JP7480316B2 - 二次電池およびこれのリチウム析出の検出方法 - Google Patents
二次電池およびこれのリチウム析出の検出方法 Download PDFInfo
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- 230000008021 deposition Effects 0.000 title claims description 44
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- 238000010586 diagram Methods 0.000 description 16
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- 238000007599 discharging Methods 0.000 description 7
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- 239000000126 substance Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
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- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/482—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for several batteries or cells simultaneously or sequentially
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/24—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in magnetic properties
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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]
-
- 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]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/12—Measuring magnetic properties of articles or specimens of solids or fluids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
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- G—PHYSICS
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- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Description
本発明は、二次電池およびこれのリチウム析出の検出方法に関する。
[先行技術文献]
[特許文献]
[特許文献1] 国際公開第2018/235846号
本実施形態のまた他の特徴によると、磁気センサは、正極のタブ領域と負極との間で発生する磁場の変化を検出するように取り付けられることができる。
本実施形態のさらに他の特徴によると、変形検知センサは、ひずみゲージであってもよい。
本実施形態のさらに他の特徴によると、電池ケースは、軟性のパウチであってもよい。
本発明の一実施形態に係る電極組立体10は、先ず、正極活物質1012、バインダー、導電材などを混合したスラリーを正極集電体1011に塗布し、負極活物質1022、バインダー、導電材などを混合したスラリーを負極集電体1021に塗布して、正極(Cathode)101および負極(Anode)102を製造する。そして、製造された正極101と負極102との間にセパレータ(Separator)103を介在して積層することで、単位セル(Unit Cell)が形成される。再び単位セルが互いに積層されることで、図1に示されたように、所定形状の電極組立体10が形成される。
パウチ型二次電池1を製造する過程は、前述したように、電極組立体10を形成した後、電極組立体10を電池ケース13に挿入し、電解液の注入後にシールする。
図4の(a)は、リチウムが正極101の厚さ方向に析出される場合を概念的に示している。リチウムが厚さ方向に析出される場合にも、正極101と負極102との間に約0.1mm以下の高さの逆転が発生した。そして、負極102に比べて高い位置に存在する正極101から発生するリチウムイオンは、負極102の最も近い領域(負極活物質1022の表面に四角形で示した部分)に移動することになる。すなわち、当該領域での電流密度が上昇することになる。
電池パック2は、電気自動車用の電池パックやエネルギー貯蔵装置用の電池ラックなどの形態で用いられることができる。
図8を参照すると、電池パック2が駆動されると(S1)、個別の電池セル201において充電および放電が行われる。この際、前述したように、充放電時、リチウムが析出されている場合、そうではない場合に比べて電流密度が変化し、その結果、周囲に発生する磁場も変わる。よって、電池セル201に取り付けられた磁気センサ20を介して磁場を測定することで、リチウムが析出されたか否かをモニターする(S2)。すなわち、リチウム析出を検出するためのパラメータとして磁場の変化を検出する。
図10を参照すると、電池パック2が駆動されると(S11)、個別の電池セル201において充電および放電が行われる。この際、前述したように、充放電時、リチウムが析出されている場合、そうではない場合に比べて電極の硬度が変化し、その結果、電極を囲んでいる電池ケース13に変形が発生し得る。よって、電池セル201に取り付けられた変形検知センサ30を介して電池ケース13の変形を測定することで、リチウムが析出されたか否かをモニターする(S12)。すなわち、リチウム析出を検出するためのパラメータとして電池ケース13の変形を検出する。
本実施形態においては、リチウム析出検出手段として磁気センサ20および変形検知センサ30が同時に形成されている。このように構成することで、磁気センサ20のみを用いるかまたは変形検知センサ30のみを用いる図5および図9による二次電池に比べて、さらに正確にリチウム析出を検出できるようになる。
Claims (12)
- 正極および負極と、
前記正極および負極を密封する電池ケースと、
前記電池ケースの表面において、前記正極の外部に突出するタブ周囲に備えられてリチウム析出を検出するリチウム析出検出手段と
を備える、二次電池。 - 前記リチウム析出検出手段は、前記電池ケースにおいて、前記正極のタブ領域に備えられる磁気センサを含む、請求項1に記載の二次電池。
- 前記磁気センサは、前記正極のタブ領域と前記負極との間で発生する磁場の変化を検出するように取り付けられる、請求項2に記載の二次電池。
- 前記磁気センサは、前記正極のタブ領域にオーバーコーティングされた部分から前記負極に流れる電流に基づいて発生する磁場を検出する、請求項2または3に記載の二次電池。
- 前記リチウム析出検出手段は、前記電池ケースにおいて、前記正極のタブ領域に備えられる変形検知センサを含む、請求項1から4のいずれか一項に記載の二次電池。
- 前記変形検知センサは、ひずみゲージである、請求項5に記載の二次電池。
- 前記ひずみゲージは、前記電池ケースの正極と接する面側、または前記電池ケースから前記正極のタブが延び出る面側に形成される、請求項6に記載の二次電池。
- 前記変形検知センサは、前記電池ケースにおいて前記正極のタブが延び出る面側に形成された第1変形検知センサと、前記電池ケースにおいて前記正極と対向する面側に形成された第2変形検知センサとを有する、請求項5に記載の二次電池。
- 前記電池ケースは、軟性のパウチである、請求項5から8のいずれか一項に記載の二次電池。
- 正極および負極を電池ケース内に収容して形成された二次電池におけるリチウム析出の検出方法であって、
前記電池ケースの表面において、前記正極の外部に突出するタブ周囲に備えられるリチウム析出検出手段を介して、予め設定されたパラメータの変化を検出するステップと、
前記パラメータの変化量が基準値以下であるか否かを判断するステップと、
前記判断の結果に基づいてリチウム析出を決めるステップと
含む、リチウム析出の検出方法。 - 前記リチウム析出検出手段として、前記電池ケースにおいて、前記正極のタブ領域に備えられる磁気センサを含み、
前記パラメータの変化を検出するステップは、前記磁気センサにより測定される磁場の変化を検出する、請求項10に記載のリチウム析出の検出方法。 - 前記リチウム析出検出手段として、前記電池ケースにおいて、前記正極のタブ領域に備えられる変形検知センサを含み、
前記パラメータの変化を検出するステップは、前記変形検知センサにより測定される、軟性のパウチである前記電池ケースの変形を検出する、請求項10または11に記載のリチウム析出の検出方法。
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