵抗値の変化を示しており、実践は第２電解液を注入した場合の抵抗値の変化を示している。上述の通り、図５における閾値は、充放電を繰り返すサイクル試験を実施した場合に抵抗値の大小が逆転する点である。   In FIG. 5, the broken line indicates the change in resistance value when the second electrolytic solution is not injected, and the practice indicates the change in resistance value when the second electrolytic solution is injected. As described above, the threshold value in FIG. 5 is a point where the magnitude of the resistance value is reversed when a cycle test in which charging and discharging are repeated is performed.

まず、第１電解液を含浸させた捲回体２０内の抵抗値を抵抗測定手段１６により測定する。その抵抗値が所定の閾値を超えた場合に、当該第１電解液より高濃度の第２電解液を捲回体２０内に供給する。図５からわかるように、第２電解液を注入した場合、注入しなかった場合と比較すると、抵抗値の上昇を抑制することができる。これにより、ハイレート劣化耐性を向上させることができ、電池の長寿命化を実現できる。   First, the resistance value in the wound body 20 impregnated with the first electrolytic solution is measured by the resistance measuring means 16. When the resistance value exceeds a predetermined threshold value, a second electrolytic solution having a higher concentration than the first electrolytic solution is supplied into the wound body 20. As can be seen from FIG. 5, when the second electrolytic solution is injected, an increase in the resistance value can be suppressed as compared to the case where the second electrolytic solution is not injected. Thereby, the high-rate deterioration resistance can be improved, and the battery life can be extended.

第２電解液を供給した後の電解液の濃度が、初期の第１電解液の濃度よりも高くなることが好ましい。これにより、さらに効果的に、ハイレート劣化耐性を向上させることが可能となる。   It is preferable that the concentration of the electrolytic solution after supplying the second electrolytic solution is higher than the initial concentration of the first electrolytic solution. Thereby, it becomes possible to improve the high-rate deterioration resistance more effectively.

本実施の形態では、第２電解液の供給手段として、所定の温度で溶解するマイクロカプセル２６を用いている。捲回体２０の抵抗値が所定の閾値を超えた場合に、加熱手段１５によりセル１１を加熱する。セル１１内の温度がマイクロカプセル２６の外殻が溶解する温度に達すると、マイクロカプセル２６が溶解し、捲回体２０内に第１電解液よりも高濃度の第２電解液が供給される。   In the present embodiment, microcapsules 26 that dissolve at a predetermined temperature are used as means for supplying the second electrolytic solution. When the resistance value of the wound body 20 exceeds a predetermined threshold value, the cell 11 is heated by the heating means 15. When the temperature in the cell 11 reaches a temperature at which the outer shell of the microcapsule 26 is dissolved, the microcapsule 26 is dissolved, and the second electrolytic solution having a higher concentration than the first electrolytic solution is supplied into the wound body 20. .

このように、本実施の形態では、セル１１の温度を上昇させることによって、捲回体２０内に高濃度の第２電解液を供給している。このため、注液栓を開けることなく、容易に第２電解液を供給して、電解液濃度を高めることができる。   Thus, in this Embodiment, the 2nd electrolyte solution with a high concentration is supplied in the winding body 20 by raising the temperature of the cell 11. For this reason, it is possible to easily supply the second electrolytic solution without opening the injection plug and increase the concentration of the electrolytic solution.

ここで、捲回体２０内に供給する第２電解液の濃度について、図６を参照して説明する。図６は、異なるリチウム濃度の電解液Ａ、Ｂ、Ｃをそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合の抵抗値の変化を示している。電解液濃度は、電解液Ａ＜電解液Ｂ＜電解液Ｃであるものとする。   Here, the density | concentration of the 2nd electrolyte solution supplied in the winding body 20 is demonstrated with reference to FIG. FIG. 6 shows a change in resistance value when a cycle test in which charge and discharge are repeated is performed in a non-aqueous secondary battery using electrolytic solutions A, B, and C having different lithium concentrations as electrolytic solutions. The electrolytic solution concentration is assumed to be electrolytic solution A <electrolytic solution B <electrolytic solution C.

図６に示すように、電解液のリチウム濃度が高くなると、ハイレート劣化耐性が向上する。しかし、ある値を超えるとそれ以上ハイレート劣化耐性は向上しなくなる。また、電解質濃度が高いと初期の抵抗値が高くなり、第２電解液を供給する際の捲回体２０の抵抗値の閾値が大きくなる。   As shown in FIG. 6, when the lithium concentration of the electrolytic solution is increased, the high-rate deterioration resistance is improved. However, when the value exceeds a certain value, the high-rate deterioration resistance is not improved any more. Further, when the electrolyte concentration is high, the initial resistance value increases, and the threshold value of the resistance value of the wound body 20 when the second electrolytic solution is supplied increases.

