JP2023534002A - 多孔性支持層を含むバイポーラー全固体電池 - Google Patents
多孔性支持層を含むバイポーラー全固体電池 Download PDFInfo
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- JP2023534002A JP2023534002A JP2023501656A JP2023501656A JP2023534002A JP 2023534002 A JP2023534002 A JP 2023534002A JP 2023501656 A JP2023501656 A JP 2023501656A JP 2023501656 A JP2023501656 A JP 2023501656A JP 2023534002 A JP2023534002 A JP 2023534002A
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- support layer
- porous support
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- positive electrode
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Images
Classifications
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
- H01M10/0418—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes with bipolar electrodes
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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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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Abstract
Description
(b)正極、固体電解質、及び第2多孔性支持層を含む単位セルが2個以上直列に連結されたバイポーラー全固体電池を提供する。
(b)正極、固体電解質、及び第2多孔性支持層を含む単位セルが2個以上直列に連結されたことを特徴とする。
前記第1固体電解質1120及び第2固体電解質1220の前記第1負極1130及び第2負極1230の対面には、リチウムデンドライトの形成を誘導するためのコーティング層があり得る。
このとき、第1多孔性支持層1300として使用された素材自体の弾性力は、ジグの駆動圧より大きくなければならない。
全固体電池の駆動時、ジグ圧力及び/又は充電時に堆積するリチウムによる圧力変化に対する第1多孔性支持層の厚さ変化を測定した。このとき、前記第1多孔性支持層としては、気孔度が類似し、厚さが異なる第1多孔性支持層#1と第1多孔性支持層#2、及び気孔度及び厚さが異なる第1多孔性支持層#3を使用した。
実験例2では、下記のような構成で形成された電池を5回充放電し、厚さ変化率を計算した。前記電池の初期容量は、60℃の条件で充放電して測定し、充電条件はCC/CV(8.5V、0.05C、0.01C電流カットオフ)とし、放電条件はCC条件(6V、0.05C、60℃)として測定した。このとき、厚さ増加率は、充電後の電池の厚さ/充電前の電池の厚さ×100として計算し、これを下記の表3に示した。また、5回充放電した後の容量維持率(retention)を測定し、これを下記の表3に示した。
正極活物質であるNCM811(LiNi0.8Co0.1Mn0.1O2)、固体電解質であるアルジロダイト(Li6PS5Cl)、導電材であるカーボン、及びPTFEバインダーを77.5:19.5:1.5:1.5の重量比でアニソールに分散及び撹拌することによって正極スラリーを製造した。前記正極スラリーを15μmの厚さのアルミニウム集電体にドクターブレードを用いて塗布した後、100℃で12時間真空乾燥することによって2mAh/cm2の容量を有する正極を製造した。
前記実施例1-1において、第1多孔性支持層1300として、前記第1多孔性支持層#2を10MPaで加圧した後のものを1枚使用したことを除いては、実施例1-1と同一に製作及び評価した。
前記実施例1-1において、容量が3mAh/cm2である正極を使用したことを除いては、実施例1-1と同一に製作及び評価した。
前記実施例1-1において第1多孔性支持層を適用していないことを除いては、実施例1-1と同一に製作及び評価した。
前記実施例1-1において、第1多孔性支持層1300として、前記第1多孔性支持層#1を20MPaで加圧した後のものを1枚使用したことを除いては、実施例1-1と同一に製作及び評価した。
前記実施例1-1において、第1多孔性支持層1300として、前記第1多孔性支持層#3を1枚使用したことを除いては、実施例1-1と同一に製作及び評価した。
全固体電池の多孔性集電体として使用するための第2多孔性支持層として、下記のようにニッケルフォーム(Ni foam)2種(ニッケルフォーム#1、ニッケルフォーム#2)を選定した。前記第2多孔性支持層を2.0cm×2.0cmに打ち抜いた後、5MPa、10MPa、15MPa、25MPa、50MPaで順次加圧し、各段階での厚さ変化を測定した後、これを下記の表4に示した。
