WO2014016956A1 - 二次電池の短絡検査方法 - Google Patents
二次電池の短絡検査方法 Download PDFInfo
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- WO2014016956A1 WO2014016956A1 PCT/JP2012/069187 JP2012069187W WO2014016956A1 WO 2014016956 A1 WO2014016956 A1 WO 2014016956A1 JP 2012069187 W JP2012069187 W JP 2012069187W WO 2014016956 A1 WO2014016956 A1 WO 2014016956A1
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- secondary battery
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/50—Testing of electric apparatus, lines, cables or components for short-circuits, continuity, leakage current or incorrect line connections
- G01R31/52—Testing for short-circuits, leakage current or ground faults
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
- G01R31/3865—Arrangements for measuring battery or accumulator variables related to manufacture, e.g. testing after manufacture
Definitions
- the present invention relates to a technique for inspecting a short circuit of a secondary battery.
- Patent Document 1 discloses a technique for charging a first SOC, discharging to a second SOC lower than the first SOC, and detecting a micro short circuit in a state where the battery temperature is lowered after the discharging step. Is done.
- the discharge current density is set to a value lower than the charge current density, and the discharge process is performed at a low rate. For this reason, the time required for the discharge becomes long, and as a result, the time required for the short circuit inspection becomes long.
- the micro short circuit is detected in a state where the battery temperature is lowered and the variation in voltage after discharge is stabilized. That is, a low-temperature facility for maintaining the battery temperature at a low temperature is required, and the equipment cost is increased.
- the secondary battery is charged to a first SOC at a predetermined charging current density, and the second SOC smaller than the first SOC is the same as the charging current density.
- the battery is discharged at a discharge current density of about a level, and is maintained within a range of ⁇ 3 ° C. of the battery temperature of the secondary battery after the discharge.
- the battery is self-discharged at room temperature, and the presence or absence of a short circuit is detected based on the amount of voltage drop after a predetermined time.
- the voltage rise by the jump of the voltage of a secondary battery can be suppressed before a short circuit inspection, the voltage fall amount of a secondary battery can be detected with high sensitivity, and the time required for a short circuit inspection can be shortened. Moreover, an increase in equipment cost can be suppressed by performing a short circuit inspection at room temperature.
- Voltage stabilization of the secondary battery is performed by leaving it to stand for 24 hours or more while maintaining the battery temperature within a range of ⁇ 3 ° C. of the battery temperature of the secondary battery after discharge. Is preferred.
- the secondary battery is preferably discharged to a low SOC of 10% or less. As described above, by performing discharge to a low SOC at which a change in voltage appears remarkably, it is possible to improve the detection sensitivity of a minute short circuit.
- the secondary battery After charging the secondary battery, the secondary battery is preferably subjected to an aging treatment at a high temperature.
- an aging treatment at a high temperature.
- a chemical substance in the secondary battery is activated, a chemical short circuit is promoted, and detection accuracy in a subsequent short circuit inspection can be improved.
- said 1st SOC is a charge state of 3.6V or more.
- a smaller short circuit can be detected, the time required for the short circuit inspection can be shortened, and an increase in equipment cost can be suppressed.
- FIG. 1 shows a schematic configuration of the secondary battery 1.
- the secondary battery 1 is a battery that can be repeatedly charged and discharged, for example, a square lithium ion secondary battery.
- the secondary battery 1 is configured by housing an electrode body 3 serving as a charge / discharge element in a sealed case 2.
- a positive electrode and a negative electrode external terminal 4 are connected to the electrode body 3 and are fixed to the case 2 so as to protrude outward.
- the electrode body 3 is a wound body configured by laminating and winding a positive electrode current collector plate, a separator, and a negative electrode current collector plate.
- the positive electrode current collector plate and the negative electrode current collector plate are coated with a positive electrode electrode mixture and a negative electrode electrode mixture, respectively.
- a positive electrode active material containing lithium ions, a positive electrode mixture containing a conductive additive, etc. are applied to the positive electrode current collector plate, and a negative electrode mixture containing a negative electrode active material containing a carbon-based material is a negative electrode It is applied to the current collector.
- FIG. 2 shows a short circuit inspection step S ⁇ b> 1 of the secondary battery 1.
- the short circuit inspection step S1 is a step of inspecting a micro short circuit existing in the assembled secondary battery 1.
- the short circuit inspection step S1 includes a charging step S11, a high temperature heat treatment step S12, a discharge step S13, a voltage stabilization step S14, and a minute inspection step S15.
- an appropriate charging / discharging device is connected to the secondary battery 1, and charging is performed up to the first SOC at a predetermined current density.
- the value of the first SOC is set as a high SOC of 80% or more, for example.
