JP2023539230A - リチウム二次電池の正極用添加剤、この製造方法及びこれを含むリチウム二次電池の正極 - Google Patents
リチウム二次電池の正極用添加剤、この製造方法及びこれを含むリチウム二次電池の正極 Download PDFInfo
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- JP2023539230A JP2023539230A JP2023513237A JP2023513237A JP2023539230A JP 2023539230 A JP2023539230 A JP 2023539230A JP 2023513237 A JP2023513237 A JP 2023513237A JP 2023513237 A JP2023513237 A JP 2023513237A JP 2023539230 A JP2023539230 A JP 2023539230A
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- positive electrode
- additive
- secondary battery
- lithium secondary
- lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 97
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- 230000000996 additive effect Effects 0.000 title claims abstract description 81
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- 150000003624 transition metals Chemical class 0.000 claims description 15
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- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
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Abstract
Description
本発明は、リチウム遷移金属酸化物、Li3PO4、Li5AlO4及びLi3BO3を含み、前記リチウム遷移金属酸化物は、アルミニウムがドーピングされた形態であるリチウム二次電池の正極用添加剤を提供する。
Li2Ni1-xAlxO2
(ここで、xは0.001~0.005である。)
本発明は、前述したリチウム二次電池の正極用添加剤の製造方法であって、(1)遷移金属ソース物質、リチウムソース物質、リンソース物質、アルミニウムソース物質及びホウ素ソース物質を混合して混合物を製造する工程;及び(2)前記混合物を熱処理する段階を含むリチウム二次電池の正極用添加剤の製造方法を提供する。
本発明の第3側面によれば、
本発明は、リチウム遷移金属酸化物、Li3PO4、Li5AlO4及びLi3BO3を含むリチウム二次電池の正極用添加剤を提供する。
Li2Ni1-xAlxO2
(ここで、xは0.001~0.005、具体的に0.0015~0.004、より具体的に0.002~0.003である。)
本発明は、前述したリチウム二次電池の正極用添加剤の製造方法を提供する。前期製造方法は、(1)遷移金属ソース物質、リチウムソース物質、リンソース物質、アルミニウムソース物質、及びホウ素ソース物質を混合して混合物を製造する段階;及び(2)前記混合物を熱処理する段階を含む。
本発明は、正極、負極、分離膜及び電解質を含むリチウム二次電池を提供する。前記リチウム二次電池において正極と負極とは対向して位置し、分離膜は正極と負極との間に介在する。正極、負極及び分離膜の電極組立体は電池容器に収納され、電池容器は電解質で満たされる。
NiO、Li2O、B(OH)3、Al(OH)3及び(NH4)2HPO4を混合した後、製造された混合物を300℃で10時間熱処理して添加剤を製造した。混合時、NiO及びLi2Oの含有量は、Li2Oのモル/NiOのモルが2.03となるように調節し、B(OH)3の含有量は、BがNiOとLi2Oの総重量を基準として1,500ppmとなるように調節した。また、Al(OH)3の含有量は、NiOのモルを基準として0.03モル%となるように調節し、(NH4)2HPO4の含有量は、PがNiOとLi2Oの総重量を基準として5.5重量%となるように調節した。
実施例1と異なり、B(OH)3を用いず、NiO、Li2O、Al(OH)3及び(NH4)2HPO4を混合した後、製造された混合物を700℃で10時間熱処理して添加剤を製造した。混合時、NiO、Li2O、Al(OH)3及び(NH4)2HPO4の含有量は実施例1と同様に調節した。
添加剤として、Li2NiO2及びLi5AlO4を含む製品(製造社:ポスコケミカル、製品名:DN20)を準備した。
添加剤として、Li2NiO2及びLi3PO4を含む製品(製造社:ポスコケミカル、製品名:DN40)を準備した。
実験例1:添加剤の構成成分分析
