JP7090807B2 - リチウム二次電池用負極、それを含むリチウム二次電池及びその製造方法 - Google Patents
リチウム二次電池用負極、それを含むリチウム二次電池及びその製造方法 Download PDFInfo
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Description
SiO(D50:3.2μm)と人造黒鉛を3:7の重量比率で混合し、負極活物質として使用した。上記負極活物質、スチレンブタジエンゴム(SBR(Styrene Butadiene Rubber))バインダー、カルボキシメチルセルロース(CMC(carboxymethyl cellulose))及びアセチレンブラックを93:3:1.5:2.5の重量比で水に投入して、負極合剤を製造した。上記合剤を10μm銅箔に均一にコーティングし、乾燥温度は90℃、コーティング速度は0.2m/mimの条件で実行された。コーティングされた負極は、気孔度30%に合わせて電極を圧延し、目標とする厚さに合わせた。続いて、180℃の真空オーブンで12時間を乾燥させた。
<リチウム拡散速度制御層及びリチウム層を備えた負極の製造>
上記製造例の負極をチェンバー(150℃、0.1torr)内に位置させ、トリメチルアルミニウムとH2O気体を17:1の比率で、圧力1torrの窒素ガスと共に注入した。下記のような(A)、(B)反応によって、負極合剤層上のAl2O3層の厚さが約3nmになるまで、原子層堆積工程を繰り返して実行した。
(A) Al-OH* + Al(CH3)3 + Al-O- Al(CH3)2* + CH4
(B) Al-CH3* + H2O + Al-OH* + CH4
その後、厚さ10μmのリチウム薄膜をラミネーションして、負極を製造した。
上記の得られた負極、製造された負極の対極としてのリチウム箔、ステンレス上下板を用いて負極/分離膜(ポリプロピレン素材の多孔性フィルム(20m、セルガード社))/リチウム箔の順番でコインセルを作成した。コインセル組立の直後に電解液を注入した。このとき、電解液は、エチレンカーボネート及びエチルメチルカーボネートを3:7の質量比率で混合したものである。
上記実施例1において、電解液の注液時点をコインセルの組立から2時間後に変更したことを除いては、実施例1と同様の方法で電池を製造した。
上記実施例1において、負極合剤層の上にAl2O3層を形成させる原子層堆積工程を省略したことを除いては、実施例1と同様の方法で電池を製造した。
電解液の注液時点をコインセルの組立から2時間後に変更したことを除いては、上記比較例1と同様の方法で電池を製造した。
<正極の製造>
正極活物質として、LiCoO2、スチレンブタジエンゴム(SBR(Styrene Butadiene Rubber))バインダー、カルボキシメチルセルロース(CMC(carboxymethyl cellulose))及びアセチレンブラックを93:3:1.5:2.5の重量比で水に投入し、正極合剤を製造した。上記合剤を10μmのアルミニウム箔に均一にコーティングし、50℃の真空オーブンで12時間を乾燥し、正極を製造した。
上記の得られた正極及び上記実施例1にて製造されたリチウム拡散速度制御層及びリチウム層を備えた負極を利用し、負極/分離膜(ポリプロピレン素材の多孔性フィルム(20μm、セルガード社)/正極の順に1-stackのモノセルを作成した。モノセルの組立から2時間後に電解液を注入した。このとき、電解液は、エチレンカーボネート及びエチルメチルカーボネートを3:7の質量比率で混合したものである。
上記比較例1のように製造された負極と上記実施例3のように製造された正極を用意した後、負極/分離膜(ポリプロピレン素材の多孔性フィルム(20μm、セルガード社)/正極の順に1-stackのモノセルを作成した。モノセルの組立から2時間後に電解液を注入した。このとき、電解液は、エチレンカーボネート及びエチルメチルカーボネートを3:7の質量比率で混合したものである。
<コーティング法によって製造されたリチウム拡散速度制御層を備えた負極の製造>
上記実施例1で、リチウム拡散速度制御層及びリチウム層が備えられた負極を用意する際、負極合剤層の上にポリメチルメタクリレート溶液(0.5wt%PMMA(Mw:890k)アニソール溶液)を溶液キャスティング法でコーティングした後、80℃で24時間乾燥し、リチウム拡散速度制御層を形成した。以後、実施例1と同様の方法で負極を製造した。このとき、ポリメチルメタクリレート層の厚さは200nmである。
上記の製造された負極と上記実施例3のように製造された正極を用意した後、負極/分離膜(ポリプロピレン素材の多孔性フィルム(20μm、セルガード社)/正極の順に1-stackのモノセルを作成した。モノセルの組立から2時間後に電解液を注入した。このとき、電解液は、エチレンカーボネート及びエチルメチルカーボネートを3:7の質量比率で混合したものである。
