JP2018147748A - System and method for determining electrode degradation of storage battery - Google Patents

System and method for determining electrode degradation of storage battery Download PDF

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JP2018147748A
JP2018147748A JP2017042101A JP2017042101A JP2018147748A JP 2018147748 A JP2018147748 A JP 2018147748A JP 2017042101 A JP2017042101 A JP 2017042101A JP 2017042101 A JP2017042101 A JP 2017042101A JP 2018147748 A JP2018147748 A JP 2018147748A
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storage battery
electrode
pressure
rate
time characteristic
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誠 川瀬
Makoto Kawase
誠 川瀬
均 内藤
Hitoshi Naito
均 内藤
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Japan Aerospace Exploration Agency JAXA
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Abstract

PROBLEM TO BE SOLVED: To enable electrode deterioration determination more simply.SOLUTION: Disclosed is an electrode deterioration determination system for a storage battery. The electrode deterioration determination system includes: a measurement part for measuring pressure versus time characteristics of the storage battery in a charging period of the storage battery at a predetermined charging rate and/or in a discharging period of the storage battery at a predetermined discharging rate; and an electrode deterioration determination part for determining the electrode deterioration of the storage battery by comparing first pressure versus time characteristics measured by the measurement part with second pressure versus time characteristics measured by the measurement part at the same charging rate and/or discharging rate as the charging rate and/or the discharging rate in the measurement of the first pressure versus time characteristics, during no deterioration of the electrode of the storage battery.SELECTED DRAWING: Figure 6

Description

この発明は、蓄電池の電極劣化判定のためのシステム及び方法に関する。   The present invention relates to a system and method for determining electrode deterioration of a storage battery.

蓄電池の状態推定や健全性確認方法としては、電圧や温度による監視が一般的である（下記特許文献１等参照）。   As a storage battery state estimation and soundness confirmation method, monitoring by voltage or temperature is generally used (see Patent Document 1 below).

また、蓄電池の電極の劣化は、充放電曲線における電圧（Ｖ）を容量（Ｑ）で微分して得られるｄＶ／ｄＱ曲線における各ピーク位置の変化により判定できることが知られている。すなわち、ｄＶ／ｄＱ曲線における各ピークは、正極又は負極の結晶相変化に対応し、正極又は負極が劣化すると各ピークの位置や形状が変化する。各ピークの同定は、例えば電池を解体して得た正極及び負極で金属リチウムを対極とするハーフセルの充放電試験を行い、それにより得られた正極及び負極のｄＶ／ｄＱ曲線のピークとの比較により行うことができる（下記非特許文献１、２等参照）。   Further, it is known that the deterioration of the electrode of the storage battery can be determined by the change of each peak position in the dV / dQ curve obtained by differentiating the voltage (V) in the charge / discharge curve by the capacity (Q). That is, each peak in the dV / dQ curve corresponds to a crystal phase change of the positive electrode or the negative electrode, and when the positive electrode or the negative electrode deteriorates, the position and shape of each peak change. For identification of each peak, for example, a positive and negative electrode obtained by disassembling a battery was subjected to a half-cell charge / discharge test using metallic lithium as a counter electrode, and compared with the obtained positive and negative dV / dQ curve peaks. (See Non-Patent Documents 1 and 2 below).

また、蓄電池の電極の劣化は、充放電期間における蓄電池の温度曲線における各ピーク位置や形状の変化により判定できることが知られている。すなわち、温度曲線における各ピークは、正極又は負極の結晶相変化に対応し、正極又は負極が劣化すると各ピークの位置や形状が変化する。各ピークの同定は、例えば電池を解体して得た正極及び負極で金属リチウムを対極とするハーフセルの充放電試験を行い、それにより得られた正極及び負極の熱挙動曲線のピークとの比較により行うことができる（下記非特許文献３等参照）。   Moreover, it is known that the deterioration of the electrode of the storage battery can be determined by a change in each peak position or shape in the temperature curve of the storage battery during the charge / discharge period. That is, each peak in the temperature curve corresponds to a change in crystal phase of the positive electrode or the negative electrode, and when the positive electrode or the negative electrode deteriorates, the position and shape of each peak change. The identification of each peak is performed by, for example, conducting a charge / discharge test of a half cell using metal lithium as a counter electrode with a positive electrode and a negative electrode obtained by disassembling the battery, and comparing with the peaks of the thermal behavior curves of the positive electrode and the negative electrode obtained thereby. (See Non-Patent Document 3 below).

特開２０１４−１９６９６７号公報JP 2014-196967 A

小林剛他，“リチウムイオン電池劣化解析手法の開発(I)−正・負極電位解析による電池容量低下要因の解析−”，電力中央研究所報告，財団法人電力中央研究所，平成２３年６月，研究報告：Q10026Takeshi Kobayashi et al., “Development of Lithium Ion Battery Degradation Analysis Method (I)-Analysis of Battery Capacity Reduction Factors by Positive / Negative Potential Analysis”, Power Central Research Institute Report, Central Research Institute of Electric Power Industry, June 2011 , Research report: Q10026 松田智行他，“1/3Cサイクル試験におけるリチウムイオン電池の劣化機構”，JARI Research Journal，研究速報：JRJ20151201Tomoyuki Matsuda et al., “Deterioration Mechanism of Lithium Ion Battery in 1 / 3C Cycle Test”, JARI Research Journal, Research Bulletin: JRJ20151201 小林陽他，“リチウムイオン電池劣化解析手法の開発(II)−断熱型ホルダーを用いた電池温度解析による容量低下要因の検証−”，電力中央研究所報告，財団法人電力中央研究所，平成２３年６月，研究報告：Q10030Yo Kobayashi et al., “Development of Lithium Ion Battery Degradation Analysis Method (II)-Verification of Capacity Decreasing Factors by Battery Temperature Analysis Using Adiabatic Holder-" June, Research Report: Q10030