従って、供給される第２電解液のリチウム濃度は、充放電を繰り返した際に抵抗値の上昇が抑制されるように設定される。また、第１電解液のリチウム濃度は、初期の抵抗が低くなるように設定される。   Therefore, the lithium concentration of the supplied second electrolytic solution is set so that an increase in resistance value is suppressed when charging and discharging are repeated. Further, the lithium concentration of the first electrolytic solution is set so that the initial resistance is lowered.

図６において、電解液Ａのリチウム濃度は１．０ｍｏｌ／Ｌであり、電解液Ｃのリチウム濃度は２．０ｍｏｌ／Ｌである。従って、第２電解液を供給した後の塩濃度範囲を、例えば１．０ｍｏｌ／Ｌより大きく、２．０ｍｏｌ／Ｌより小さい範囲とすることにより、充放電を繰り返した際に抵抗値の上昇を抑制することが可能となる。   In FIG. 6, the lithium concentration of the electrolytic solution A is 1.0 mol / L, and the lithium concentration of the electrolytic solution C is 2.0 mol / L. Therefore, by increasing the salt concentration range after supplying the second electrolytic solution, for example, to a range larger than 1.0 mol / L and smaller than 2.0 mol / L, the resistance value increases when charging and discharging are repeated. It becomes possible to suppress.

以上説明したように、本発明では、第１電解液を含浸させた捲回体２０内の抵抗値が所定の閾値を超えた場合に、第１電解液より高濃度の第２電解液を捲回体２０内に供給する。これにより、抵抗値の上昇を抑制することができ、ハイレート劣化耐性を向上させることができ、電池の長寿命化を実現できる。   As described above, in the present invention, when the resistance value in the wound body 20 impregnated with the first electrolyte exceeds a predetermined threshold value, the second electrolyte having a higher concentration than the first electrolyte is removed. It is supplied into the rotary body 20. Thereby, an increase in resistance value can be suppressed, high-rate deterioration resistance can be improved, and the battery life can be extended.

なお、上述の実施の形態では、供給手段としてマイクロカプセルを用いた例について説明したが、これに限定されるものではない。例えば、注液栓を開け、注射器等で第２電解液を補充してもよい。また、マイクロカプセル内に第２電解液を内包する例に限らず、マイクロカプセル内に第１電解液に含まれる支持塩と同一のものを内包してもよい。   In the above-described embodiment, the example in which the microcapsule is used as the supply unit has been described. However, the present invention is not limited to this. For example, the injection plug may be opened and the second electrolytic solution may be replenished with a syringe or the like. Further, the present invention is not limited to the example in which the second electrolytic solution is included in the microcapsule, and the same support salt contained in the first electrolytic solution may be included in the microcapsule.

上述の実施の形態では、セパレータ２５にマイクロカプセル２６が保持されている例を示したが、これに限定されない。マイクロカプセル２６が捲回体２０内のいずれの場所に保持されていても、同様の効果が得られる。   In the above-described embodiment, an example in which the microcapsule 26 is held in the separator 25 has been described, but the present invention is not limited to this. The same effect can be obtained regardless of where the microcapsule 26 is held in the wound body 20.

１０ 非水二次電池
１１ セル
１２ 蓋体
１３ 正極端子
１４ 負極端子
１５ 加熱手段
１６ 抵抗測定手段
２０ 捲回体
２１ 正極シート
２２ 負極シート
２３ 正極活物質層
２４ 負極活物質層
２５ セパレータ
２６ マイクロカプセル DESCRIPTION OF SYMBOLS 10 Nonaqueous secondary battery 11 Cell 12 Cover body 13 Positive electrode terminal 14 Negative electrode terminal 15 Heating means 16 Resistance measuring means 20 Winding body 21 Positive electrode sheet 22 Negative electrode sheet 23 Positive electrode active material layer 24 Negative electrode active material layer 25 Separator 26 Microcapsule

Claims (10)

