JP4472415B2 - Non-aqueous electrolyte secondary battery charging method and charger - Google Patents

Non-aqueous electrolyte secondary battery charging method and charger Download PDF

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JP4472415B2
JP4472415B2 JP2004133728A JP2004133728A JP4472415B2 JP 4472415 B2 JP4472415 B2 JP 4472415B2 JP 2004133728 A JP2004133728 A JP 2004133728A JP 2004133728 A JP2004133728 A JP 2004133728A JP 4472415 B2 JP4472415 B2 JP 4472415B2
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剛平 鈴木
万郷 藤川
秀治 武澤
克己 高津
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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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
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Description

本発明は、リチウムイオン二次電池等の非水電解質二次電池の寿命特性を向上させることのできる充電方法および充電器に関する。   The present invention relates to a charging method and a charger that can improve the life characteristics of a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery.

アルカリ水溶液系の電解液を含む二次電池においては、正極活物質として用いられる水酸化ニッケルの相転移によるメモリー効果（不活性化）を解消する手段として、充電器にセット後に、二次電池を強制放電させる方法が知られている（例えば、特許文献１、特許文献２参照）。   In a secondary battery containing an alkaline aqueous electrolyte, the secondary battery is installed after being set in a charger as a means to eliminate the memory effect (inactivation) due to the phase transition of nickel hydroxide used as the positive electrode active material. A method of forcibly discharging is known (see, for example, Patent Document 1 and Patent Document 2).

一方、非水溶媒系の電解液を含む二次電池（非水電解質二次電池）においては、電極に用いられる材料に、メモリー効果のような不具合は認められない。そのため、充電器にセット後に、電池電圧をチェックし、充電終止電圧以上もしくは短絡を示唆する低電圧以下のいずれでもない場合には、直ちに充電を開始する充電方法が一般的である。   On the other hand, in a secondary battery (nonaqueous electrolyte secondary battery) containing a nonaqueous solvent-based electrolyte, there is no problem such as a memory effect in the material used for the electrode. For this reason, a battery charging method is generally used in which the battery voltage is checked after being set in the charger, and charging is started immediately when the battery voltage is not higher than the end-of-charge voltage or lower than the low voltage indicating a short circuit.

近年、携帯電話を中心に、非水電解質二次電池の主電源としての用途が拡大している。それに伴い、非水電解質二次電池においても、残存容量が多い状態で充電を行うと、電池容量の低下が大きくなることが明らかになってきた。このような容量低下の原因は、詳細は明らかではないが、次のように考えられている。   In recent years, applications as a main power source for non-aqueous electrolyte secondary batteries have been expanding mainly in mobile phones. Along with this, it has become clear that, even in nonaqueous electrolyte secondary batteries, when the battery is charged with a large remaining capacity, the battery capacity decreases greatly. The cause of such a decrease in capacity is not clear in detail, but is considered as follows.

すなわち、リチウムイオン二次電池の負極は、正極よりもサイズが大きい。従って、充電状態で放置されているリチウムイオン二次電池の場合、負極に吸蔵されているリチウムイオンが、正極と対向しない負極位置に拡散する。そのように拡散したリチウムイオンは、放電に寄与できなくなると考えられる（特許文献３）。
特開平７−１４６１３号公報 特開平８−３３２２１号公報 特開２００３−３６８９１号公報 That is, the negative electrode of the lithium ion secondary battery is larger in size than the positive electrode. Therefore, in the case of a lithium ion secondary battery left in a charged state, lithium ions occluded in the negative electrode diffuse to a negative electrode position that does not face the positive electrode. It is considered that lithium ions diffused in such a manner cannot contribute to discharge (Patent Document 3).
JP 7-14613 A Japanese Patent Laid-Open No. 8-33221 JP 2003-36891 A

特許文献３では、非水電解質二次電池の容量低下を抑制するために、電池電圧の測定と、定電流放電と、放電後電池の放置とを、繰り返し、電池電圧が所定電圧以下になってから充電を行う方法が提案されている。しかし、このような方法は、以下の問題を有する。   In patent document 3, in order to suppress the capacity | capacitance fall of a nonaqueous electrolyte secondary battery, the measurement of a battery voltage, constant current discharge, and leaving the battery after discharge are repeated, and a battery voltage becomes below a predetermined voltage. A method of charging is proposed. However, such a method has the following problems.

一律に所定電圧以下になるまで電池の強制放電を行う場合、残存容量が少なければ問題はない。しかし、残存容量が多いと、強制放電に要する時間が長くなり、充電を完了するまでに長時間を要するという問題がある。容量が８０％以上も残されている状態の二次電池が充電器にセットされることも希ではない。顧客の使い勝手を考慮すれば、上記方法は実用的ではない。   When the battery is forcibly discharged until it reaches a predetermined voltage or less uniformly, there is no problem if the remaining capacity is small. However, if the remaining capacity is large, there is a problem that the time required for forced discharge becomes long and it takes a long time to complete the charging. It is not rare that a secondary battery having a capacity of 80% or more is set in the charger. The above method is not practical considering the convenience of the customer.

また、一律に強制放電を行うと、当然、充放電サイクルの繰り返し回数も多くなる。そのため、結局、活物質の劣化などの他の要因に基づく容量低下を引き起こす。従って、寿命特性を向上させるという目的を達することはできなくなる。   In addition, when the forced discharge is uniformly performed, the number of repetitions of the charge / discharge cycle is naturally increased. Therefore, the capacity is eventually reduced based on other factors such as deterioration of the active material. Therefore, the purpose of improving the life characteristics cannot be achieved.

さらに、残存容量が多い状態で強制放電することは、多量のエネルギーを浪費することに等しい。このような方法は、多くの環境問題やエネルギー問題を抱える現代社会において、推奨し得る方法ではない。   Furthermore, forcible discharge with a large remaining capacity is equivalent to wasting a large amount of energy. Such a method is not a method that can be recommended in a modern society with many environmental and energy problems.

本発明は、上記諸問題を鑑みて成されたものであり、非水電解質二次電池の寿命特性を向上させることのできる充電方法および充電器に関する。   The present invention has been made in view of the above-described problems, and relates to a charging method and a charger that can improve the life characteristics of a nonaqueous electrolyte secondary battery.

すなわち、本発明は、リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池の充電方法であって、（ａ）前記二次電池の開回路電圧を検出し、検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する工程、および（ｂ）前記判定に応じて、〔イ〕検出値が領域Ａに含まれる場合には、充電を停止し、〔ロ〕検出値が領域Ｂに含まれる場合には、充電を行い、〔ハ〕検出値が領域Ｃに含まれる場合には、前記二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う工程、を有する充電方法（以下、充電方法Ｘともいう）に関する。 That is, the present invention relates to a method for charging a nonaqueous electrolyte secondary battery comprising a positive electrode including a lithium-containing composite oxide as an active material, a negative electrode including a material capable of inserting and extracting lithium ions as an active material, and a nonaqueous electrolyte. And (a) an open circuit voltage of the secondary battery is detected, and a detected value is a voltage region A that is equal to or greater than a predetermined value X, a voltage region B that is less than a predetermined value X and exceeds a predetermined value Y (Y <X). And (b) in response to the determination, [b] if the detected value is included in the region A, the charging is stopped, [B] When the detected value is included in the region B, charging is performed, and [c] When the detected value is included in the region C, the closed circuit voltage of the secondary battery is a predetermined value Z (Z <Y ) A charging method having a step of charging after discharging until , Charging method X).