しかしながら、電圧による監視については、充放電時の電圧変化が小さい電池であると電圧変化を捉えることが困難な場合がある。また、温度による監視については、温度センサの配置場所によって測定温度が異なる場合があり、大型電池では電池の部位によって温度自体が異なる場合もあるなど、温度の測定が困難な場合がある。   However, with regard to monitoring by voltage, it may be difficult to capture the voltage change if the battery has a small voltage change during charging and discharging. For monitoring by temperature, the measurement temperature may be different depending on the location of the temperature sensor, and in a large battery, the temperature itself may be different depending on the location of the battery.

また、上記のｄV／ｄQ曲線のピーク位置の変化による電極劣化判定においては、電流センサの測定値から容量Ｑを算出し、更に、電圧センサの測定値に基づいて、電圧Ｖの容量Ｑに対する微分を演算するという複雑な計算が必要となり、迅速に電極劣化判定ができない場合がある。   Further, in the electrode deterioration determination based on the change in the peak position of the dV / dQ curve, the capacity Q is calculated from the measured value of the current sensor, and further, the differential of the voltage V with respect to the capacity Q is calculated based on the measured value of the voltage sensor. It is necessary to perform a complicated calculation to calculate, and electrode deterioration determination cannot be performed quickly.

また、上記の温度曲線のピーク位置の変化による電極劣化判定手法は、正確な熱量計測が必要であり、実際に使用する形態でのセルもしくはバッテリの熱量計測は困難な場合がある。   In addition, the electrode deterioration determination method based on the change in the peak position of the temperature curve described above requires accurate calorie measurement, and it may be difficult to measure the calorie of a cell or battery in a form of actual use.

そこで、本発明は、より簡素に電極劣化判定を可能とすることを目的の１つとする。   Accordingly, an object of the present invention is to make it possible to determine electrode deterioration more simply.

本発明の１つの態様は、蓄電池の電極劣化判定システムであって、所定の充電レートでの前記蓄電池の充電期間及び／又は所定の放電レートでの前記蓄電池の放電期間における前記蓄電池の圧力対時間特性を測定する測定部と、前記蓄電池の電極が劣化していない時に前記測定部により測定された第１の圧力対時間特性と、前記第１の圧力対時間特性の測定における充電レート及び／又は放電レートと同じ充電レート及び／又は放電レートで前記測定部により測定された第２の圧力対時間特性とを比較し、前記蓄電池の電極劣化を判定する電極劣化判定部と、を含む電極劣化判定システムを提供するものである。   One aspect of the present invention is an electrode deterioration determination system for a storage battery, wherein the storage battery pressure vs. time during the storage battery charging period at a predetermined charging rate and / or the storage battery discharging period at a predetermined discharging rate. A measurement unit for measuring characteristics, a first pressure-time characteristic measured by the measurement unit when the electrode of the storage battery is not deteriorated, a charge rate and / or a measurement of the first pressure-time characteristic An electrode deterioration determination unit including an electrode deterioration determination unit that compares the second pressure versus time characteristic measured by the measurement unit at the same charge rate and / or discharge rate as the discharge rate and determines electrode deterioration of the storage battery. A system is provided.

前記電極劣化判定部は、前記第１の圧力対時間特性におけるピーク及び／又は傾きが変化する点の位置及び／又は形状と、前記第２の圧力対時間特性におけるピーク及び／又は傾きが変化する点の位置及び／又は形状とを比較し、前記蓄電池の電極劣化を判定するものとすることができる。   The electrode deterioration determining unit changes a position and / or shape of a point at which a peak and / or slope in the first pressure-time characteristic changes and a peak and / or slope in the second pressure-time characteristic. The position and / or shape of the points can be compared to determine electrode deterioration of the storage battery.

前記所定のレートは、低レートであるものとすることができる。   The predetermined rate may be a low rate.

前記電極劣化判定部は、予め取得された、前記所定の充電レートでの前記蓄電池の充電期間及び／又は所定の放電レートでの前記蓄電池の放電期間における前記蓄電池の圧力対時間特性の各ピークや傾きが変化する点が、前記蓄電池の正極又は負極のいずれに由来するのかを同定するためのデータを参照して、前記蓄電池の正極又は負極のいずれが劣化したかを判定することができる。   The electrode deterioration determination unit obtains each peak of the storage battery's pressure vs. time characteristics during the storage battery charging period and / or the storage battery discharging period at a predetermined discharging rate obtained in advance. It can be determined whether the positive electrode or the negative electrode of the storage battery has deteriorated with reference to data for identifying whether the point at which the slope changes originates from the positive electrode or the negative electrode of the storage battery.