- the predetermined current density used in the charging step S11 indicates a C rate of 0.02 [C] or more. Moreover, it charges to 3.6V or more charge state as 1st SOC. Thereby, in the next high-temperature heat treatment step S12, the dissolution of the foreign matter proceeds, and the generation of a positive micro short circuit can be promoted.
- the secondary battery 1 is held in a high temperature atmosphere to activate a chemical substance (electrode active material) contained therein. For example, it is exposed to a high temperature atmosphere (about 40 ° C. to 85 ° C.) that is higher than normal temperature and that does not melt the separator included in the secondary battery 1. In this way, by aging the secondary battery 1 at a high temperature, the chemical reaction inside the secondary battery 1 can be promoted, and a micro short circuit (chemical short circuit) resulting from the chemical reaction is actively generated. The detection accuracy in the minute inspection step S15 is improved.
- a charging / discharging apparatus is connected to the secondary battery 1, and it discharges to 2nd SOC with the current density equivalent to charge process S11. That is, in the discharge step S13, high-rate discharge (discharge of 0.02C or more) is performed.
- the value of the second SOC is set as a low SOC of 20% or less.
- FIG. 3 shows a discharge curve of the secondary battery 1, wherein the horizontal axis shows SOC (%) and the vertical axis shows voltage (V). As shown in FIG. 3, it is preferable to discharge to a low SOC of 10% or less where a large voltage change appears (the gradient of voltage / SOC becomes large), and 3 to 3 in the vicinity of the inflection point where the voltage change appears more prominently. It is more preferable to set the value to 5%.
- the detection sensitivity of defective products is improved by adjusting to a low SOC in which the voltage drop amount (voltage change amount) of the secondary battery 1 is large.
- the secondary battery 1 is left at a normal temperature (about 10 ° C. to about 30 ° C.) and within a range of ⁇ 3 ° C. of the battery temperature after the discharge step S13 for a predetermined time.
- the voltage of the secondary battery 1 is stabilized. Thereby, the jump of the voltage after the discharge of the secondary battery 1 (the voltage increase caused by the diffusion of the electrode active material) is reset.
- FIG. 4 shows a result of preparing a plurality of secondary batteries 1 that have undergone the charging step S11, the high-temperature heat treatment step S12, and the discharging step S13, and measuring the magnitude of voltage variations of the plurality of secondary batteries 1.
- the horizontal axis represents elapsed time (day)
- the vertical axis represents variation magnitude ( ⁇ ).
- the magnitude of variation becomes smaller than the standard value.
- This standard value is set to, for example, about 25% of the magnitude of variation after the discharge step S13.
- the aging time in the voltage stabilization step S14 is preferably 1 day (24 hours) or longer, and more preferably 2 days (48 hours) or longer in consideration of manufacturing variations between cells. .
- the secondary battery 1 after discharge is aged to stabilize the voltage, that is, by holding the internal chemical substance until it is stabilized, each secondary battery due to a rise in voltage. 1 can be absorbed.
- voltage variations due to changes in battery temperature can be suppressed, and detection accuracy can be improved.
- the voltage is measured while the secondary battery 1 is self-discharged at room temperature, and the presence or absence of a micro short circuit is detected based on the voltage difference from the good product group after a predetermined time has elapsed.
- the voltage stabilization process S14 ends, and the voltage of each secondary battery 1 when moving to the micro inspection process S15 is set to zero.
- the voltage of each secondary battery 1 after predetermined time progress is measured, it determines with the short circuit existing in the secondary battery 1 whose difference with the voltage of a good product group is larger than a threshold value, and determines as a defective product. .
- the threshold voltage difference between the non-defective product group and the defective product is reduced by moving to the micro inspection step S15 in a state in which the voltage variation between the secondary batteries 1 is suppressed by the voltage stabilization step S14. It becomes possible to set. In other words, the voltage drop amount of the defective secondary battery 1 including a micro short circuit or the like can be detected with high sensitivity, and the inspection time can be shortened.
- FIG. 5 shows the result of the defective product determination test in the micro inspection step S15.
- the horizontal axis of FIG. 5 shows the elapsed time (day), the vertical axis shows the voltage change ( ⁇ V) and the degree of variation of the voltage, and when the process proceeds to the micro inspection process S15 immediately after the discharge process S13 through the voltage stabilization process S14.
- the voltage change and the voltage variation in the non-defective product group and the defective products A and B are shown.
- the judgment test prepare two types of defective products including multiple non-defective products and forcibly generated short-circuits, and after self-discharge for 5 days, detect the voltage difference with the non-defective products group, Detected. As defective products, a defective product A having a short circuit resistance and a defective product B having a large short circuit resistance were prepared.