本発明は、また、リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池を複数個直列に接続して充電する充電方法であって、（ａ）少なくとも１つの二次電池の開回路電圧を検出し、検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する工程、および（ｂ）前記判定に応じて、〔イ〕いずれかの検出値が領域Ａに含まれる場合には、充電を停止し、〔ロ〕すべての検出値が領域Ｂに含まれる場合には、充電を行い、〔ハ〕いずれかの検出値が領域Ｃに含まれる場合には、いずれかの二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う工程、を有する充電方法（以下、充電方法Ｙともいう）に関する。 The present invention also includes a plurality of non-aqueous electrolyte secondary batteries each including a positive electrode including a lithium-containing composite oxide as an active material, a negative electrode including a material capable of inserting and extracting lithium ions as an active material, and a non-aqueous electrolyte. A charging method in which charging is performed by connecting in series, wherein (a) an open circuit voltage of at least one secondary battery is detected, and a detected value is a voltage region A greater than or equal to a predetermined value X, less than a predetermined value X, and a predetermined value Determining whether the voltage region B exceeds Y (Y <X) or the voltage region C equal to or less than the predetermined value Y; and (b) depending on the determination, [a] any detected value is When it is included in the area A, charging is stopped. [B] When all the detected values are included in the area B, charging is performed. [C] When any of the detected values are included in the area C The closed circuit voltage of any secondary battery is a predetermined value Z (Z <Y) The present invention relates to a charging method (hereinafter, also referred to as charging method Y) having a step of charging after discharging until the following.

本発明は、また、リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池の充電を行う充電器であって、（ａ）前記二次電池の開回路電圧を検出する電圧検知手段、（ｂ）検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する判定手段、および（ｃ）前記判定に応じて、〔イ〕検出値が領域Ａに含まれる場合には、充電を停止し、〔ロ〕検出値が領域Ｂに含まれる場合には、充電を行い、〔ハ〕検出値が領域Ｃに含まれる場合には、前記二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う選択的充電手段、を有する充電器（以下、充電器Ｘともいう）に関する。 The present invention also charges a non-aqueous electrolyte secondary battery comprising a positive electrode containing a lithium-containing composite oxide as an active material, a negative electrode containing a material capable of occluding and releasing lithium ions as an active material, and a non-aqueous electrolyte. (A) voltage detection means for detecting an open circuit voltage of the secondary battery, (b) a voltage value A in which the detected value is equal to or greater than a predetermined value X, less than a predetermined value X and a predetermined value Y ( Determining means for determining whether the voltage region B exceeds Y <X) or the voltage region C equal to or less than the predetermined value Y; and (c) the detected value is included in the region A according to the determination. If the detected value is included in the area B, the charging is performed. If the detected value is included in the area C, the secondary battery is closed. Charging is performed after discharging until the circuit voltage falls below a predetermined value Z (Z <Y) The present invention relates to a charger having selective charging means (hereinafter also referred to as charger X).

本発明は、さらに、リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池を複数個直列に接続して充電する充電器であって、（ａ）少なくとも１つの二次電池の開回路電圧を検出する電圧検知手段、（ｂ）検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する判定手段、および（ｃ）前記判定に応じて、〔イ〕いずれかの検出値が領域Ａに含まれる場合には、充電を停止し、〔ロ〕すべての検出値が領域Ｂに含まれる場合には、充電を行い、〔ハ〕いずれかの検出値が領域Ｃに含まれる場合には、いずれかの二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う選択的充電手段、を有する充電器（以下、充電器Ｙともいう）に関する。 The present invention further includes a plurality of non-aqueous electrolyte secondary batteries each including a positive electrode including a lithium-containing composite oxide as an active material, a negative electrode including a material capable of inserting and extracting lithium ions as an active material, and a non-aqueous electrolyte. A charger for connecting and charging in series, wherein (a) voltage detection means for detecting an open circuit voltage of at least one secondary battery, (b) a voltage region A in which a detected value is a predetermined value X or more, a predetermined value Determining means for determining which of the voltage region B is less than the value X and exceeding the predetermined value Y (Y <X) and the voltage region C less than or equal to the predetermined value Y; and (c) ] When any detection value is included in the area A, charging is stopped. [B] When all the detection values are included in the area B, charging is performed. Is included in region C, any of the secondary batteries Charger circuit voltage has a selective charging means, for charging after discharged to below a predetermined value Z (Z <Y) (hereinafter also referred to as a charger Y) relates.

充電器ＸおよびＹにおいて、電圧検知手段、判定手段および選択的充電手段の２つ以上は、１つの装置に組み込まれていてもよい。   In the chargers X and Y, two or more of the voltage detection means, the determination means, and the selective charging means may be incorporated in one device.

前記所定値Ｘは、前記二次電池において推奨される充電終止電圧±０．０３Ｖ以内の値である。
前記所定値Ｘは、前記二次電池の公称電圧の±１％の値が好適である。
前記所定値Ｙは、前記二次電池の残存容量が公称容量の２０％以下のときの値である。
前記所定値Ｚは、２．７Ｖ以上２．９Ｖ以下の値である。 The predetermined value X is a value within a charge end voltage ± 0.03 V recommended for the secondary battery.
The predetermined value X is preferably a value of ± 1% of the nominal voltage of the secondary battery.
The predetermined value Y is a value when the remaining capacity of the secondary battery is 20% or less of the nominal capacity.
Wherein the predetermined value Z is 2.9V following values than 2.7V.

充電方法Ｘにおいては、二次電池の閉回路電圧が、所定値Ｘに達したときに、充電を停止することが好ましい。
充電方法Ｙにおいては、いずれかの二次電池の閉回路電圧が、所定値Ｘに達したときに、充電を停止することが好ましい。 In the charging method X, it is preferable to stop charging when the closed circuit voltage of the secondary battery reaches a predetermined value X.
In the charging method Y, it is preferable to stop charging when the closed circuit voltage of any secondary battery reaches a predetermined value X.

本発明によれば、時間的およびエネルギー的に効率よく非水電解質二次電池の充電を行うことができるとともに、充放電の繰り返しに伴う容量低下を抑制することができる。   ADVANTAGE OF THE INVENTION According to this invention, while being able to charge a nonaqueous electrolyte secondary battery efficiently in time and energy, the capacity | capacitance fall accompanying the repetition of charging / discharging can be suppressed.

