JP7320019B2 - 非水電解液二次電池およびその製造方法 - Google Patents
非水電解液二次電池およびその製造方法 Download PDFInfo
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- JP7320019B2 JP7320019B2 JP2021067927A JP2021067927A JP7320019B2 JP 7320019 B2 JP7320019 B2 JP 7320019B2 JP 2021067927 A JP2021067927 A JP 2021067927A JP 2021067927 A JP2021067927 A JP 2021067927A JP 7320019 B2 JP7320019 B2 JP 7320019B2
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- aqueous electrolyte
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Description
Lix(M1yM2zMn2-x-y-z)O4-δ・・・(I)
正極活物質としてのLiMn2O4と、正極活物質に対して表1に示す量のオルトリン酸とをN-メチル-2-ピロリドン(NMP)中で混合し、LiMn2O4とオルトリン酸とを接触させて表面処理を行った。この混合物に、導電材としてのカーボンブラック(CB)と、バインダとしてのポリフッ化ビニリデン(PVDF)とを、LiMn2O4:CB:PVDF=90:8:2の質量比となるように添加して、固形分を分散させて正極活物質層形成用スラリーを調製した。ただし、実施例4~8では、リン酸三リチウム(LPO)を、正極活物質に対し表1に示す量となるようにさらに添加して、正極活物質層形成用スラリーを調製した。なお、オルトリン酸にはメルク社製の試薬を用いた。
正極活物質としてのLiMn2O4と、CBと、PVDFとを、LiMn2O4:CB:PVDF=90:8:2の質量比となるようにNMP中で混合し、固形分を分散させて正極活物質層形成用スラリーを調製した。この正極活物質層形成用スラリーを用いた以外は実施例1と同じ方法で、評価用リチウムイオン二次電池を作製し、初期充電処理を行って正極上に被膜を作製した。
正極活物質としてのLiMn2O4と、CBと、PVDFとを、LiMn2O4:CB:PVDF=90:8:2の質量比となるようにNMP中で混合し、固形分を分散させて正極活物質層形成用スラリーを調製した。この正極活物質層形成用スラリーを用いた以外は実施例1と同じ方法で、評価用リチウムイオン二次電池を作製し、初期充電処理を行って正極上に被膜を作製した。
比較例1と同様にして正極活物質層形成用スラリーを調製した。この正極活物質層形成用スラリーを用い、非水電解液にLiBOBを添加しなかった以外は実施例1と同じ方法で、評価用リチウムイオン二次電池を作製し、初期充電処理を行って正極上に被膜を作製した。
初期充電後の放電の際の容量を測定し、これを初期容量とした。初期充電を施した各評価用リチウムイオン二次電池を60℃の環境下に置き、0.5Cで4.2Vまで定電流充電および0.5Cで3.0Vまで定電流放電を1サイクルとする充放電を50サイクル繰り返した。50サイクル後の放電容量を、初期容量と同様の方法で求めた。サイクル特性(容量劣化耐性)の指標として、(充放電50サイクル後の放電容量/初期容量)×100より、容量維持率(%)を求めた。結果を表1に示す。
上記の評価を行った実施例5の評価用リチウムイオン二次電池をアルゴン雰囲気下で解体し、正極を取り出した。この正極をエチルメチルカーボネートで洗浄して電解液を除去し、乾燥した。正極を樹脂包埋し、集束イオンビーム(FIB)で切断して、測定用資料を作製した。これを球面収差補正機能付き走査型透過電子顕微鏡(Cs-STEM)を用いて観察し、STEM-HAADF像を取得した。このSTEM-HAADF像を図3に示す。図3に示すように、分析領域7~11を設定し、これらの領域における構成元素とその含有量(原子%)をエネルギー分散型X線分析(EDX)により求めた。分析領域7~10の測定結果を表2に示す。
30 電池ケース
36 安全弁
42 正極端子
42a 正極集電板
44 負極端子
44a 負極集電板
50 正極シート(正極)
52 正極集電体
52a 正極活物質層非形成部分
54 正極活物質層
60 負極シート(負極)
62 負極集電体
62a 負極活物質層非形成部分
64 負極活物質層
70 セパレータシート(セパレータ)
80 非水電解液
100 リチウムイオン二次電池
Claims (7)
- 正極と、負極と、非水電解液とを備える非水電解液二次電池であって、
前記正極は、正極活物質を含有する正極活物質層を備え、
前記正極活物質は、スピネル型結晶構造を有し、かつMnを含有するリチウム複合酸化物を含み、
前記正極活物質層は、前記正極活物質に対してオルトリン酸を0.05質量%以上1.0質量%以下含有し、
前記負極は、負極活物質を含有する負極活物質層を備え、
前記負極活物質は、黒鉛であり、
前記非水電解液は、フッ素含有リチウム塩を含有し、
前記非水電解液が、オキサラト錯体リチウム塩をさらに含有する、
非水電解液二次電池。 - 前記正極活物質層は、前記正極活物質に対してオルトリン酸を0.1質量%以上0.5質量%以下含有する、請求項1に記載の非水電解液二次電池。
- 正極と、負極と、非水電解液とを備える非水電解液二次電池であって、
前記正極は、正極活物質を含有する正極活物質層を備え、
前記正極活物質は、スピネル型結晶構造を有し、かつMnを含有するリチウム複合酸化物を含み、
前記正極活物質層は、前記正極活物質に対してオルトリン酸を0.05質量%以上1.0質量%以下含有し、
前記負極は、負極活物質を含有する負極活物質層を備え、
前記負極活物質は、黒鉛であり、
前記非水電解液は、フッ素含有リチウム塩を含有し、
前記正極活物質層が、リン酸三リチウムをさらに含有する、
非水電解液二次電池。 - 前記正極活物質層は、前記正極活物質に対してオルトリン酸を0.1質量%以上0.5質量%以下含有する、請求項3に記載の非水電解液二次電池。
- 請求項1または2に記載の非水電解液二次電池を用意する工程と、
前記用意した非水電解液二次電池に、4.7V以上の電圧で初期充電を施す工程と、
を包含する、正極活物質の表面に被膜を有する非水電解液二次電池の製造方法。 - 請求項3または4に記載の非水電解液二次電池を用意する工程と、
前記用意した非水電解液二次電池に、4.7V以上の電圧で初期充電を施す工程と、
を包含する、正極活物質の表面に被膜を有する非水電解液二次電池の製造方法。 - 正極と、負極と、非水電解液とを備える非水電解液二次電池であって、
前記正極は、正極活物質を含有する正極活物質層を備え、
前記正極活物質は、スピネル型結晶構造を有し、かつMnを含有するリチウム複合酸化物を含み、
前記負極は、負極活物質を含有する負極活物質層を備え、
前記負極活物質は、黒鉛であり、
前記非水電解液は、フッ素含有リチウム塩を含有し、
前記正極活物質は、その表面に被膜を有し、
前記被膜の少なくとも一部が、第1層と、前記第1層上に位置する第2層と、を備える複層構造を有し、
前記第1層において、走査型透過電子顕微鏡/エネルギー分散型X線分析によって求まるP元素とF元素の合計含有量(原子%)に対するP元素の含有量(原子%)の割合が、67%以上であり、
前記第2層において、走査型透過電子顕微鏡/エネルギー分散型X線分析によって求まるP元素とF元素の合計含有量(原子%)に対するF元素の含有量(原子%)の割合が、38%以上である、
非水電解液二次電池。
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