本発明の１つの態様は、蓄電池の電極劣化を該蓄電池の圧力を測定することによって判定する方法であって、前記蓄電池の電極が劣化していない時に、所定の充電レートでの前記蓄電池の充電期間及び／又は所定の放電レートでの前記蓄電池の放電期間における、第１の圧力対時間特性を測定するステップと、前記第１の前記蓄電池の圧力対時間特性を測定した後に、前記所定の充電レートでの前記蓄電池の充電期間及び／又は前記所定の放電レートでの前記蓄電池の放電期間における、第２の圧力対時間特性を測定するステップと、前記第１の圧力対時間特性と前記第２の圧力対時間特性とを比較し、前記蓄電池の電極劣化を判定するステップとを含む電極劣化判定方法を提供するものである。   One aspect of the present invention is a method for determining electrode deterioration of a storage battery by measuring the pressure of the storage battery, and charging the storage battery at a predetermined charge rate when the electrode of the storage battery is not deteriorated. Measuring a first pressure versus time characteristic during a discharge period of the storage battery at a period and / or a predetermined discharge rate; and measuring the pressure versus time characteristic of the first storage battery, and then Measuring a second pressure versus time characteristic during a charging period of the storage battery at a rate and / or a discharging period of the storage battery at the predetermined discharge rate, the first pressure versus time characteristic and the second And a step of determining the electrode deterioration of the storage battery by comparing the pressure vs. time characteristics of the battery.

上記構成を有する本発明によれば、従来の手法よりもより簡素に電極劣化判定を行うことができる。   According to the present invention having the above configuration, it is possible to perform the electrode deterioration determination more simply than in the conventional method.

蓄電池の正面図である。It is a front view of a storage battery. 蓄電池の上面図である。It is a top view of a storage battery. 図１ＡのII−II線に沿った断面における各センサの配置を示す図である。It is a figure which shows arrangement | positioning of each sensor in the cross section along the II-II line | wire of FIG. 1A. GEO運用模擬試験の結果を示す図である。It is a figure which shows the result of a GEO operation simulation test. 低充電レート充放電試験の結果を示す図である。It is a figure which shows the result of a low charge rate charging / discharging test. 低レート充放電試験で得られた測定値から算出されたｄＶ／ｄＱと電圧、圧力の関係を示す図である。It is a figure which shows the relationship between dV / dQ computed from the measured value obtained by the low-rate charge / discharge test, voltage, and pressure. 本発明の１つの実施形態に係る電極劣化判定システムの全体構成図である。1 is an overall configuration diagram of an electrode deterioration determination system according to an embodiment of the present invention. 本発明の１つの実施形態に係る電極劣化判定システムのハードウエア構成の例を示す図である。It is a figure which shows the example of the hardware constitutions of the electrode deterioration determination system which concerns on one Embodiment of this invention. 本発明の１つの実施形態に係る電極劣化判定システムの処理の例のフローチャートである。It is a flowchart of the example of a process of the electrode deterioration determination system which concerns on one Embodiment of this invention. 本発明の１つの実施形態に係る電極劣化判定システムの処理の例のフローチャートである。It is a flowchart of the example of a process of the electrode deterioration determination system which concerns on one Embodiment of this invention.

以下、本発明の実施形態（以下、本実施形態）について図面を参照して説明する。   Hereinafter, embodiments of the present invention (hereinafter referred to as “this embodiment”) will be described with reference to the drawings.

（電極劣化判定の原理）
まず、本実施形態の電極劣化判定の原理について説明する。 (Principle of electrode deterioration judgment)
First, the principle of electrode deterioration determination according to this embodiment will be described.

本発明者らは、蓄電池の充放電において、電極を構成する物質の結晶構造変化と、蓄電池の圧力、蓄電池の温度、ｄＶ／ｄＱに相関性があることを見出した。以下、それらの相関性を示すために本発明者らが実施した実験内容について説明する。   The present inventors have found that in charging / discharging of a storage battery, there is a correlation between a change in the crystal structure of a substance constituting the electrode, the storage battery pressure, the storage battery temperature, and dV / dQ. Hereinafter, the contents of the experiment conducted by the present inventors in order to show the correlation between them will be described.

蓄電池として、定格容量１１０Ａｈ、コバルト系正極／グラファイト負極の宇宙用リチウムイオン電池（株式会社ジーエス・ユアサテクノロジー製、JMG110相当品、２０８×１３０×５０ｍｍ）を用いた。図１Ａ、図１Ｂは、それぞれ蓄電池３の正面図、上面図である。図１Ａ、図１Ｂに示されるように蓄電池は、四隅が丸みづけられた長方形の横断面を有する比較的肉薄の直方体形状を有しており、長手方向に延びる同様の直方体形状の中空部を有するものであった。   As the storage battery, a space-use lithium ion battery with a rated capacity of 110 Ah and a cobalt-based positive electrode / graphite negative electrode (manufactured by GS Yuasa Technology Co., Ltd., JMG110 equivalent, 208 × 130 × 50 mm) was used. 1A and 1B are a front view and a top view of the storage battery 3, respectively. As shown in FIGS. 1A and 1B, the storage battery has a relatively thin rectangular parallelepiped shape having a rectangular cross section with rounded corners, and has a similar rectangular parallelepiped hollow portion extending in the longitudinal direction. It was a thing.

充放電試験装置としては、株式会社エイ・イー・エス製、バッテリー試験装置を用いた。そして、蓄電池３の表面と裏面に配置した２枚の挟み板５で挟み、恒温槽（エスペック製、PU-2K）内に設置し、１５℃で各実験を行った。   As the charge / discharge test apparatus, a battery test apparatus manufactured by AES Co., Ltd. was used. And it pinched | interposed with the two clamping plates 5 arrange | positioned at the surface and the back surface of the storage battery 3, installed in the thermostat (product made from ESPEC, PU-2K), and each experiment was conducted at 15 degreeC.