実験例4では、下記の構成で形成された全固体電池の充放電を行い、厚さ変化率を計算した。前記初期容量は、60℃の条件で充放電を行って測定し、充電条件はCC/CV(8.5V、0.05C、0.01C電流カットオフ)とし、放電条件はCC条件(6V、0.05C、60℃)として測定した。このとき、厚さ増加率は、充電後、電池の厚さ/充電前の電池厚さ×100として計算し、これを下記の表7に示した。
正極活物質であるNCM811(LiNi0.8Co0.1Mn0.1O2)、固体電解質であるアルジロダイト(Li6PS5Cl)、導電材であるカーボン、及びPTFEバインダーを77.5:19.5:1.5:1.5の重量比でアニソールに分散及び撹拌することによって正極スラリーを製造した。前記正極スラリーを15μmの厚さのアルミニウム集電体にドクターブレードを用いて塗布した後、100℃で12時間真空乾燥することによって4mAh/cm2の容量を有する正極を製造し、これを最外郭正極として使用した。
前記実施例2-1において、第2多孔性支持層として、50MPaで加圧したニッケルフォーム#2を適用したことを除いては、実施例2-1と同一に製作及び評価した。
前記実施例2-1において、正極の容量が6mAh/cm2で、第2多孔性支持層として、50MPaで加圧したニッケルフォーム#2を適用したことを除いては、実施例2-1と同一に製作及び評価した。
前記実施例2-1において、第2多孔性支持層として10μmの厚さのニッケルホイルを適用したことを除いては、実施例2-1と同一に製作及び評価した。
前記実施例2-1において、正極の容量が6mAh/cm2で、第2多孔性支持層として10μmの厚さのニッケルホイルを適用したことを除いては、実施例2-1と同一に製作及び評価した。
100、1100、2100:第1単位セル
110、1110、2110:第1正極
111、1111、2111:第1正極活物質
112、1112、2112:第1正極集電体
120、1120、2120:第1固体電解質
130、1130:第1負極
131、1131:第1負極活物質
132、1132:第1負極集電体
2140、2240:第2多孔性支持層
200、1200、2200:第2単位セル
210、1210、2210:第2正極
211、1211、2211:第2正極活物質
212、1212、2212:第2正極集電体
220、1220、2220:第2固体電解質
230、1230:第2負極
231、1231:第2負極活物質
232、1232:第2負極集電体
300:バイポーラー電極
1300:第1多孔性支持層
400、1400、2400:リチウム層
F1:加圧力
F2:内部圧力
m:加圧前の厚さ
M:加圧後の厚さ
JIG:ジグ
Claims (24)
- (a)正極、固体電解質、及び負極を含む単位セルが2個以上直列に連結され、前記連結された部分の中央に第1多孔性支持層が設けられたり、
(b)正極、固体電解質、及び第2多孔性支持層を含む単位セルが2個以上直列に連結されたバイポーラー全固体電池。 - 前記第1多孔性支持層の一面には、前記一つの単位セルの前記負極が配置され、その対向面には、前記他の単位セルの前記正極が配置される、請求項1に記載のバイポーラー全固体電池。
- 前記負極は、リチウム金属又は活物質層のない集電体である、請求項1に記載のバイポーラー全固体電池。
- 前記第2多孔性支持層の前記固体電解質の対面は、負極としての役割をし、前記正極の対面は、分離膜としての役割をする、請求項1に記載のバイポーラー全固体電池。
- 前記第2多孔性支持層は、リチウム負極又は負極集電体を含む、請求項1に記載のバイポーラー全固体電池。
- 前記負極集電体は金属又は金属酸化物である、請求項5に記載のバイポーラー全固体電池。
- 前記リチウム負極又は前記負極集電体は別途の活物質層を含まない、請求項5に記載のバイポーラー全固体電池。
- 前記第1多孔性支持層は、
オレフィン系多孔性基材;及び
ガラス繊維又はポリエチレンを含むグループから選ばれる一つ以上で製造されたシートや不織布;
を少なくとも一つ以上含む、請求項1に記載のバイポーラー全固体電池。 - 前記第1多孔性支持層は、
前記オレフィン系多孔性基材、又は前記シートや前記不織布を1層以上で積層した、請求項8に記載のバイポーラー全固体電池。 - 前記第1多孔性支持層が二つの層以上である場合、
前記第1多孔性支持層の各層は、それぞれ互いに異なる素材からなったり、
前記第1多孔性支持層の各層は、全て同一の素材からなる、請求項9に記載の全固体電池。 - 前記第1多孔性支持層及び前記第2多孔性支持層は、圧力が加えられるときに厚さが減少し、前記圧力が解消されるときに厚さが元に戻り、前記全固体電池内部の応力を調節する、請求項1に記載のバイポーラー全固体電池。
- 前記圧力は、充電によって前記正極のリチウムイオンが前記負極に移動しながら前記負極と前記固体電解質との間で堆積したり、前記第2多孔性支持層と前記固体電解質との間で堆積することによって発生する、請求項11に記載のバイポーラー全固体電池。
- 前記第1多孔性支持層は、リチウム堆積による厚さ変化による応力を調節する、請求項12に記載のバイポーラー全固体電池。
- 前記第2多孔性支持層の厚さは、前記堆積したリチウムの厚さより大きい、請求項12に記載のバイポーラー全固体電池。
- 前記第1多孔性支持層及び前記第2多孔性支持層は、それぞれの厚さ及び気孔度に比例して前記応力を調節する、請求項11に記載のバイポーラー全固体電池。