X線回折計装置(製造社:BRUKER NANO、製品名:Bruker D8 Advance)を用いてX線回折分析法で実施例1と比較例1~3の添加剤の構成成分を分析し、下記表1に示す。
実施例1及び比較例1~3により製造された添加剤の性能を確認するためにリチウム二次電池を製造した。具体的に、実施例1と比較例1~5のそれぞれの添加剤を正極活物質であるLiNi0.83Co0.11Mn0.06O2と9:1(正極活物質:添加剤)の重量比で混合後、N‐メチルピロリドン溶媒中でカーボンブラック導電材とPVDFバインダーと85:10:5(添加剤+正極活物質:導電材:バインダー)の重量比で混合して正極活物質スラリーを製造し、これをアルミニウム集電体(20μm)の一面に塗布した後(ローディング量:0.2~0.3mg/25cm2)、130℃で20分以上乾燥後、空隙率26%となるように1~2回圧延して正極を製造した。
製造されたそれぞれのリチウム二次電池について、45℃で10時間保管後、2.5~4.2V領域で0.1C(Cレート)で充放電して形成した後、SOC0状態で初期形成ガス発生量を測定した。この後、0.33C(Cレート)で10、30、50サイクル毎にセルのガス発生変化量をアルキメデス原理を用いて体積で測定した。測定結果を下記表2に示す。
製造されたそれぞれのリチウム二次電池について、45℃で10時間保管後、2.5~4.2V領域で0.1C(Cレート)で充電させてSOC100にセッティングした後、60℃の高温チャンバーで4週間保管し、1週間毎にセルのガス発生変化量をアルキメデスの原理を用いて測定した。測定結果を下記表3に示す。
前述した実施例1の添加剤を用いたリチウム二次電池について、リチウム二次電池の製造時、正極活物質と添加剤の混合重量比を100:0、90:10、80:20、0:100にそれぞれ調節してリチウム二次電池を製造した。製造されたそれぞれのリチウム二次電池について、45℃で10時間保管後、2.5~4.2V領域で0.1C(Cレート)で充・放電時の初期充・放電容量を測定し、下記表4に示す。
Claims (13)
- リチウム遷移金属酸化物、Li3PO4、Li5AlO4及びLi3BO3を含み、
前記リチウム遷移金属酸化物は、アルミニウムがドーピングされた形態であることを特徴とするリチウム二次電池の正極用添加剤。 - 前記リチウム遷移金属酸化物は、下記化学式1で表され、
[化学式1]
Li2Ni1-xAlxO2
xは0.001~0.005であることを特徴とする請求項1に記載のリチウム二次電池の正極用添加剤。 - 前記リチウム遷移金属酸化物は、添加剤の総重量を基準として75~90重量%で含まれることを特徴とする請求項1または2に記載のリチウム二次電池の正極用添加剤。
- 前記Li3PO4は、添加剤の総重量を基準として1~10重量%で含まれることを特徴とする請求項1から3のいずれか一項に記載のリチウム二次電池の正極用添加剤。
- 前記Li5AlO4は、添加剤の総重量を基準として0.5~5重量%で含まれることを特徴とする請求項1から4のいずれか一項に記載のリチウム二次電池の正極用添加剤。
- 前記Li3BO3は、添加剤の総重量を基準として0.1~3重量%で含まれることを特徴とする請求項1から5のいずれか一項に記載のリチウム二次電池の正極用添加剤。
- 前記Li3BO3の一部は、リチウム遷移金属酸化物にコーティングされた状態で存在することを特徴とする請求項1から6のいずれか一項に記載のリチウム二次電池の正極用添加剤。
- 前記リチウム二次電池の正極用添加剤は、NiOをさらに含むことを特徴とする請求項1から7のいずれか一項に記載のリチウム二次電池の正極用添加剤。
- 前記NiOは、添加剤の総重量を基準として5~15重量%で含まれることを特徴とする請求項8に記載のリチウム二次電池の正極用添加剤。
- 請求項1から9のいずれか一項に記載のリチウム二次電池の正極用添加剤の製造方法であって、
(1)遷移金属ソース物質、リチウムソース物質、リンソース物質、アルミニウムソース物質及びホウ素ソース物質を混合して混合物を製造する段階、及び
(2)前記混合物を熱処理する段階を含むリチウム二次電池の正極用添加剤の製造方法。 - 前記(1)の段階において、遷移金属ソース物質はNiOであり、リチウムソース物質はLi2O、LiOHまたはLi2CO3であり、リンソース物質は(NH4)2HPO4であり、アルミニウムソース物質はAl(OH)3であり、ホウ素ソース物質はB(OH)3であることを特徴とする請求項10に記載のリチウム二次電池の正極用添加剤の製造方法。
- 前記(2)の段階において、混合物を300~700℃で10~32時間熱処理することを特徴とする請求項10または11に記載のリチウム二次電池の正極用添加剤の製造方法。
- 請求項1から9のいずれか一項に記載のリチウム二次電池の正極用添加剤及び正極活物質を含み、
前記リチウム二次電池の正極用添加剤は、正極活物質100重量部を基準として10~40重量部で含まれることを特徴とするリチウム二次電池の正極。
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KR20210156630A (ko) | 2020-06-18 | 2021-12-27 | 김태종 | 스마트 온열 착용물 및 이의 자동 온도 조절 방법 |
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