図２は、図１ＡのII−II線に沿った断面における各センサの配置を示す図である。図２に示すように、温度センサ７を、蓄電池３の表面に１つ、中空部を規定する内周面の表面側に３つ配置した。蓄電池３の表面の温度センサ７は、表面の中央付近に配置した。また、内周面の表面側の温度センサ７は、内周面の表面の幅方向において中央付近且つ長手方向において一端及び他端から２０ｍｍ付近及び中央付近に配置した。温度センサとしては、熱電対（チノー製、シートカップル C061-K）を用いた。また、畜電池３の表面の中央付近と挟み板の間にシート状の圧力センサ９（ニッタ製、フレキシフォース センサーシート A201-25）を設置した。   FIG. 2 is a diagram showing the arrangement of sensors in a cross section taken along line II-II in FIG. 1A. As shown in FIG. 2, one temperature sensor 7 is arranged on the surface of the storage battery 3 and three on the surface side of the inner peripheral surface defining the hollow portion. The temperature sensor 7 on the surface of the storage battery 3 was arranged near the center of the surface. Further, the temperature sensor 7 on the surface side of the inner peripheral surface was arranged near the center in the width direction of the surface of the inner peripheral surface and near 20 mm and near the center from one end and the other end in the longitudinal direction. A thermocouple (manufactured by Chino, sheet couple C061-K) was used as the temperature sensor. Further, a sheet-like pressure sensor 9 (made by Nitta, flexiforce sensor sheet A201-25) was installed between the vicinity of the center of the surface of the battery 3 and the sandwiching plate.

（１）GEO（geosynchronous orbit：対地同期軌道）運用模擬試験
上記の実験装置により、標準的なGEOでの運用を模擬した充放電を実施した。具体的には、以下の充放電を５サイクル実施した。
充電：CC/CV 0.1C/4.1V, 22.8h, 15℃
放電：CC 0.67C 1.2h, 15℃
結果を図３に示す。なお、温度の測定結果は、各温度センサ７による温度の測定結果が同様の特性を示したため、畜電池３の内周面の表面の中央付近の温度センサ７による測定結果のみを示す。また、圧力センサ出力の絶対値については校正を行っていないものである。 (1) GEO (geosynchronous orbit) operation simulation test Charge / discharge simulating the operation in standard GEO was carried out using the above experimental equipment. Specifically, the following charging / discharging was performed 5 cycles.
Charging: CC / CV 0.1C / 4.1V, 22.8h, 15 ℃
Discharge: CC 0.67C 1.2h, 15 ℃
The results are shown in FIG. In addition, since the measurement result of temperature by each temperature sensor 7 showed the same characteristic, the measurement result of temperature shows only the measurement result by the temperature sensor 7 near the center of the surface of the inner peripheral surface of the battery 3. Further, the absolute value of the pressure sensor output is not calibrated.

図３から、SOC90％付近で温度特性と圧力特性にピークが認められ、両者がほぼ同期していることが分かった。このピークについて、正極に使用しているコバルト酸リチウムの結晶格子が充電時に伸びる方向かつ満充電付近で六方晶と単斜晶の間での結晶構造の相転移付近で格子定数が最大となることが知られており、当該事象を捉えているものと推定される。   As can be seen from FIG. 3, peaks were observed in the temperature characteristics and pressure characteristics in the vicinity of SOC 90%, and both were almost synchronized. With regard to this peak, the lattice constant becomes maximum near the phase transition of the crystal structure between the hexagonal crystal and the monoclinic crystal in the direction in which the crystal lattice of lithium cobaltate used for the positive electrode extends during charging and near full charge. Is known and is presumed to capture the event.

GEO運用模擬において、放電時には、電流レートが大きいため、後述の低レート充放電試験で確認できていた温度特性と圧力特性における細かいピークや傾きが変化する点は確認できないものの、SOC90%付近のピークは充電時及び放電時のいずれでも確認できた。   In the GEO operation simulation, since the current rate is large during discharge, the peak in the vicinity of SOC 90% cannot be confirmed although the fine peaks and slopes in the temperature and pressure characteristics that were confirmed in the low rate charge / discharge test described later cannot be confirmed. Was confirmed both during charging and discharging.

（２）低レート充放電試験
充放電中の微小変化をより詳細に把握するために低レートでの充放電を上記の実験装置を用いて実施した。具体的には、以下の充放電を１サイクル実施した。
充電：CC/CV 0.05C/4.1V, 23h, 15℃
放電：CC 0.05C to 2.75V, 15℃
結果を、図４に示す。なお、上記のGEO運用模擬試験と同様に、温度の測定結果は、各温度センサ７による温度の測定結果が同様の特性を示したため、蓄電池３の内周面の表面の中央付近の温度センサ７による測定結果のみを示す。また、圧力センサ出力の絶対値については校正を行っていないものである。 (2) Low-rate charge / discharge test In order to grasp in detail the minute changes during charge / discharge, charge / discharge at a low rate was performed using the above-described experimental apparatus. Specifically, the following charge / discharge was performed for one cycle.
Charging: CC / CV 0.05C / 4.1V, 23h, 15 ℃
Discharge: CC 0.05C to 2.75V, 15 ℃
The results are shown in FIG. Similar to the GEO operation simulation test described above, the temperature measurement results of the temperature measurement results by the temperature sensors 7 showed similar characteristics, and therefore the temperature sensor 7 near the center of the inner peripheral surface of the storage battery 3. Only the measurement result by is shown. Further, the absolute value of the pressure sensor output is not calibrated.