- the variation of the non-defective product group is kept small, and the difference between the voltage drop amount of the defective product A and B and the voltage drop amount of the non-defective product after 5 days is noticeable.
- B and non-defective products can be easily distinguished. This is due to the fact that each secondary battery 1 has gone through the voltage stabilization step S14 and has shifted to the micro inspection step S15 in a state where the voltage rise after the discharge is reset.
- the required number of days for the micro inspection process S15 is tested as 5 days, it can be set to a shorter period as long as the voltage difference between the non-defective product group and the defective product is noticeable. .
- the short circuit inspection step S1 of the present embodiment includes the voltage stabilization step S14, thereby suppressing variations in voltage between the secondary batteries 1 and improving the detection accuracy in the subsequent micro inspection step S15.
- the discharge process S13 the time required for the discharge process S13 is shortened by performing discharge at a high discharge current density.
- the detection sensitivity in the micro inspection process S15 is improved.
- FIG. 6 shows the result of detecting a micro short-circuit of a defective product using a non-defective product and a defective product A / B in the same manner as in the determination test of the present embodiment according to a conventional micro inspection process.
- This micro inspection process is performed after the discharge process at a low rate.
- the horizontal axis in FIG. 6 indicates the elapsed time (day), the vertical axis indicates the voltage change ( ⁇ V) and the degree of voltage variation, the voltage change at the time of the minute inspection, and the voltage variation in the non-defective product group and the defective products A and B. Is shown.
- FIG. 6 shows the result of detecting a micro short-circuit of a defective product using a non-defective product and a defective product A / B in the same manner as in the determination test of the present embodiment according to a conventional micro inspection process.
- This micro inspection process is performed after the discharge process at a low rate.
- the horizontal axis in FIG. 6 indicates the elapsed
- the short-circuit inspection step S1 of the present embodiment it is possible to detect a finer short-circuit as compared with the conventional case, and the time required for the short-circuit inspection can be significantly shortened.
- the present invention can be used in a process for inspecting the presence or absence of a micro short circuit in a secondary battery.
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- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Tests Of Electric Status Of Batteries (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
Abstract
Description
これにより、短絡検査前に二次電池の電圧の跳ね上がりによる電圧上昇を抑え、二次電池の電圧低下量を高感度に検出でき、短絡検査に要する時間を短縮化できる。また、常温下で短絡検査を行うことで、設備コストの増加を抑えることができる。
このように、電圧の変化が顕著に現れる低SOCまで放電を行うことにより、微小短絡の検出感度を向上できる。
二次電池を高温エージングすることによって、二次電池内の化学物質を活性化させて、化学短絡を促進させ、後の短絡検査での検出精度を向上できる。
また、前記第一のSOCは、3.6V以上の充電状態であることが好ましい。これにより、高温熱処理時に二次電池内の異物を確実に溶解させて、後の短絡検査で検出する微小短絡を促進させることができる。