以下、本発明の一実施形態について図面を参照しながら説明する。
図１は、非水電解質二次電池の充電方法を説明するためのフローチャートであり、図２は、充電装置の回路図である。この回路は、放電回路１３と充電回路１４とを具備する。充電装置に非水電解質二次電池１１をセットすると、二次電池１１は、その開回路電圧を検出するための電圧検知部を具備する処理部１２と並列接続される。処理部１２は、また、電圧の検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する判定回路等の判定部を備えている。 Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a flowchart for explaining a method for charging a nonaqueous electrolyte secondary battery, and FIG. 2 is a circuit diagram of a charging device. This circuit includes a discharging circuit 13 and a charging circuit 14. When the nonaqueous electrolyte secondary battery 11 is set in the charging device, the secondary battery 11 is connected in parallel with the processing unit 12 including a voltage detection unit for detecting the open circuit voltage. The processing unit 12 also includes a voltage region A in which a detected voltage value is greater than or equal to a predetermined value X, a voltage region B that is less than the predetermined value X and exceeds a predetermined value Y (Y <X), and a voltage region C that is less than or equal to the predetermined value Y. A determination unit such as a determination circuit for determining which is included is provided.

充電回路１４と外部電源１５とは閉回路を構成している。二次電池１１の充電時には、切替回路１６の動作により、充電回路１４と二次電池１１とが閉回路を構成する。その結果、二次電池１１は、充電回路１４を介して外部電源１５とも閉回路を構成する。一方、二次電池１１の放電時には、切替回路１６の動作により、放電回路１３と二次電池１１とが閉回路を構成する。   The charging circuit 14 and the external power supply 15 constitute a closed circuit. When the secondary battery 11 is charged, the charging circuit 14 and the secondary battery 11 form a closed circuit by the operation of the switching circuit 16. As a result, the secondary battery 11 forms a closed circuit with the external power supply 15 via the charging circuit 14. On the other hand, when the secondary battery 11 is discharged, the operation of the switching circuit 16 causes the discharge circuit 13 and the secondary battery 11 to form a closed circuit.

二次電池１１の負極、放電回路１３の負極側端子および充電回路１４の負極側端子は、それぞれ外部電源１５の負極端子と同電位を有する。二次電池１１の正極、放電回路１３の正極側端子および充電回路１４の正極側端子は、それぞれ切替回路１６が具備する所定の端子１７、１８および１９と接続されている。   The negative electrode of the secondary battery 11, the negative electrode side terminal of the discharge circuit 13, and the negative electrode side terminal of the charging circuit 14 have the same potential as the negative electrode terminal of the external power supply 15. The positive electrode of the secondary battery 11, the positive electrode side terminal of the discharge circuit 13, and the positive electrode side terminal of the charging circuit 14 are respectively connected to predetermined terminals 17, 18, and 19 provided in the switching circuit 16.

切替回路１６は、二次電池１１の正極と放電回路１３の正極側端子との間の接続を制御する放電スイッチと、二次電池１１の正極と充電回路１４の正極側端子との接続を制御する充電スイッチとを具備する。放電スイッチがＯＮされると、二次電池１１の正極と放電回路１３の正極側端子とが接続され、放電スイッチがＯＦＦされると、その接続が切断される。また、充電スイッチがＯＮされると、二次電池１１の正極と充電回路１４の正極側端子とが接続され、充電スイッチがＯＦＦされると、その接続が切断される。   The switching circuit 16 controls the connection between the positive electrode of the secondary battery 11 and the positive terminal of the discharge circuit 13, and the connection between the positive electrode of the secondary battery 11 and the positive terminal of the charging circuit 14. A charging switch. When the discharge switch is turned on, the positive electrode of the secondary battery 11 and the positive electrode side terminal of the discharge circuit 13 are connected, and when the discharge switch is turned off, the connection is cut. Further, when the charging switch is turned on, the positive electrode of the secondary battery 11 and the positive terminal of the charging circuit 14 are connected, and when the charging switch is turned off, the connection is cut.

切替回路１６は、二次電池１１の電圧を検出する電圧検知部および検出値が電圧領域Ａ、ＢおよびＣのいずれに含まれるかを判定する判定部を有する処理部１２と相互に連絡し合っている。判定部における判定結果によって、切替回路１６が制御される。なお、判定部は、切替回路１６が備えていてもよく、その場合には、電圧検出値の情報が、そのまま切替回路１６に伝達される。   The switching circuit 16 communicates with the processing unit 12 having a voltage detection unit that detects the voltage of the secondary battery 11 and a determination unit that determines in which of the voltage regions A, B, and C the detected value is included. ing. The switching circuit 16 is controlled by the determination result in the determination unit. Note that the determination unit may be included in the switching circuit 16, and in this case, information on the voltage detection value is transmitted to the switching circuit 16 as it is.

切替回路１６の放電スイッチがＯＮされて、二次電池１１の正極と放電回路１３の正極側端子とが接続されると、放電回路１３は、二次電池１１をその閉回路電圧が所定値Ｚ以下になるまで放電させる。放電中の二次電池１１の閉回路電圧は、放電回路１３または処理部１２などによりモニタされ、電圧が所定値Ｚ以下に達した時点で、放電スイッチがＯＦＦされて、放電回路１３の正極側端子と二次電池１１の正極との接続が切断される。   When the discharge switch of the switching circuit 16 is turned on and the positive electrode of the secondary battery 11 and the positive terminal of the discharge circuit 13 are connected, the discharge circuit 13 connects the secondary battery 11 to a predetermined value Z. Discharge until: The closed circuit voltage of the secondary battery 11 during discharge is monitored by the discharge circuit 13 or the processing unit 12. When the voltage reaches a predetermined value Z or less, the discharge switch is turned off and the positive side of the discharge circuit 13 is turned on. The connection between the terminal and the positive electrode of the secondary battery 11 is disconnected.

一方、切替回路１６の充電スイッチがＯＮされて、二次電池１１の正極と充電回路１４の正極側端子とが接続されると、充電回路１４は、二次電池１１をその閉回路電圧が所定値に達するまで充電する。充電中の二次電池１１の閉回路電圧は、充電回路または処理部１２などによりモニタされ、電圧が所定値に達した時点で、充電スイッチがＯＦＦされて、充電回路１４の正極側端子と二次電池１１の正極との接続が切断される。   On the other hand, when the charging switch of the switching circuit 16 is turned on and the positive electrode of the secondary battery 11 and the positive terminal of the charging circuit 14 are connected, the charging circuit 14 sets the secondary battery 11 to a predetermined closed circuit voltage. Charge until the value is reached. The closed circuit voltage of the secondary battery 11 being charged is monitored by the charging circuit or the processing unit 12 or the like. When the voltage reaches a predetermined value, the charging switch is turned off and the charging circuit 14 is connected to the positive side terminal. The connection with the positive electrode of the secondary battery 11 is disconnected.