図４から、GEO運用模擬試験で確認されたSOC90％付近のピーク以外にも温度特性と圧力特性共にいくつかのピークや傾きが変化する点が認められ、その一部のピークや傾きが変化する点については、両者で同期している部分が見受けられた。   Figure 4 shows that some peaks and slopes of temperature and pressure characteristics change in addition to the peak near SOC 90% confirmed in the GEO operation simulation test, and some of the peaks and slopes change. About the point, the part which both synchronized was seen.

上述のとおり、低電流充放電曲線における電圧（Ｖ）を容量（Ｑ）で微分して得られるｄＶ／ｄＱ曲線におけるピークは、正極又は負極の結晶相変化に対応し、正極又は負極が劣化するとピークの位置が変化することが知られている。各ピークの同定は、例えば電池を解体して得た正極及び負極で金属リチウムを対極とするハーフセルの充放電試験を行い、それにより得られた正極及び負極のｄＶ／ｄＱ曲線のピークとの比較により行うことができる。   As described above, the peak in the dV / dQ curve obtained by differentiating the voltage (V) in the low current charge / discharge curve by the capacity (Q) corresponds to the crystal phase change of the positive electrode or the negative electrode, and the positive electrode or the negative electrode deteriorates. It is known that the position of the peak changes. For identification of each peak, for example, a positive and negative electrode obtained by disassembling a battery was subjected to a half-cell charge / discharge test using metallic lithium as a counter electrode, and compared with the obtained positive and negative dV / dQ curve peaks. Can be performed.

図５は、低レート充放電試験で得られた測定値から算出されたｄＶ／ｄＱと電圧、圧力の関係を示す図である。図５のｄＶ／ｄＱ曲線においては、正極由来のピークが１つ、負極由来のピークが２つ認められる。そして、これらのピークに対応して圧力特性においてもピークや傾きが変化する点が認められる。   FIG. 5 is a diagram showing the relationship between dV / dQ, voltage, and pressure calculated from the measured values obtained in the low rate charge / discharge test. In the dV / dQ curve of FIG. 5, one peak derived from the positive electrode and two peaks derived from the negative electrode are observed. And the point in which a peak and inclination change also in a pressure characteristic corresponding to these peaks is recognized.

以上の実験結果から、蓄電池の充放電において、電極劣化と、蓄電池の圧力、蓄電池の温度、ｄＶ／ｄＱに相関性があることが分かった。   From the above experimental results, it has been found that there is a correlation between electrode deterioration, storage battery pressure, storage battery temperature, and dV / dQ in charge / discharge of the storage battery.

したがって、圧力特性におけるピーク又は傾きが変化する点の位置や形状が、蓄電池が劣化していない時から変化していれば、電極が劣化していると判定できる。   Therefore, if the position or shape of the point where the peak or slope of the pressure characteristic changes has changed since the storage battery has not deteriorated, it can be determined that the electrode has deteriorated.

（実施形態）
図６は、本発明の１つの実施形態に係る電極劣化判定システムの全体構成図である。図６に示されるように、本実施形態に係る電極劣化判定システム１は、圧力センサ１１１、電流センサ１１３、電圧センサ１１５、測定部１３、記憶部１５、電極劣化判定部１７を備える。 (Embodiment)
FIG. 6 is an overall configuration diagram of an electrode deterioration determination system according to one embodiment of the present invention. As shown in FIG. 6, the electrode deterioration determination system 1 according to the present embodiment includes a pressure sensor 111, a current sensor 113, a voltage sensor 115, a measurement unit 13, a storage unit 15, and an electrode deterioration determination unit 17.

圧力センサ１１１、電流センサ１１３、電圧センサ１１５は、蓄電池３の圧力、電流、電圧を検出し、検出された圧力データ、電流データ、電圧データが測定部１３に送られる。   The pressure sensor 111, the current sensor 113, and the voltage sensor 115 detect the pressure, current, and voltage of the storage battery 3, and the detected pressure data, current data, and voltage data are sent to the measurement unit 13.

測定部１３は、電流センサ１１３や電圧センサ１１５からの測定データに基づいて、所定の充電レート又は所定の放電レートで、蓄電池３の充電又は放電を行いつつ、圧力対時間特性を測定する。   Based on the measurement data from the current sensor 113 and the voltage sensor 115, the measurement unit 13 measures the pressure versus time characteristic while charging or discharging the storage battery 3 at a predetermined charge rate or a predetermined discharge rate.

記憶部１５は、測定された圧力対時間特性等のデータを記憶する。   The storage unit 15 stores data such as measured pressure versus time characteristics.