- 前記第1多孔性支持層は、20μm乃至50μmの厚さである、請求項1に記載のバイポーラー全固体電池。
- 前記正極は、正極集電体、及び前記正極集電体の一面に塗布された正極活物質を含む、請求項1に記載のバイポーラー全固体電池。
- 前記正極活物質は前記固体電解質に対面し、前記正極集電体は、前記第1多孔性支持層及び前記第2多孔性支持層に対面する、請求項17に記載のバイポーラー全固体電池。
- 前記第1多孔性支持層の一面に配置される前記一つの単位セルの前記負極は、別途の活物質層のないリチウム金属であり、前記第1多孔性支持層の対向面に配置される前記他の単位セルの前記正極は正極集電体である、請求項1に記載のバイポーラー全固体電池。
- 前記正極のうち前記第2多孔性支持層と前記固体電解質との間に配置された前記正極は、正極活物質のみで構成され、
このときの最外郭正極は、正極集電体、及び前記正極集電体の前記固体電解質の対面に塗布された正極活物質である、請求項1に記載のバイポーラー全固体電池。 - 前記2個以上の単位セルは一つのパウチ型電池ケース内に収納される、請求項1に記載のバイポーラー全固体電池。
- 前記2個以上の単位セルには、充放電時に外部ジグによって圧力が加えられる、請求項1に記載のバイポーラー全固体電池。
- 前記正極、前記固体電解質、及び前記第2多孔性支持層を含む前記単位セルが2個以上直列に連結された前記バイポーラー全固体電池は、
最外郭正極、前記最外郭正極に対面する固体電解質及び最外郭負極の間に、
第2多孔性支持層-正極活物質-固体電解質が積層された単位体が一つ以上反復された、請求項1に記載のバイポーラー全固体電池。 - 前記正極、前記固体電解質、及び前記第2多孔性支持層を含む前記単位セルが2個以上直列に連結された前記バイポーラー全固体電池は、
最外郭正極、前記最外郭正極に対面する固体電解質及び最外郭負極の間に、
第2多孔性支持層-正極集電体-正極活物質-固体電解質が積層された単位体が一つ以上反復された、請求項1に記載のバイポーラー全固体電池。
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JP2004273436A (ja) | 2003-02-18 | 2004-09-30 | Matsushita Electric Ind Co Ltd | 全固体薄膜積層電池 |
WO2016197098A1 (en) * | 2015-06-04 | 2016-12-08 | Ionic Materials, Inc. | Solid state bipolar battery |
EP3179549B1 (en) * | 2014-07-22 | 2019-04-17 | Rekrix Co., Ltd. | Micro-battery, and pcb and semiconductor chip using same |
JP6445601B2 (ja) * | 2016-06-01 | 2018-12-26 | トヨタ自動車株式会社 | 全固体電池の製造方法、全固体電池の製造装置及び全固体電池 |
KR101905984B1 (ko) * | 2016-10-17 | 2018-10-08 | 현대자동차주식회사 | 바이폴라 전고체 전지 및 그 제조방법 |
KR102100445B1 (ko) * | 2018-10-18 | 2020-04-13 | 한국생산기술연구원 | 집전체간 계면접착제 적용 바이폴라 적층 구조체, 그를 포함하는 전고체 리튬이차전지 및 그의 제조방법 |
KR20200142129A (ko) | 2019-06-11 | 2020-12-22 | 주식회사 미루시스템즈 | 검사대상물의 도전성패턴 결함 보수장치 |
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2021
- 2021-10-29 EP EP21886877.6A patent/EP4239752A1/en active Pending
- 2021-10-29 JP JP2023501656A patent/JP2023534002A/ja active Pending
- 2021-10-29 WO PCT/KR2021/015404 patent/WO2022092883A1/ko unknown
- 2021-10-29 CN CN202180067333.4A patent/CN116325282A/zh active Pending
- 2021-10-29 US US18/033,764 patent/US20230402655A1/en active Pending
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Publication number | Publication date |
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WO2022092883A1 (ko) | 2022-05-05 |
EP4239752A1 (en) | 2023-09-06 |
US20230402655A1 (en) | 2023-12-14 |
CN116325282A (zh) | 2023-06-23 |
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