充電と放電の両方を停止する場合には、放電スイッチおよび充電スイッチの両方がＯＦＦされる。
切替回路１６が、上記のようなスイッチ機能を制御する制御部を備える場合、その制御部には、処理部１２などから必要な情報が入力される。
なお、電圧検知部、判定部および制御部は、マイクロコンピュータ、ワイヤードロジック回路等によって構成することができる。 When both charging and discharging are stopped, both the discharging switch and the charging switch are turned off.
When the switching circuit 16 includes a control unit that controls the switch function as described above, necessary information is input to the control unit from the processing unit 12 or the like.
The voltage detection unit, the determination unit, and the control unit can be configured by a microcomputer, a wired logic circuit, or the like.

次に、上記充電装置を用いる場合を例にとって、本発明の充電方法の一例について、図１のフローチャートを参照しながら説明する。
まず、二次電池１１を充電装置にセットする（Ｓ0）。すると、切替回路１６が両スイッチをＯＦＦにした状態で、処理部１２の電圧検知部が二次電池の開回路電圧を検出する。 Next, taking the case of using the above charging device as an example, an example of the charging method of the present invention will be described with reference to the flowchart of FIG.
First, the secondary battery 11 is set in the charging device (S 0 ). Then, the voltage detection part of the process part 12 detects the open circuit voltage of a secondary battery in the state which switched circuit 16 turned off both switches.

次いで、検出値（ＯＣＶ）が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙを超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを、処理部１２の判定部が判定する（Ｓ1）。 Next, the processing unit determines whether the detected value (OCV) is included in a voltage region A that is greater than or equal to the predetermined value X, a voltage region B that is less than the predetermined value X and exceeds the predetermined value Y, and a voltage region C that is less than or equal to the predetermined value Y. Twelve determination units determine (S 1 ).

判定の結果、Ｘ≦ＯＣＶの場合、二次電池１１は満充電状態と考えられる。その場合、それ以上の充電は不要であるから、切替回路１６は充電を停止する。このとき、充電スイッチと放電スイッチの両方はＯＦＦ状態のままである。   As a result of the determination, when X ≦ OCV, the secondary battery 11 is considered to be fully charged. In that case, since no further charging is necessary, the switching circuit 16 stops charging. At this time, both the charge switch and the discharge switch remain in the OFF state.

また、Ｙ＜ＯＣＶ＜Ｘの場合、切替回路１６は、充電スイッチをＯＮにするとともに、放電スイッチをＯＦＦにする。その結果、充電が開始される（Ｓ2）。
そして、充電開始から所定時間経過後に二次電池１１の閉回路電圧（ＣＣＶ）が測定される（Ｓ3）。ＣＣＶが所定値Ｘに達していない場合には、再度充電が開始される。一方、ＣＣＶが所定値Ｘに達している場合には、充電が停止される（Ｓ4）。ステップＳ2およびＳ3は、ＣＣＶが所定値Ｘに達するまで繰り返される。 When Y <OCV <X, the switching circuit 16 turns on the charge switch and turns off the discharge switch. As a result, charging is started (S 2 ).
Then, the closed circuit voltage (CCV) of the secondary battery 11 is measured after a predetermined time has elapsed from the start of charging (S 3 ). If the CCV has not reached the predetermined value X, charging is started again. On the other hand, if the CCV has reached the predetermined value X, charging is stopped (S 4 ). Steps S 2 and S 3 are repeated until CCV reaches a predetermined value X.

ステップＳ1において、判定の結果、ＯＣＶ≦Ｙの場合、切替回路１６は、充電スイッチをＯＦＦにするとともに、放電スイッチをＯＮにする。その結果、放電が開始される（Ｓ12）。 In Step S 1, the result of the determination, if the OCV ≦ Y, the switching circuit 16 is configured to turn OFF the charging switch, the discharging switch to ON. As a result, discharge is started (S 12 ).

そして、放電開始から所定時間経過後に二次電池１１の閉回路電圧（ＣＣＶ）が測定される（Ｓ13）。ＣＣＶが所定値Ｚに達していない場合には、再度放電が開始される。一方、ＣＣＶが所定値Ｚに達している場合には、切替回路１６は、充電スイッチをＯＮにするとともに、放電スイッチをＯＦＦにする。その結果、充電が開始される（Ｓ2）。ステップＳ12およびＳ13は、ＣＣＶが所定値Ｚに達するまで繰り返される。 Then, the closed circuit voltage (CCV) of the secondary battery 11 is measured after a predetermined time has elapsed from the start of discharge (S 13 ). If the CCV has not reached the predetermined value Z, the discharge is started again. On the other hand, when the CCV has reached the predetermined value Z, the switching circuit 16 turns on the charge switch and turns off the discharge switch. As a result, charging is started (S 2 ). Step S 12 and S 13 are repeated until the CCV reaches a predetermined value Z.

所定値Ｘは、二次電池において推奨される充電終止電圧±０．０３Ｖ以内の値である。また、二次電池の公称電圧±１％の値であれば採用することができる。 The predetermined value X is a value within a charge end voltage ± 0.03 V recommended for the secondary battery. Further, a value of the nominal voltage of the secondary battery ± 1% can be adopted.

また、所定値Ｙは、二次電池の公称容量に対する残存容量に基づいて決定することが好ましい。なお、公称容量は、通常、２０℃で定電流−定電圧充電の後、電池の定電流放電を行うことにより求められる。具体的には、公称容量を求める場合と同じ条件で電池を充電し、その後、公称容量を求める場合と同じ条件で、残存容量が公称容量の２０％になるまで電池を放電する。所定値Ｙは、こうして得られた残存容量が公称容量の２０％のときの電圧以下とすることが好ましい。また、リフレッシュに要する時間を短縮する観点からは、残存容量が公称容量の１０％のときの電圧以下とすることが好ましい。   The predetermined value Y is preferably determined based on the remaining capacity with respect to the nominal capacity of the secondary battery. In addition, a nominal capacity is normally calculated | required by performing constant current discharge of a battery after constant current-constant voltage charge at 20 degreeC. Specifically, the battery is charged under the same conditions as when the nominal capacity is obtained, and then the battery is discharged under the same conditions as when the nominal capacity is obtained until the remaining capacity reaches 20% of the nominal capacity. The predetermined value Y is preferably set to be equal to or lower than the voltage when the remaining capacity thus obtained is 20% of the nominal capacity. Further, from the viewpoint of shortening the time required for refreshing, it is preferable that the voltage be equal to or lower than the voltage when the remaining capacity is 10% of the nominal capacity.

所定値Ｙをあまり大きい値に設定すると、残存容量が多い状態で充電を行う回数が多くなり、サイクルの繰り返しによる容量劣化を防止する効果が小さくなる。所定値Ｙは、残存容量が公称容量の２０％以下のときの値である。 When the predetermined value Y is set to a very large value, the number of times of charging is increased in a state where the remaining capacity is large, and the effect of preventing capacity deterioration due to repeated cycles is reduced. Predetermined value Y, the remaining capacity is a value when the following 2 0% of the nominal capacity.