電極劣化判定部１７は、蓄電池３の電極が劣化していない時に、例えば蓄電池３が初期状態にある時に、測定部１３により測定された第１の圧力対時間特性と、第１の蓄電池の圧力対時間特性が測定された後に該測定における充電レート及び／又は放電レートと同じ充電レート及び／又は放電レートで測定部１３により測定された第２の圧力対時間特性を比較し、両者が実質的に相違した場合、前記蓄電池の電極が劣化したと判定する。例えば、第１の圧力対時間特性における各ピークや変曲点の位置と、第２の圧力対時間特性における各ピークや変曲点の位置が実質的に相違した場合、蓄電池３の電極が劣化したと判定することができる。   The electrode deterioration determination unit 17 includes a first pressure-time characteristic measured by the measurement unit 13 and a pressure of the first storage battery when the electrode of the storage battery 3 is not deteriorated, for example, when the storage battery 3 is in an initial state. After the time characteristics are measured, the second pressure-time characteristics measured by the measurement unit 13 at the same charge rate and / or discharge rate as the charge rate and / or discharge rate in the measurement are compared. If it is different, it is determined that the electrode of the storage battery has deteriorated. For example, when the position of each peak or inflection point in the first pressure versus time characteristic is substantially different from the position of each peak or inflection point in the second pressure versus time characteristic, the electrode of the storage battery 3 deteriorates. Can be determined.

図７は、本発明の１つの実施形態に係る電極劣化判定システム１のハードウエア構成の例を示す図である。電極劣化判定システム１は、ＣＰＵ１０ａ、ＲＡＭ１０ｂ、ＲＯＭ１０ｃ、外部メモリ１０ｄ、入力部１０ｅ、出力部１０ｆ、通信部１０ｇを含む。ＲＡＭ１０ｂ、ＲＯＭ１０ｃ、外部メモリ１０ｄ、入力部１０ｅ、出力部１０ｆ、通信部１０ｇは、システムバス１０ｈを介して、ＣＰＵ１０ａに接続されている。   FIG. 7 is a diagram illustrating an example of a hardware configuration of the electrode deterioration determination system 1 according to an embodiment of the present invention. The electrode deterioration determination system 1 includes a CPU 10a, a RAM 10b, a ROM 10c, an external memory 10d, an input unit 10e, an output unit 10f, and a communication unit 10g. The RAM 10b, ROM 10c, external memory 10d, input unit 10e, output unit 10f, and communication unit 10g are connected to the CPU 10a via the system bus 10h.

図６に示される電極劣化判定システム１の各部は、ＲＯＭ１０ｃや外部メモリ１０ｄに記憶された各種プログラムが、ＣＰＵ１０ａ、ＲＡＭ１０ｂ、ＲＯＭ１０ｃ、外部メモリ１０ｄ、入力部１０ｅ、出力部１０ｆ、通信部１０ｇ等を資源として使用することで実現される。   Each part of the electrode deterioration determination system 1 shown in FIG. 6 includes various programs stored in the ROM 10c and the external memory 10d, such as a CPU 10a, a RAM 10b, a ROM 10c, an external memory 10d, an input unit 10e, an output unit 10f, and a communication unit 10g. Realized by using as a resource.

以上のシステム構成を前提に、本発明の１つの実施形態に係る電極劣化判定システムの処理の例を図６を参照して、以下に説明する。図８Ａ及び図８Ｂは、本発明の１つの実施形態に係る電極劣化判定システムの処理の例のフローチャートである。   Based on the above system configuration, an example of processing of the electrode deterioration determination system according to one embodiment of the present invention will be described below with reference to FIG. 8A and 8B are flowcharts of an example of processing of the electrode deterioration determination system according to one embodiment of the present invention.

図８Ａは、電極劣化判定を行う際に参照するための、第１の圧力対時間特性の測定に係るフローチャートである。蓄電池３の電極が劣化していない時に、例えば蓄電池３が初期状態にある時に、ユーザからの指示等に応じて、測定部１３が、電流センサ１１３や電圧センサ１１５からの測定データに基づいて、所定の充電レートで、蓄電池３の充電を行いつつ（ステップＳ１１）、第１の圧力対時間特性を測定し（ステップＳ１２）、記憶部１５に記憶させる（ステップＳ１３）。   FIG. 8A is a flowchart relating to the measurement of the first pressure-time characteristic for reference when performing electrode deterioration determination. When the electrode of the storage battery 3 is not deteriorated, for example, when the storage battery 3 is in an initial state, the measuring unit 13 is based on the measurement data from the current sensor 113 or the voltage sensor 115 in accordance with an instruction from the user. While charging the storage battery 3 at a predetermined charging rate (step S11), the first pressure-time characteristic is measured (step S12) and stored in the storage unit 15 (step S13).

図８Ｂは、第１の圧力対時間特性を測定した後に、ユーザからの指示等に応じて実行される、電極劣化判定に係るフローチャートである。ユーザからの、入力部１０ｅを介した指示等に応じて測定部１３が、電流センサ１１３や電圧センサ１１５からの測定データに基づいて、図８ＡのステップＳ１１の第１の圧力対時間特性の測定と同じ充電レートで、蓄電池３の充電を行いつつ（ステップＳ２１）、第２の圧力対時間特性を測定し（ステップＳ２２）、記憶部１５に記憶させる（ステップＳ２３）。   FIG. 8B is a flowchart relating to electrode deterioration determination, which is executed in accordance with an instruction from the user after measuring the first pressure-time characteristic. In response to an instruction from the user via the input unit 10e, the measurement unit 13 measures the first pressure-time characteristic in step S11 of FIG. 8A based on the measurement data from the current sensor 113 and the voltage sensor 115. While charging the storage battery 3 at the same charging rate (step S21), the second pressure versus time characteristic is measured (step S22) and stored in the storage unit 15 (step S23).