電極体3は、正極集電板、セパレータ、及び、負極集電板を積層し、巻回して構成される巻回体である。正極集電板及び負極集電板の表面には、正極及び負極の電極合剤がそれぞれ塗布されている。リチウムイオン二次電池では、リチウムイオンを含む正極活物質、導電助剤等を含有する正極合剤が正極集電板に塗布され、炭素系材料を含む負極活物質を含有する負極合剤が負極集電板に塗布される。
短絡検査工程S1は、充電工程S11、高温熱処理工程S12、放電工程S13、電圧安定化工程S14、微短検査工程S15を含む。
また、第一のSOCとして、3.6V以上の充電状態まで充電される。これにより、次の高温熱処理工程S12において、異物の溶解が進み、積極的な微小短絡の発生を促進できる。
このように、二次電池1を高温下でエージングすることによって、二次電池1内部の化学反応を促進させることができ、それに起因する微小短絡(化学短絡)を積極的に発生させ、後の微短検査工程S15での検出精度を向上している。
図3は、二次電池1の放電曲線を示し、横軸はSOC(%)、縦軸は電圧(V)を示す。図3に示されるように、電圧変化が大きく現れる(電圧/SOCの勾配が大きくなる)10%以下の低いSOCまで放電することが好ましく、電圧変化がより顕著に表れる変曲点付近の3~5%の値に設定することがより好ましい。
このように、放電工程S13において、二次電池1の電圧低下量(電圧変化量)が大きくなる低SOCに調整することによって、不良品の検出感度が向上する。
図4は、充電工程S11、高温熱処理工程S12、放電工程S13を経た複数の二次電池1を用意して、それら複数の二次電池1の電圧のばらつきの大きさを計測した結果を示す。図4における横軸は経過時間(day)、縦軸はばらつきの大きさ(σ)を示す。
このように、電圧安定化工程S14において、放電後の二次電池1をエージングして電圧を安定させる、つまり、内部の化学物質が安定するまで保持することによって、電圧の上昇による各二次電池1の電圧のばらつきを吸収できる。また、放電直後の二次電池1の温度をできる限り維持した状態で行うことにより、電池温度の変化に起因する電圧のばらつきが抑えられ、検出精度を向上できる。
このとき、電圧安定化工程S14が終了し、微短検査工程S15に移行する時の各二次電池1の電圧をゼロとして設定する。そして、所定時間経過後の各二次電池1の電圧を測定し、良品群の電圧との差が閾値よりも大きい二次電池1に短絡が存在していると判定し、不良品として判定する。
判定試験では、複数の良品と、強制的に発生させた短絡を含む不良品を二種類用意し、5日間自己放電させた後に、良品群との電圧差を検出し、不良品の微小短絡を検出した。不良品は、短絡抵抗の小さい不良品Aと短絡抵抗の大きい不良品Bを用意した。
これは、各二次電池1が電圧安定化工程S14を経ることによって、放電後の電圧上昇がリセットされた状態で微短検査工程S15に移行していることに起因する。
なお、微短検査工程S15の所要日数を5日として試験しているが、良品群と不良品の電圧差が顕著に現れるタイミングであれば、それよりも短い期間に設定することも可能である。
また、放電工程S13において、高レートの放電電流密度で放電を行うことによって、放電工程S13に要する時間を短縮している。さらに、放電工程S13で低SOCまで放電を行うことによって、微短検査工程S15での検出感度を向上している。
図6に示されるように、良品群内のばらつきが大きく検出されることにより、短絡抵抗の小さい不良品Aとの電圧差を検出できるようになるまでにかかる日数が長くなってしまう。つまり、不良品の誤検出を避けるために、良品群内の電圧差よりも不良品Aとの電圧差が大きくなるまで放置する必要があり、検査時間を長くする必要がある。
Claims (5)
- 二次電池を所定の充電電流密度で第一のSOCまで充電し、
前記第一のSOCよりも小さい第二のSOCまで、前記充電電流密度と同程度の放電電流密度で放電し、
前記放電後の二次電池の電池温度の±3℃の範囲内で維持した状態で、所定時間放置して電圧を安定化し、
前記電圧安定化後の二次電池を常温下で自己放電させて、所定時間後の電圧低下量に基づいて短絡の有無を検出することを特徴とする二次電池の短絡検査方法。 - 前記二次電池の電圧安定化は、電池温度を常温、かつ、前記放電後の二次電池の電池温度の±3℃の範囲内で維持した状態で、24時間以上放置することにより行われる請求項1に記載の二次電池の短絡検査方法。
- 前記二次電池の放電は、10%以下の低SOCまで行われる請求項1又は2に記載の二次電池の短絡検査方法。
- 前記二次電池を充電した後に、当該二次電池を高温下でエージング処理する請求項1から3の何れか一項に記載の二次電池の短絡検査方法。
- 前記第一のSOCは、3.6V以上の充電状態である請求項4に記載の二次電池の短絡検査方法。
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CN201280074894.8A CN104487857B (zh) | 2012-07-27 | 2012-07-27 | 二次电池的短路检查方法 |
PCT/JP2012/069187 WO2014016956A1 (ja) | 2012-07-27 | 2012-07-27 | 二次電池の短絡検査方法 |
US14/417,473 US9588183B2 (en) | 2012-07-27 | 2012-07-27 | Short-circuit inspection method for secondary cell |
JP2014526686A JP5930342B2 (ja) | 2012-07-27 | 2012-07-27 | 二次電池の短絡検査方法 |
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CN105929333A (zh) * | 2015-02-27 | 2016-09-07 | 丰田自动车株式会社 | 二次电池的检查方法 |
JP2018132487A (ja) * | 2017-02-17 | 2018-08-23 | プライムアースEvエナジー株式会社 | 二次電池の劣化判定方法及び二次電池の劣化判定装置 |
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JP7508711B2 (ja) | 2021-10-13 | 2024-07-01 | エルジー エナジー ソリューション リミテッド | バッテリー診断装置、バッテリーパック、電気車両、及びバッテリー診断方法 |
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JP5930342B2 (ja) | 2016-06-08 |
CN104487857A (zh) | 2015-04-01 |
US9588183B2 (en) | 2017-03-07 |
JPWO2014016956A1 (ja) | 2016-07-07 |
US20150212162A1 (en) | 2015-07-30 |
CN104487857B (zh) | 2017-03-08 |
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