各実施例及び比較例において、用意された電池の初放電を0.1C、1.5Vまで、CCモードで先に行った後、引き続きの充電はCC/CVモードで、0.1C、5mV、0.005Ccut条件で、放電は0.1C、1.5VまでCCモードで進み、初回充放電時の不可逆容量を実行した。ドーピング総量(Total dosage)は、Li挿入(intercalation)容量とSEI生成容量を合わせたものである。ここで、Li挿入(intercalation)容量は、1.5V放電までの初容量を測定して、負極内に挿入されたリチウムの容量が求められる。また、SEI生成容量は、リチウム化する前の負極の1st不可逆容量からリチウム化された負極の1st不可逆容量を除いたものである。
実施例3、比較例3、4の電池について、抵抗を測定するためにSOC50状態で2.5C放電電流を30秒間流し、電流を流す前/後の電圧変化を通じて、下記のような式に代入して抵抗を測定し、その結果を表2に示した。
抵抗=(Vi-Vf)/I
(上記式において、Viは電流を流す前の電圧を、Vfは電流を流した後の電圧を、Iは電流量を示す)
30:金属原子
30’:化学吸着された金属原子の第1部分
30”:物理吸着されたり漂ったりする金属原子の第2部分
30a:化学吸着された金属原子の第1部分の前駆体
40:酸化剤
50:金属酸化物層
100:負極
10’、110:集電体
20’、120:負極合剤層
130:リチウム拡散速度制御層
20、140:リチウム層
10、150:剥離板
Claims (13)
- 集電体と、
前記集電体の上に形成された負極合剤層と、
前記負極合剤層の上に形成されたリチウム拡散速度制御層と、及び
前記リチウム拡散速度制御層の上に形成されたリチウム層と、を含み、
前記リチウム拡散速度制御層の厚さは0.1~100nmであり、
前記リチウム拡散速度制御層はAl 2 O 3 、TiO 2 、ZrO 2 、HfO 2 、Ta 2 O 5 、Nb 2 O 5 、Y 2 O 3 、CeO 2 、La 2 O 3 、Ln 2 O 3 、Lu 2 O 3 、PrAlO 3 、Er 2 O 3 、HfAlO、HfSiO、ZrSiO、ZrAlO、HfON、HfSiON、SrTiO 3 、BaTiO 3 、及びBST(チタン酸バリウムストロンチウム)からなる群から選択された1種または2種以上を含む、リチウム二次電池用負極。 - 前記リチウム拡散速度制御層は、電解液の注液時まで、前記リチウム層のリチウムが負極合剤層に拡散されるのを制御する、請求項1に記載のリチウム二次電池用負極。
- 前記リチウム拡散速度制御層は、初回充放電時まで、前記リチウム層のリチウムが負極合剤層に拡散されるのを制御する、請求項1に記載のリチウム二次電池用負極。
- 前記リチウム拡散速度制御層の厚さは0.5~50nmである、請求項1から3の何れか一項に記載のリチウム二次電池用負極。
- 前記負極合剤層は、SiOx(0<x≦2)、SnO及びSnO2からなる群から選択された1種の化合物または2種以上の混合物を含む、請求項1から4の何れか一項に記載のリチウム二次電池用負極。
- 前記リチウム拡散速度制御層はAl2O3である、請求項1から5の何れか一項に記載のリチウム二次電池用負極。
- 前記リチウム拡散速度制御層及びリチウム層の厚さ比は、1:100~1:20000である、請求項1から6の何れか一項に記載のリチウム二次電池用負極。
- (S11)集電体の上に負極合剤層を形成する段階と、
(S12)剥離板の表面にリチウム薄膜層を形成する段階と、
(S13)前記リチウム薄膜層の上に金属酸化物を導入する原子層堆積工程を繰り返し、リチウム拡散速度制御層を形成する段階と、
(S14)前記負極合剤層と前記リチウム拡散速度制御層が対面するように、前記(S11)と前記(S13)の結果物を積層させて負極を準備する段階と、
(S15)前記(S14)段階で準備された負極を含む電極組立体を製造する段階と、及び
(S16)前記電極組立体に電解液を注液する段階と、を含む、リチウム二次電池を製造する方法。 - 請求項1から7の何れか一項に記載のリチウム二次電池用負極を製造する方法であって、
(S21)集電体の上に負極合剤層を形成する段階と、
(S22)前記負極合剤層の上に金属酸化物を導入する原子層堆積工程を繰り返し、リチウム拡散速度制御層を形成する段階と、
(S23)前記リチウム拡散速度制御層の上にリチウム薄膜を積層して負極を製造する段階と、
(S24)前記(S23)段階で製造された負極を含む電極組立体を製造する段階と、及び
(S25)前記電極組立体に電解液を注液する段階と、を含む、リチウム二次電池を製造する方法。 - 前記リチウム拡散速度制御層の厚さが0.1~100nmになるまで、前記原子層堆積工程を実行する、請求項8または9に記載のリチウム二次電池を製造する方法。
- 前記リチウム拡散速度制御層の厚さが0.5~50nmになるまで、前記原子層堆積工程を実行する、請求項8または9に記載のリチウム二次電池を製造する方法。
- 前記(S13)段階は、
(S12)の結果物をチェンバー内に位置させる段階と、
前記チェンバー内に金属原子を供給する段階と、