また、所定値Ｚは、二次電池の過放電を防止する観点から、２．７Ｖ以上２．９Ｖ以下の値である。２．９Ｖより高いとリフレッシュ放電の効果が小さくなり、２．７Ｖより低いと過放電となって電池特性が低下する可能性がある。 Moreover, the predetermined value Z is a value of 2.7 V or more and 2.9 V or less from the viewpoint of preventing overdischarge of the secondary battery. When the voltage is higher than 2.9 V, the effect of refresh discharge is reduced, and when the voltage is lower than 2.7 V, the battery characteristics may be deteriorated due to overdischarge.

図３に、コバルト酸リチウムを正極活物質とする正極およびグラファイトを負極活物質とする負極を具備するリチウムイオン二次電池（以下、電池Ｐという）の０．２Ｃ電流での放電カーブを示す。ここで、充電では、１Ｃの定電流で４．２Ｖまで定電流充電の後、電流値が０．０５Ｃになるまで定電圧充電を行った。電池Ｐの公称容量は８５０ｍＡｈであり、０．２Ｃ電流は、１７０ｍＡである。なお、公称容量は、正極活物質から求められる理論容量をベースに決定される。   FIG. 3 shows a discharge curve at 0.2 C current of a lithium ion secondary battery (hereinafter referred to as battery P) having a positive electrode using lithium cobaltate as a positive electrode active material and a negative electrode using graphite as a negative electrode active material. Here, in charging, constant voltage charging was performed until the current value reached 0.05 C after constant current charging to 4.2 V with a constant current of 1 C. The nominal capacity of the battery P is 850 mAh, and the 0.2C current is 170 mA. The nominal capacity is determined based on the theoretical capacity obtained from the positive electrode active material.

図３より、電池Ｐを満充電状態から０．２Ｃ電流で約２４０分間放電したとき、すなわち残存容量が公称容量の２０％のとき、ＯＣＶが３．７５Ｖ付近にあることがわかる。従って、所定値Ｙとして、例えば３．７５Ｖ以下の値が好適であると言える。   FIG. 3 shows that the OCV is around 3.75 V when the battery P is discharged for about 240 minutes at 0.2 C current from the fully charged state, that is, when the remaining capacity is 20% of the nominal capacity. Accordingly, it can be said that a value of 3.75 V or less is suitable as the predetermined value Y, for example.

なお、非水電解質二次電池の正極活物質として用いられるリチウム含有複合酸化物としては、コバルト酸リチウムの他に、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4などが挙げられる。ただし、これらに限定されるものではない。また、負極活物質であるリチウムイオンを吸蔵・放出可能な材料としては、グラファイト、易黒鉛化性炭素、難黒鉛化性炭素、炭素繊維等の炭素材料が好ましい。また、グラファイトとしては、各種の人造黒鉛および天然黒鉛が用いられている。電池の充放電時において、グラファイトからなる負極の電位曲線は、比較的平坦である。そのため、対向する正極の電位によって、電池の充放電状態を検知しやすく、充放電の制御も比較的容易である。 Note that examples of the lithium-containing composite oxide used as the positive electrode active material of the non-aqueous electrolyte secondary battery include LiNiO 2 and LiMn 2 O 4 in addition to lithium cobaltate. However, it is not limited to these. In addition, as a material capable of inserting and extracting lithium ions which are negative electrode active materials, carbon materials such as graphite, graphitizable carbon, non-graphitizable carbon, and carbon fiber are preferable. As the graphite, various artificial graphites and natural graphites are used. During charging / discharging of the battery, the potential curve of the negative electrode made of graphite is relatively flat. Therefore, it is easy to detect the charge / discharge state of the battery by the potential of the opposing positive electrode, and charge / discharge control is relatively easy.

次に、複数の非水電解質二次電池を同時に充電する場合の一例について説明する。
図４は、複数の非水電解質二次電池の充電方法を説明するためのフローチャートであり、図５は、充電装置の回路図である。なお、図２に示した装置と同じ機能を有する構成要素には、図２と同じ番号を付記する。 Next, an example of charging a plurality of nonaqueous electrolyte secondary batteries at the same time will be described.
FIG. 4 is a flowchart for explaining a method for charging a plurality of nonaqueous electrolyte secondary batteries, and FIG. 5 is a circuit diagram of the charging apparatus. Components having the same functions as those of the apparatus shown in FIG. 2 are denoted by the same reference numerals as those in FIG.

この回路は、２並列×２直列の二次電池群を同時に充電する場合を示している。並列接続された２個の二次電池１１ａおよびｂは、それらの開回路電圧を検出するための第１電圧検知部を具備する第１処理部１２ａと並列接続されている。同じく並列接続された２個の二次電池１１ｃおよびｄは、それらの開回路電圧を検出するための第２電圧検知部を具備する第２処理部１２ｂと並列接続されている。そして、二次電池１１ａおよびｂの対と、二次電池１１ｃおよびｄの対とが、直列に接続されている。また、第１処理部および第２処理部は、それぞれ電圧の検出値が、電圧領域Ａ、ＢおよびＣのいずれに含まれるかを判定する第１判定部および第２判定部を具備する。   This circuit shows a case where 2 parallel × 2 series secondary battery groups are charged simultaneously. The two secondary batteries 11a and 11b connected in parallel are connected in parallel with a first processing unit 12a including a first voltage detection unit for detecting their open circuit voltages. Similarly, two secondary batteries 11c and d connected in parallel are connected in parallel with a second processing unit 12b including a second voltage detection unit for detecting their open circuit voltages. A pair of secondary batteries 11a and b and a pair of secondary batteries 11c and d are connected in series. The first processing unit and the second processing unit each include a first determination unit and a second determination unit that determine which of the voltage regions A, B, and C includes the detected voltage value.

ここで、並列接続された２個の二次電池は、これらを合わせて１個の二次電池と見なされる。すなわち、本発明においては、並列接続された複数の二次電池は、１個の二次電池として取り扱われる。このことは、本発明が並列接続された複数の二次電池を充電する充電方法および充電器を含み、本発明がこれらを排除しないことを意味する。   Here, the two secondary batteries connected in parallel are regarded as one secondary battery. That is, in the present invention, a plurality of secondary batteries connected in parallel are handled as one secondary battery. This means that the present invention includes a charging method and a charger for charging a plurality of secondary batteries connected in parallel, and the present invention does not exclude them.

第１処理部１２ａおよび第２処理部１２ｂは、それぞれ切替回路１６と相互に連絡し合っており、第１および第２電圧検知部における判定結果が切替回路１６に伝達される。   The first processing unit 12 a and the second processing unit 12 b are in communication with the switching circuit 16, and the determination results in the first and second voltage detection units are transmitted to the switching circuit 16.