第１電解液を含浸させた捲回体と、
前記捲回体内の抵抗値を測定する抵抗測定手段と、
前記抵抗値が所定の閾値を超えた場合に、前記第１電解液より高濃度の第２電解液又は支持塩を前記捲回体内に供給する供給手段と、
を備える非水二次電池。 A wound body impregnated with a first electrolytic solution;
Resistance measuring means for measuring a resistance value in the wound body;
A supply means for supplying a second electrolytic solution or supporting salt having a higher concentration than the first electrolytic solution into the wound body when the resistance value exceeds a predetermined threshold;
A non-aqueous secondary battery. 前記閾値は、前記第１電解液と前記第２電解液をそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合に抵抗値の大小が逆転する点での抵抗値である請求項１に記載の非水二次電池。   In the non-aqueous secondary battery using the first electrolytic solution and the second electrolytic solution as the electrolytic solutions, the threshold value is that the resistance value is reversed when a cycle test is repeated. The nonaqueous secondary battery according to claim 1, which has a resistance value. 前記第２電解液を供給する供給手段は、
前記捲回体内に配置され、所定の温度で溶解する、前記第２電解液又は支持塩を内包したマイクロカプセルと、
前記第１電解液の抵抗値が閾値を超えた場合に、前記捲回体が配置されるセル内の温度を前記所定の温度以上に上昇させる手段と、
をさらに備える請求項１又は２に記載の非水二次電池。 Supply means for supplying the second electrolyte solution comprises:
A microcapsule that is disposed within the wound body and that dissolves at a predetermined temperature and that contains the second electrolyte or supporting salt;
Means for increasing the temperature in the cell in which the wound body is disposed above the predetermined temperature when the resistance value of the first electrolyte exceeds a threshold;
The nonaqueous secondary battery according to claim 1 or 2, further comprising: 前記第２電解液を供給した後の電解液の濃度は、前記第１電解液の濃度よりも高いことを特徴とする請求項１〜３のいずれか１項に記載の非水二次電池。   4. The nonaqueous secondary battery according to claim 1, wherein the concentration of the electrolytic solution after supplying the second electrolytic solution is higher than the concentration of the first electrolytic solution. 5. 前記供給手段は、
前記捲回体内に前記第２電解液又は支持塩を供給するための注液栓を有し、
前記注液栓から、シリンジを介して前記第２電解液又は支持塩を注入する請求項１〜４のいずれか１項に記載の非水二次電池。 The supply means includes
An injection stopper for supplying the second electrolyte or supporting salt into the wound body;
The nonaqueous secondary battery according to any one of claims 1 to 4, wherein the second electrolytic solution or the supporting salt is injected from the liquid injection stopper through a syringe. 第１電解液を含浸させた捲回体内の抵抗値を測定し、
前記抵抗値が所定の閾値を超えた場合に、当該第１電解液より高濃度の第２電解液又は支持塩を前記捲回体内に供給する、
非水二次電池の制御方法。 Measure the resistance value in the wound body impregnated with the first electrolyte,
When the resistance value exceeds a predetermined threshold value, a second electrolytic solution or a supporting salt having a higher concentration than the first electrolytic solution is supplied into the wound body.
Control method of non-aqueous secondary battery. 前記閾値は、前記第１電解液と前記第２電解液をそれぞれ電解液として用いた非水二次電池において、充放電を繰り返すサイクル試験を実施した場合に抵抗値の大小が逆転する点での抵抗値である請求項６に記載の非水二次電池の制御方法。   In the non-aqueous secondary battery using the first electrolytic solution and the second electrolytic solution as the electrolytic solutions, the threshold value is that the resistance value is reversed when a cycle test is repeated. The method for controlling a non-aqueous secondary battery according to claim 6, wherein the control value is a resistance value. 前記第１電解液の抵抗値が閾値を超えた場合に、前記捲回体が配置されるセル内の温度を上昇させ、前記第２電解液又は支持塩を内包したマイクロカプセルを溶解させ、前記第２電解液を前記捲回体内に流出させることを特徴とする請求項６又は７に記載の非水二次電池の制御方法。   When the resistance value of the first electrolyte exceeds a threshold value, the temperature in the cell in which the wound body is disposed is increased, the microcapsules containing the second electrolyte or supporting salt are dissolved, The method for controlling a non-aqueous secondary battery according to claim 6 or 7, wherein the second electrolytic solution is allowed to flow into the wound body. 前記第２電解液を供給した後の電解液の濃度が、前記第１電解液の濃度よりも高くなるように、前記第２電解液を供給することを特徴とする請求項６〜８のいずれか１項に記載の非水二次電池の制御方法。   The said 2nd electrolyte solution is supplied so that the density | concentration of the electrolyte solution after supplying the said 2nd electrolyte solution may become higher than the density | concentration of the said 1st electrolyte solution. The control method of the non-aqueous secondary battery of Claim 1. 前記捲回体内に前記第２電解液又は支持塩を供給するための注液栓を開け、前記注液栓から前記第２電解液又は支持塩を注入する請求項６〜９のいずれか１項に記載の非水二次電池の制御方法。   The liquid injection plug for supplying the second electrolytic solution or the supporting salt into the wound body is opened, and the second electrolytic solution or the supporting salt is injected from the liquid injection plug. The control method of the non-aqueous secondary battery as described in 2.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015049571A1 (en) * 2013-10-04 2015-04-09 Toyota Jidosha Kabushiki Kaisha Nonaqueous electrolyte secondary battery and method for producing same
CN109186711A (en) * 2018-08-28 2019-01-11 合肥国轩高科动力能源有限公司 A kind of decision procedure of lithium ion battery liquid injection amount

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015049571A1 (en) * 2013-10-04 2015-04-09 Toyota Jidosha Kabushiki Kaisha Nonaqueous electrolyte secondary battery and method for producing same
CN105612650A (en) * 2013-10-04 2016-05-25 丰田自动车株式会社 Nonaqueous electrolyte secondary battery and method for producing same
CN109186711A (en) * 2018-08-28 2019-01-11 合肥国轩高科动力能源有限公司 A kind of decision procedure of lithium ion battery liquid injection amount

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