前記チェンバー内にパージガスを供給する段階と、
前記チェンバー内に酸化剤を供給し、金属酸化物層を形成する段階と、及び
前記チェンバー内にパージガスを供給して未反応酸化剤を除去する段階を含む、請求項8に記載のリチウム二次電池を製造する方法。 - 前記(S22)段階は、
(S21)の結果物をチェンバー内に位置させる段階と、
前記チェンバー内に金属原子を供給する段階と、
前記チェンバー内にパージガスを供給する段階と、
前記チェンバー内に酸化剤を供給し、金属酸化物層を形成する段階と、及び
前記チェンバー内にパージガスを供給し、未反応酸化剤を除去する段階を含む、請求項9に記載のリチウム二次電池を製造する方法。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009266737A (ja) | 2008-04-28 | 2009-11-12 | Panasonic Corp | リチウムイオン二次電池およびその製造方法 |
JP2010160984A (ja) | 2009-01-08 | 2010-07-22 | Nissan Motor Co Ltd | リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池 |
JP2012199216A (ja) | 2010-07-29 | 2012-10-18 | Nec Corp | リチウムイオン二次電池及びその製造方法 |
JP2013519968A (ja) | 2010-02-12 | 2013-05-30 | フォルツ・インテレクチュアル・プロパティ・アー・ゲー | 再充電可能電気化学バッテリセル |
JP2013143375A (ja) | 2012-01-06 | 2013-07-22 | National Taiwan Univ Of Science & Technology | リチウムイオン電池のアノードプロテクタ及びその製造方法 |
JP2018056126A (ja) | 2016-09-27 | 2018-04-05 | 三星電子株式会社Samsung Electronics Co.,Ltd. | 正極、それを含むリチウム空気電池、及び該正極の製造方法 |
JP2018190692A (ja) | 2017-05-11 | 2018-11-29 | 株式会社豊田自動織機 | リチウムドープ負極の製造方法 |
CN110828778A (zh) | 2019-10-30 | 2020-02-21 | 复阳固态储能科技(溧阳)有限公司 | 一种三明治结构预锂化负极及锂离子电池 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08208776A (ja) * | 1995-02-07 | 1996-08-13 | Nippon Kayaku Co Ltd | 樹脂組成物、レンズ用組成物及びその硬化物 |
JP3697812B2 (ja) * | 1997-01-28 | 2005-09-21 | 宇部興産株式会社 | リチウム二次電池の製造方法 |
JP2000182602A (ja) | 1998-12-14 | 2000-06-30 | Fuji Photo Film Co Ltd | 非水二次電池 |
JP4465578B2 (ja) * | 2002-11-15 | 2010-05-19 | ソニー株式会社 | リチウムイオン二次電池用負極およびリチウムイオン二次電池、並びにそれらの製造方法 |
JP5008180B2 (ja) | 2006-02-13 | 2012-08-22 | 日立マクセルエナジー株式会社 | 非水二次電池 |
JP5151188B2 (ja) * | 2006-03-09 | 2013-02-27 | パナソニック株式会社 | 転写用フィルム、およびそれを用いて形成された電気化学素子用の極板ならびにリチウム二次電池 |
KR101297888B1 (ko) * | 2008-01-08 | 2013-08-19 | 주식회사 엘지화학 | 음극, 이의 제조방법, 및 이를 포함하는 리튬 이차 전지 |
KR20130105219A (ko) | 2012-03-15 | 2013-09-25 | 삼성전자주식회사 | 음성 인식을 이용하여 전원을 제어하는 전자 장치 및 이의 전원 제어 방법 |
KR101440843B1 (ko) * | 2013-02-28 | 2014-09-23 | 한국과학기술원 | 나트륨 이차전지용 금속산화물이 코팅된 황화 몰리브덴 전극활물질 및 그 제조방법 |
KR101499787B1 (ko) * | 2013-08-12 | 2015-03-18 | 성균관대학교산학협력단 | 고내열성 분리막, 이의 제조 방법, 및 이를 포함하는 전지 |