なお、判定回路等の判定部は、切替回路１６が備えていてもよく、その場合には、開回路電圧の検出値がそのまま切替回路１６に伝達される。図５の回路は、以上の点以外は、図２と同様の構成を有する。   Note that a determination unit such as a determination circuit may be included in the switching circuit 16, and in this case, the detection value of the open circuit voltage is transmitted to the switching circuit 16 as it is. The circuit of FIG. 5 has the same configuration as that of FIG. 2 except for the above points.

次に、上記充電装置を用いる場合を例にとって、本発明の充電方法の一例について、図４のフローチャートを参照しながら説明する。
まず、二次電池１１ａ〜ｄを充電装置にセットする（Ｓ0）。すると、切替回路１６が、充電スイッチと放電スイッチの両方をＯＦＦにした状態で、第１処理部１２ａの第１電圧検知部が、二次電池１１ａおよび１１ｂからなる並列電池の開回路電圧を測定する。 Next, taking the case of using the above charging device as an example, an example of the charging method of the present invention will be described with reference to the flowchart of FIG.
First sets the charging apparatus of the secondary battery 11a~d (S 0). Then, the switching circuit 16 turns off both the charge switch and the discharge switch, and the first voltage detection unit of the first processing unit 12a measures the open circuit voltage of the parallel battery including the secondary batteries 11a and 11b. To do.

そして、電圧の検出値（ＯＣＶ）が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙを超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかが、第１処理部１２ａの判定部により判定される（Ｓ1）。 Then, whether the detected voltage value (OCV) is included in the voltage region A that is equal to or greater than the predetermined value X, the voltage region B that is less than the predetermined value X and exceeds the predetermined value Y, and the voltage region C that is equal to or less than the predetermined value Y. It is determined by the determination unit of the first processing unit 12a (S 1 ).

判定の結果、Ｘ≦ＯＣＶの場合、二次電池１１ａおよび１１ｂからなる並列電池は満充電状態と考えられ、それ以上の充電は過充電となる。そのため、切替回路１６により、充電は停止される。このとき、充電スイッチと放電スイッチの両方はＯＦＦ状態のままである。   As a result of the determination, when X ≦ OCV, the parallel battery including the secondary batteries 11a and 11b is considered to be in a fully charged state, and further charging is overcharged. Therefore, charging is stopped by the switching circuit 16. At this time, both the charge switch and the discharge switch remain in the OFF state.

一方、Ｙ＜ＯＣＶ＜Ｘの場合、続いて、第２処理部１２ｂの第２電圧検知部が、二次電池１１ｃおよび１１ｄからなる並列電池の開回路電圧を測定し、第２処理部１２ｂの判定部が検出値を判定する（Ｓ2）。 On the other hand, if Y <OCV <X, then, the second voltage detection unit of the second processing unit 12b measures the open circuit voltage of the parallel battery including the secondary batteries 11c and 11d, and the second processing unit 12b The determination unit determines the detection value (S 2 ).

判定の結果、Ｘ≦ＯＣＶの場合、二次電池１１ｃおよび１１ｄからなる並列電池は満充電状態と考えられ、それ以上の充電は過充電となる。そのため、切替回路１６により、充電は停止される。このとき、充電スイッチと放電スイッチの両方はＯＦＦ状態のままである。   As a result of the determination, when X ≦ OCV, the parallel battery including the secondary batteries 11c and 11d is considered to be in a fully charged state, and further charging is overcharged. Therefore, charging is stopped by the switching circuit 16. At this time, both the charge switch and the discharge switch remain in the OFF state.

第２電圧検知部における検出値が、Ｙ＜ＯＣＶ＜Ｘの場合、２つの並列電池は、いずれも満充電状態ではない。従って、それ以上の充電を行うことができる。そして、２つの並列電池のいずれかの電圧が所定値Ｘに達した時点で充電を停止すれば、二次電池１１ａ〜ｄのいずれも過充電になることはない。   When the detection value in the second voltage detector is Y <OCV <X, neither of the two parallel batteries is fully charged. Therefore, further charging can be performed. If charging is stopped when the voltage of one of the two parallel batteries reaches the predetermined value X, none of the secondary batteries 11a to 11d is overcharged.

そこで、切替回路１６は、充電スイッチをＯＮにするとともに、放電スイッチをＯＦＦにする。その結果、充電回路１４により、二次電池１１ａ〜ｄの充電が開始される（Ｓ3）。 Therefore, the switching circuit 16 turns on the charge switch and turns off the discharge switch. As a result, the charging circuit 14, charging of the secondary battery 11a~d is started (S 3).

そして、充電開始から所定時間経過後に、二次電池１１ａおよび１１ｂからなる並列電池の閉回路電圧（ＣＣＶ）が測定され（Ｓ4）、ＣＣＶが所定値Ｘに達している場合には、充電が停止される（Ｓ6）。 After a predetermined time has elapsed from start of charging, a closed circuit voltage of the parallel cell comprising the secondary battery 11a and 11b (CCV) is measured (S 4), when the CCV has reached the predetermined value X, charging Stopped (S 6 ).

一方、ＣＣＶが所定値Ｘに達していない場合には、引き続き二次電池１１ｃおよび１１ｄからなる並列電池の閉回路電圧（ＣＣＶ）が測定され、検出値が判定される（Ｓ5）。判定の結果、ＣＣＶが所定値Ｘに達している場合には、充電が停止される（Ｓ6）。 On the other hand, CCV is, if you have not yet reached the predetermined value X, continues closed circuit voltage of the parallel cell comprising the secondary battery 11c and 11d (CCV) is measured, the detected value is determined (S 5). As a result of the determination, if the CCV has reached the predetermined value X, charging is stopped (S 6 ).

一方、ＣＣＶが所定値Ｘに達していない場合には、いずれの並列電池も未だ満充電に達していないため、再度充電が行われる（Ｓ3）。Ｓ3〜Ｓ5は、いずれかの並列電池のＣＣＶが所定値Ｘに達するまで繰り返される。 On the other hand, if the CCV has not reached the predetermined value X, none of the parallel batteries has yet reached full charge, so that charging is performed again (S 3 ). S 3 to S 5 are repeated until the CCV of any parallel battery reaches a predetermined value X.

ステップＳ1またはＳ2において、判定の結果、ＯＣＶ≦Ｙの場合、切替回路１６は、充電スイッチをＯＦＦにするとともに、放電スイッチをＯＮにする。その結果、放電回路１３により、二次電池１１ａ〜ｄの放電が開始される（Ｓ22）。 In step S 1 or S 2 , if OCV ≦ Y as a result of the determination, the switching circuit 16 turns off the charge switch and turns on the discharge switch. As a result, the discharge circuit 13, discharge is initiated in the secondary battery 11a~d (S 22).