電極劣化判定部１７が、記憶部１５に記憶された第１の圧力対時間特性と第２の圧力対時間特性を比較し（ステップＳ２４）、両者が実質的に相違した場合、蓄電池３の電極が劣化したと判定する（ステップＳ２５）。例えば、第１の圧力対時間特性に現れた各ピークや傾きが変化する点の位置や形状に対して、そのピークに対応する第２の圧力対時間特性の各ピークや傾きが変化する点の位置や形状が変化していた場合、蓄電池３の電極が劣化したと判定する。   The electrode deterioration determination unit 17 compares the first pressure versus time characteristic and the second pressure versus time characteristic stored in the storage unit 15 (step S24), and if both are substantially different, the electrode of the storage battery 3 Is determined to have deteriorated (step S25). For example, with respect to the position and shape of each peak or slope changing in the first pressure vs. time characteristic, each peak or slope of the second pressure vs. time characteristic corresponding to that peak changes. When the position and shape have changed, it determines with the electrode of the storage battery 3 having deteriorated.

この場合、各ピークや傾きが変化する点が正極又は負極のいずれに由来するのかを同定するためのデータ（例えば、上述のようなｄＶ／ｄＱ曲線に基づいて得られた各ピークが正極又は負極のいずれに由来するのかのデータ）を予め記憶部１５に記憶させておけば、蓄電池３の正極又は負極のいずれが劣化したかと判定することができる。   In this case, data for identifying whether each peak or the point at which the slope changes is derived from the positive electrode or the negative electrode (for example, each peak obtained based on the dV / dQ curve as described above is the positive electrode or the negative electrode. If it is previously stored in the storage unit 15, it can be determined which of the positive electrode and the negative electrode of the storage battery 3 has deteriorated.

ステップＳ２５で電極の劣化を判定した場合には、例えば、出力部１０ｆに電極の劣化を報知するアラートを表示したり、通信部１０ｇを介して電極の劣化を通知することで、ユーザーは、蓄電池３で駆動される装置への給電に支障が生じる前に、蓄電池３の運用方法を変更したり、蓄電池３の交換を行うことができる。   When it is determined in step S25 that the electrode has deteriorated, for example, an alert for notifying the electrode deterioration is displayed on the output unit 10f or the electrode is notified of the electrode deterioration via the communication unit 10g. The operation method of the storage battery 3 can be changed or the storage battery 3 can be replaced before the power supply to the device driven by 3 is hindered.

本実施形態では、圧力対時間特性の測定は、比較的低レートかつ定電流の制御が容易な、蓄電池３の充電において行ったが、同様の動作により、蓄電池３の放電並びに蓄電池３の充電及び放電による圧力対時間特性の測定による電極劣化の判定が可能である。   In the present embodiment, the measurement of the pressure vs. time characteristic was performed in the charging of the storage battery 3 with a relatively low rate and easy control of the constant current. However, by the same operation, the discharge of the storage battery 3 and the charging of the storage battery 3 It is possible to determine electrode deterioration by measuring pressure vs. time characteristics due to discharge.

また、圧力センサ１１１による圧力検知は、蓄電池３の包装体の適宜な選択により、高精度かつ安定した検知が可能となり、ｄＶ／ｄＱ曲線と相関の高い圧力対時間特性の測定が可能となるので、電極劣化判定が難しかった場合や複雑であった場合でも電極劣化判定を可能もしくは簡単化することができる。   In addition, pressure detection by the pressure sensor 111 can be performed with high accuracy and stability by appropriately selecting the package of the storage battery 3, and pressure-time characteristics having a high correlation with the dV / dQ curve can be measured. Even when the electrode deterioration determination is difficult or complicated, the electrode deterioration determination can be made possible or simplified.

上記実施形態では、圧力対時間特性のみによって電極劣化の判定を行ったが、上記実施形態において測定されている電圧対時間特性や、温度対時間特性も測定し、圧力対時間特性に加えて、電圧対時間特性や温度対時間特性を併せて解析することにより、電極劣化判定の精度を高めることができる場合もある。   In the above embodiment, the electrode deterioration was determined only by the pressure vs. time characteristic, but the voltage vs. time characteristic measured in the above embodiment and the temperature vs. time characteristic were also measured, in addition to the pressure vs. time characteristic, In some cases, the accuracy of electrode deterioration determination can be improved by analyzing the voltage versus time characteristic and the temperature versus time characteristic together.

本実施形態によれば、従来の手法では電極劣化判定が難しかった場合や複雑であった場合でも電極劣化判定を可能もしくは簡単化することができる。   According to the present embodiment, the electrode deterioration determination can be made or simplified even when the electrode deterioration determination is difficult or complicated by the conventional method.

以上、本発明について、例示のためにいくつかの実施形態に関して説明してきたが、本発明はこれに限定されるものでなく、本発明の範囲及び精神から逸脱することなく、形態及び詳細について、様々な変形及び修正を行うことができることは、当業者に明らかであろう。   Although the present invention has been described above with reference to several embodiments for purposes of illustration, the present invention is not limited thereto, and forms and details are within the scope and spirit of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made.