US20150162602A1 (en) * | 2013-12-10 | 2015-06-11 | GM Global Technology Operations LLC | Nanocomposite coatings to obtain high performing silicon anodes |
EP3090461A4 (en) * | 2014-01-02 | 2017-06-14 | Applied Materials, Inc. | Solid state electrolyte and barrier on lithium metal and its methods |
CN106663750A (zh) * | 2014-06-23 | 2017-05-10 | 肖特股份有限公司 | 包含片状不连续元件的蓄电系统、片状不连续元件及其制造方法和应用 |
KR101787631B1 (ko) * | 2014-10-16 | 2017-10-18 | 주식회사 엘지화학 | 배리어 층을 포함하는 이차 전지용 양극 활물질 및 이의 제조 방법 |
KR101995064B1 (ko) * | 2015-05-22 | 2019-07-02 | 주식회사 엘지화학 | 다공성 물질의 박막을 포함하는 리튬 이차전지 |
KR102368307B1 (ko) * | 2015-09-16 | 2022-03-02 | 삼성전자주식회사 | 전극 활물질, 이를 포함하는 전극 및 이차전지, 및 상기 전극 활물질의 제조방법 |
KR101984727B1 (ko) | 2016-11-21 | 2019-05-31 | 주식회사 엘지화학 | 전극 및 이를 포함하는 리튬 이차 전지 |
KR101833974B1 (ko) * | 2016-12-23 | 2018-03-02 | 주식회사 포스코 | 리튬 이차 전지용 음극, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
-
2018
- 2018-10-31 KR KR1020180132011A patent/KR102459678B1/ko active IP Right Grant
-
2019
- 2019-09-26 WO PCT/KR2019/012542 patent/WO2020091234A1/ko unknown
- 2019-09-26 US US17/255,670 patent/US20210242457A1/en active Pending
- 2019-09-26 JP JP2021519520A patent/JP7090807B2/ja active Active
- 2019-09-26 CN CN201980039436.2A patent/CN112292771A/zh active Pending
- 2019-09-26 EP EP19878789.7A patent/EP3796428B1/en active Active
- 2019-09-26 PL PL19878789.7T patent/PL3796428T3/pl unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009266737A (ja) | 2008-04-28 | 2009-11-12 | Panasonic Corp | リチウムイオン二次電池およびその製造方法 |
JP2010160984A (ja) | 2009-01-08 | 2010-07-22 | Nissan Motor Co Ltd | リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池 |
JP2013519968A (ja) | 2010-02-12 | 2013-05-30 | フォルツ・インテレクチュアル・プロパティ・アー・ゲー | 再充電可能電気化学バッテリセル |
JP2012199216A (ja) | 2010-07-29 | 2012-10-18 | Nec Corp | リチウムイオン二次電池及びその製造方法 |
JP2013143375A (ja) | 2012-01-06 | 2013-07-22 | National Taiwan Univ Of Science & Technology | リチウムイオン電池のアノードプロテクタ及びその製造方法 |
JP2018056126A (ja) | 2016-09-27 | 2018-04-05 | 三星電子株式会社Samsung Electronics Co.,Ltd. | 正極、それを含むリチウム空気電池、及び該正極の製造方法 |
JP2018190692A (ja) | 2017-05-11 | 2018-11-29 | 株式会社豊田自動織機 | リチウムドープ負極の製造方法 |
CN110828778A (zh) | 2019-10-30 | 2020-02-21 | 复阳固态储能科技(溧阳)有限公司 | 一种三明治结构预锂化负极及锂离子电池 |
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