そして、放電開始から所定時間経過後に、二次電池１１ａおよび１１ｂからなる並列電池の閉回路電圧（ＣＣＶ）が測定され、検出値が判定される（Ｓ23）。このときＣＣＶが所定値Ｚに達していない場合には、引き続き二次電池１１ｃおよび１１ｄからなる並列電池の閉回路電圧（ＣＣＶ）が測定され、検出値が判定される（Ｓ24）。 After a predetermined time has elapsed from the start of discharge closed circuit voltage of the parallel cell comprising the secondary battery 11a and 11b (CCV) is measured, the detected value is determined (S 23). At this time CCV is, if you have not yet reached the predetermined value Z is subsequently closed circuit voltage of the parallel cell comprising the secondary battery 11c and 11d (CCV) is measured, the detected value is determined (S 24).

一方、二次電池１１ａおよび１１ｂからなる並列電池の閉回路電圧（ＣＣＶ）が所定値Ｚに達している場合には、充電が開始される（Ｓ3）。
ステップＳ24における判定の結果、二次電池１１ｃおよび１１ｄからなる並列電池のＣＣＶが所定値Ｚに達していない場合には、いずれの並列電池も未だ十分にリフレッシュされていないため、再度放電が行われる（Ｓ22）。一方、Ｓ24における判定の結果、二次電池１１ｃおよび１１ｄからなる並列電池のＣＣＶが所定値Ｚに達している場合には、充電が開始される（Ｓ3）。ステップＳ22〜Ｓ24は、いずれかの並列電池のＣＣＶが所定値Ｚに達するまで繰り返される。 On the other hand, when the closed circuit voltage of the parallel cell comprising the secondary battery 11a and 11b (CCV) has reached a predetermined value Z, the charging is started (S 3).
If the result of determination in step S 24, when the CCV parallel cell comprising the secondary battery 11c and 11d has not reached the predetermined value Z, since any parallel battery also not yet fully refreshed, discharge line again (S 22 ). On the other hand, the result of determination in S 24, when the CCV parallel cell comprising the secondary battery 11c and 11d has reached the predetermined value Z, the charging is started (S 3). Steps S 22 to S 24 are repeated until the CCV of any parallel battery reaches a predetermined value Z.

以上のような充電方法によれば、いずれの電池も過放電もしくは過充電の状態になることはない。   According to the charging method as described above, none of the batteries are overdischarged or overcharged.

本発明の充電方法および充電器によれば、時間的およびエネルギー的に効率よく非水電解質二次電池の充電を行うことができるとともに、充放電の繰り返しに伴う容量低下を抑制することができる。本発明の充電方法および充電器は、特にリチウムイオン二次電池の充電に好適である。   According to the charging method and the charger of the present invention, it is possible to charge the nonaqueous electrolyte secondary battery efficiently in terms of time and energy, and it is possible to suppress a decrease in capacity due to repeated charge and discharge. The charging method and charger of the present invention are particularly suitable for charging lithium ion secondary batteries.

本発明の一実施形態に係る非水電解質二次電池の充電方法を説明するためのフローチャートである。It is a flowchart for demonstrating the charging method of the nonaqueous electrolyte secondary battery which concerns on one Embodiment of this invention. 本発明の一実施形態に係る非水電解質二次電池の充電方法を実施する充電装置の回路図である。It is a circuit diagram of the charging device which enforces the charging method of the nonaqueous electrolyte secondary battery concerning one embodiment of the present invention. コバルト酸リチウムを正極活物質とする正極およびグラファイトを負極活物質とする負極を具備するリチウムイオン二次電池の０．２Ｃ電流での放電カーブを示す図である。It is a figure which shows the discharge curve in the 0.2C electric current of the lithium ion secondary battery which comprises the positive electrode which uses lithium cobaltate as a positive electrode active material, and the negative electrode which uses graphite as a negative electrode active material. 本発明の一実施形態に係る複数の非水電解質二次電池の充電方法を説明するためのフローチャートである。It is a flowchart for demonstrating the charging method of the some nonaqueous electrolyte secondary battery which concerns on one Embodiment of this invention. 本発明の一実施形態に係る複数の非水電解質二次電池の充電方法を実施する充電装置の回路図である。It is a circuit diagram of the charging device which implements the charging method of a plurality of nonaqueous electrolyte secondary batteries concerning one embodiment of the present invention.

符号の説明Explanation of symbols

１１ 二次電池
１１ａ 二次電池
１１ｂ 二次電池
１１ｃ 二次電池
１１ｄ 二次電池
１２ 処理部
１２ａ 第１処理部
１２ｂ 第２処理部
１３ 放電回路
１４ 充電回路
１５ 外部電源
１６ 切替回路
１７ 端子
１８ 端子
１９ 端子
DESCRIPTION OF SYMBOLS 11 Secondary battery 11a Secondary battery 11b Secondary battery 11c Secondary battery 11d Secondary battery 12 Processing part 12a 1st processing part 12b 2nd processing part 13 Discharge circuit 14 Charging circuit 15 External power supply 16 Switching circuit 17 Terminal 18 Terminal 19 Terminal

Claims (7)

リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池の充電方法であって、
（ａ）前記二次電池の開回路電圧を検出し、検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する工程、および
（ｂ）前記判定に応じて、
〔イ〕検出値が領域Ａに含まれる場合には、充電を停止し、
〔ロ〕検出値が領域Ｂに含まれる場合には、充電を行い、
〔ハ〕検出値が領域Ｃに含まれる場合には、前記二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う工程、を有し、
前記所定値Ｘが、前記二次電池において推奨される充電終止電圧±０．０３Ｖ以内の値であり、
前記所定値Ｙが、前記二次電池の残存容量が公称容量の２０％以下のときの値であり、
前記所定値Ｚが、２．７Ｖ以上２．９Ｖ以下の値である充電方法。 A method for charging a non-aqueous electrolyte secondary battery comprising a positive electrode including a lithium-containing composite oxide as an active material, a negative electrode including a material capable of occluding and releasing lithium ions as an active material, and a non-aqueous electrolyte solution,
(A) An open circuit voltage of the secondary battery is detected, and a detected value is a voltage region A greater than or equal to a predetermined value X, a voltage region B that is less than a predetermined value X and exceeds a predetermined value Y (Y <X), and a predetermined value Y A step of determining which of the following voltage regions C is included, and (b) according to the determination,
[A] When the detected value is included in the area A, the charging is stopped,
[B] When the detected value is included in the region B, charge is performed,
When the [C] detected value is included in the region C, have a step, for charging after the closed circuit voltage of the secondary battery was discharged until the predetermined value or less Z (Z <Y),
The predetermined value X is a value within a charge end voltage ± 0.03 V recommended in the secondary battery,
The predetermined value Y is a value when the remaining capacity of the secondary battery is 20% or less of the nominal capacity,
Wherein the predetermined value Z is, 2.9 V or less values Der Ru charging method or 2.7V. リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池を複数個直列に接続して充電する充電方法であって、
（ａ）少なくとも１つの二次電池の開回路電圧を検出し、検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する工程、および
（ｂ）前記判定に応じて、
〔イ〕いずれかの検出値が領域Ａに含まれる場合には、充電を停止し、
〔ロ〕すべての検出値が領域Ｂに含まれる場合には、充電を行い、
〔ハ〕いずれかの検出値が領域Ｃに含まれる場合には、いずれかの二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う工程、を有し、
前記所定値Ｘが、前記二次電池において推奨される充電終止電圧±０．０３Ｖ以内の値であり、
前記所定値Ｙが、前記二次電池の残存容量が公称容量の２０％以下のときの値であり、
前記所定値Ｚが、２．７Ｖ以上２．９Ｖ以下の値である充電方法。 Charging a plurality of non-aqueous electrolyte secondary batteries connected in series with a positive electrode containing a lithium-containing composite oxide as an active material, a negative electrode containing a material capable of occluding and releasing lithium ions as an active material, and a non-aqueous electrolyte Charging method,
(A) An open circuit voltage of at least one secondary battery is detected, and a detected value is a voltage region A greater than or equal to a predetermined value X, a voltage region B that is less than a predetermined value X and exceeds a predetermined value Y (Y <X), and a predetermined value A step of determining which of the voltage regions C below the value Y is included, and ( b ) according to the determination,
[A] When any detection value is included in the area A, the charging is stopped,
[B] When all the detected values are included in the region B, charge is performed,
[C] If any of the detected values is included in the region C, the step of charging after discharging until the closed circuit voltage of any of the secondary batteries is equal to or lower than a predetermined value Z (Z <Y) , Yes, and
The predetermined value X is a value within a charge end voltage ± 0.03 V recommended in the secondary battery,
The predetermined value Y is a value when the remaining capacity of the secondary battery is 20% or less of the nominal capacity,
Wherein the predetermined value Z is, 2.9 V or less values Der Ru charging method or 2.7V. 前記所定値Ｘが、前記二次電池の公称電圧±１％の値である請求項１または２記載の充電方法。   The charging method according to claim 1 or 2, wherein the predetermined value X is a value of a nominal voltage ± 1% of the secondary battery. 前記二次電池の閉回路電圧が、所定値Ｘに達したときに、充電を停止する請求項１記載の充電方法。 Closed circuit voltage of the secondary battery, when it reaches a predetermined value X, charging method according to claim 1, wherein charging is stopped. いずれかの二次電池の閉回路電圧が、所定値Ｘに達したときに、充電を停止する請求項２記載の充電方法。 When a closed circuit voltage of any secondary battery, has reached a predetermined value X, charging method according to claim 2, wherein the charging is stopped. リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池の充電を行う充電器であって、
（ａ）前記二次電池の開回路電圧を検出する電圧検知手段、
（ｂ）検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する判定手段、および
（ｃ）前記判定に応じて、
〔イ〕検出値が領域Ａに含まれる場合には、充電を停止し、
〔ロ〕検出値が領域Ｂに含まれる場合には、充電を行い、
〔ハ〕検出値が領域Ｃに含まれる場合には、前記二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う選択的充電手段、を有し、
前記所定値Ｘが、前記二次電池において推奨される充電終止電圧±０．０３Ｖ以内の値であり、
前記所定値Ｙが、前記二次電池の残存容量が公称容量の２０％以下のときの値であり、
前記所定値Ｚが、２．７Ｖ以上２．９Ｖ以下の値である充電器。 A charger for charging a non-aqueous electrolyte secondary battery including a positive electrode including a lithium-containing composite oxide as an active material, a negative electrode including a material capable of occluding and releasing lithium ions as an active material, and a non-aqueous electrolyte. ,
(A) voltage detection means for detecting an open circuit voltage of the secondary battery;
(B) Whether the detected value is included in the voltage region A that is greater than or equal to the predetermined value X, the voltage region B that is less than the predetermined value X and exceeds the predetermined value Y (Y <X), and the voltage region C that is less than or equal to the predetermined value Y Determining means for determining, and (c) according to said determination,
[A] When the detected value is included in the area A, the charging is stopped,
[B] When the detected value is included in the region B, charge is performed,
When the [C] detected value is included in the region C, it has a selective charging means for charging after the closed circuit voltage of the secondary battery was discharged until the predetermined value or less Z (Z <Y) ,
The predetermined value X is a value within a charge end voltage ± 0.03 V recommended in the secondary battery,
The predetermined value Y is a value when the remaining capacity of the secondary battery is 20% or less of the nominal capacity,
Wherein the predetermined value Z is, the charger Ru 2.9V following values der than 2.7V. リチウム含有複合酸化物を活物質として含む正極、リチウムイオンを吸蔵・放出可能な材料を活物質として含む負極および非水電解液を具備する非水電解質二次電池を複数個直列に接続して充電する充電器であって、
（ａ）少なくとも１つの二次電池の開回路電圧を検出する電圧検知手段、
（ｂ）検出値が、所定値Ｘ以上の電圧領域Ａ、所定値Ｘ未満かつ所定値Ｙ（Ｙ＜Ｘ）を超える電圧領域Ｂおよび所定値Ｙ以下の電圧領域Ｃのいずれに含まれるかを判定する判定手段、および
（ｃ）前記判定に応じて、
〔イ〕いずれかの検出値が領域Ａに含まれる場合には、充電を停止し、
〔ロ〕すべての検出値が領域Ｂに含まれる場合には、充電を行い、
〔ハ〕いずれかの検出値が領域Ｃに含まれる場合には、いずれかの二次電池の閉回路電圧が所定値Ｚ（Ｚ＜Ｙ）以下になるまで放電した後に充電を行う選択的充電手段、を有し、
前記所定値Ｘが、前記二次電池において推奨される充電終止電圧±０．０３Ｖ以内の値であり、
前記所定値Ｙが、前記二次電池の残存容量が公称容量の２０％以下のときの値であり、
前記所定値Ｚが、２．７Ｖ以上２．９Ｖ以下の値である充電器。 Charging a plurality of non-aqueous electrolyte secondary batteries connected in series with a positive electrode containing a lithium-containing composite oxide as an active material, a negative electrode containing a material capable of occluding and releasing lithium ions as an active material, and a non-aqueous electrolyte A charger that
(A) voltage detection means for detecting an open circuit voltage of at least one secondary battery;
(B) Whether the detected value is included in the voltage region A that is greater than or equal to the predetermined value X, the voltage region B that is less than the predetermined value X and exceeds the predetermined value Y (Y <X), and the voltage region C that is less than or equal to the predetermined value Y Determining means for determining, and (c) according to said determination,
[A] When any detection value is included in the area A, the charging is stopped,
[B] When all the detected values are included in the region B, charge is performed,
[C] When any detection value is included in the region C, selective charging is performed after charging until the closed circuit voltage of any secondary battery becomes equal to or lower than a predetermined value Z (Z <Y). means, to possess,
The predetermined value X is a value within a charge end voltage ± 0.03 V recommended in the secondary battery,
The predetermined value Y is a value when the remaining capacity of the secondary battery is 20% or less of the nominal capacity,
Wherein the predetermined value Z is, the charger Ru 2.9V following values der than 2.7V.
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