１ 電極劣化判定システム
１１１ 圧力センサ
１１３ 電流センサ
１１５ 電圧センサ
１３ 測定部
１５ 記憶部
１７ 電極劣化判定部
３ 蓄電池
５ 挟み板
７ 温度センサ
９ 圧力センサ DESCRIPTION OF SYMBOLS 1 Electrode deterioration determination system 111 Pressure sensor 113 Current sensor 115 Voltage sensor 13 Measuring part 15 Storage part 17 Electrode deterioration determination part 3 Storage battery 5 Clamping plate 7 Temperature sensor 9 Pressure sensor

Claims (5)

蓄電池の電極劣化判定システムであって、
所定の充電レートでの前記蓄電池の充電期間及び／又は所定の放電レートでの前記蓄電池の放電期間における前記蓄電池の圧力対時間特性を測定する測定部と、
前記蓄電池の電極が劣化していない時に前記測定部により測定された第１の圧力対時間特性と、前記第１の圧力対時間特性の測定における充電レート及び／又は放電レートと同じ充電レート及び／又は放電レートで前記測定部により測定された第２の圧力対時間特性とを比較し、前記蓄電池の電極劣化を判定する電極劣化判定部と、
を含む電極劣化判定システム。 A storage battery electrode deterioration determination system,
A measuring unit for measuring a pressure-time characteristic of the storage battery during a charge period of the storage battery at a predetermined charge rate and / or a discharge period of the storage battery at a predetermined discharge rate;
The first pressure-time characteristic measured by the measurement unit when the electrode of the storage battery is not deteriorated, and the same charge rate and / or discharge rate as the charge rate and / or discharge rate in the measurement of the first pressure-time characteristic Alternatively, an electrode deterioration determination unit that compares the second pressure versus time characteristic measured by the measurement unit at a discharge rate and determines electrode deterioration of the storage battery;
Electrode degradation determination system including 前記電極劣化判定部は、前記第１の圧力対時間特性におけるピーク及び／又は傾きが変化する点の位置及び／又は形状と、前記第２の圧力対時間特性におけるピーク及び／又は傾きが変化する点の位置及び／又は形状とを比較し、前記蓄電池の電極劣化を判定する請求項１に記載の電極劣化判定システム。   The electrode deterioration determining unit changes a position and / or shape of a point at which a peak and / or slope in the first pressure-time characteristic changes and a peak and / or slope in the second pressure-time characteristic. The electrode deterioration determination system according to claim 1, wherein the electrode deterioration of the storage battery is determined by comparing the position and / or shape of a point. 前記所定のレートは、低レートである請求項１又は２に記載の電極劣化判定システム。   The electrode deterioration determination system according to claim 1 or 2, wherein the predetermined rate is a low rate. 前記電極劣化判定部は、予め取得された、前記所定の充電レートでの前記蓄電池の充電期間及び／又は所定の放電レートでの前記蓄電池の放電期間における前記蓄電池の圧力対時間特性の各ピークや傾きが変化する点が、前記蓄電池の正極又は負極のいずれに由来するのかを同定するためのデータを参照して、前記蓄電池の正極又は負極のいずれが劣化したかを判定する請求項２又は３に記載の電極劣化判定システム。   The electrode deterioration determination unit obtains each peak of the storage battery's pressure vs. time characteristics during the storage battery charging period and / or the storage battery discharging period at a predetermined discharging rate obtained in advance. 4. The method of determining whether the positive or negative electrode of the storage battery has deteriorated by referring to data for identifying whether the point at which the slope changes originates from the positive or negative electrode of the storage battery. The electrode deterioration determination system described in 1. 蓄電池の電極劣化を該蓄電池の圧力を測定することによって判定する方法であって、
前記蓄電池の電極が劣化していない時に、所定の充電レートでの前記蓄電池の充電期間及び／又は所定の放電レートでの前記蓄電池の放電期間における、第１の圧力対時間特性を測定するステップと、
前記第１の前記蓄電池の圧力対時間特性を測定した後に、前記所定の充電レートでの前記蓄電池の充電期間及び／又は前記所定の放電レートでの前記蓄電池の放電期間における、第２の圧力対時間特性を測定するステップと、
前記第１の圧力対時間特性と前記第２の圧力対時間特性とを比較し、前記蓄電池の電極劣化を判定するステップと、
を含む電極劣化判定方法。 A method for determining electrode deterioration of a storage battery by measuring the pressure of the storage battery,
Measuring a first pressure versus time characteristic during a charge period of the storage battery at a predetermined charge rate and / or a discharge period of the storage battery at a predetermined discharge rate when the electrode of the storage battery is not degraded; ,
After measuring the pressure versus time characteristic of the first storage battery, a second pressure pair during a charge period of the storage battery at the predetermined charge rate and / or a discharge period of the storage battery at the predetermined discharge rate. Measuring time characteristics;
Comparing the first pressure versus time characteristic and the second pressure versus time characteristic to determine electrode degradation of the storage battery;
An electrode deterioration determination method including:
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112363069A (en) * 2020-09-18 2021-02-12 万向一二三股份公司 Lithium ion battery tab fracture detection method
JP7452780B2 (en) 2020-12-07 2024-03-19 エルジー エナジー ソリューション リミテッド Battery diagnostic device and method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112363069A (en) * 2020-09-18 2021-02-12 万向一二三股份公司 Lithium ion battery tab fracture detection method
CN112363069B (en) * 2020-09-18 2023-07-07 万向一二三股份公司 Method for detecting breakage of tab of lithium ion battery
JP7452780B2 (en) 2020-12-07 2024-03-19 エルジー エナジー ソリューション リミテッド Battery diagnostic device and method

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