JP3721678B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary battery Download PDFInfo
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- JP3721678B2 JP3721678B2 JP33513096A JP33513096A JP3721678B2 JP 3721678 B2 JP3721678 B2 JP 3721678B2 JP 33513096 A JP33513096 A JP 33513096A JP 33513096 A JP33513096 A JP 33513096A JP 3721678 B2 JP3721678 B2 JP 3721678B2
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Description
【０００１】
【技術分野】
本発明は，例えばコードレス電源，電気自動車等における電源として用いられる，充電により再利用可能な，非水電解液二次電池に関する。
【０００２】
【従来技術】
リチウム等を吸蔵，放出できる正極及び負極と非水電解液とからなる非水電解液二次電池は，高電圧で，高エネルギー密度を有する。そのため，近年，コードレス電源，小型携帯用電源，或いは電気自動車等における電源としての利用が期待されている。そのため，非水電解液二次電池の電解質として，電気化学的，熱的に安定な有機リチウム塩電解質の実用化が望まれている。
【０００３】
【解決しようとする課題】
しかしながら，上記従来の非水電解液二次電池においては，電解質として有機リチウム塩を用いた場合には，３．５Ｖ以上の高い電圧になると，正極集電体の溶出が起こり，集電性が劣化し，電気容量が急激に低下するという問題がある。
【０００４】
本発明はかかる従来の問題点に鑑み，正極集電体の集電性が高く，電気容量の劣化を抑制することができる非水電解液二次電池を提供しようとするものである。
【０００５】
【課題の解決手段】
第１の発明は，リチウムを吸蔵，放出できる正極と，リチウム金属，リチウム合金若しくはリチウムを吸蔵，放出できる物質又は導電性物質からなる負極と，上記正極と負極との間に設けたセパレータと，該セパレータに含浸させた非水電解液と，電池容器とを有する非水電解液二次電池において，
上記正極は，正極活物質と，正極集電体とからなり，
上記正極集電体は，クマリン類を少なくとも含有する表面保護剤により被覆されていることを特徴とする非水電解液二次電池である（請求項１）。
また，第２の発明として，リチウムを吸蔵，放出できる正極と，リチウム金属，リチウム合金若しくはリチウムを吸蔵，放出できる物質又は導電性物質からなる負極と，上記正極と負極との間に設けたセパレータと，該セパレータに含浸させた非水電解液と，電池容器とを有する非水電解液二次電池において，
上記正極は，正極活物質と，正極集電体とからなり，
上記非水電解液は，Ｌｉ（ＣＦ 3 ＳＯ 2 ） 2 Ｎ若しくはＬｉ（ＣＦ 3 ＳＯ 2 ） 3 Ｃの少なくとも１種からなるリチウム塩，又は該リチウム塩の誘導体から選ばれる１種又は２種以上を含み，
上記正極集電体は，トリアゾール類を少なくとも含有する表面保護剤により被覆されていることを特徴とする非水電解液二次電池がある（請求項４）。
【０００６】
上記両発明においては，正極集電体に上記のクマリン類又はトリアゾール類からなる複素環式化合物を含有する表面保護剤が施されている。このクマリン類又はトリアゾール類は，正極集電体と非水電解液中の電解質との反応を抑制する。そのため，正極集電体の劣化を防止でき，正極集電体の集電性を高くすることができる。また，電気容量の劣化を抑制することができる。
【０００７】
即ち，トリアゾール類又はクマリン類は，正極集電体の劣化をより効果的に抑制でき，優れた集電性を発揮することができる。また，電気容量の劣化を一層抑制できる。
【０００８】
また，上記トリアゾール類は，１，２，４−トリアゾール，３−アミノ−１，２，４−トリアゾール，１，２，３−ベンゾトリアゾールから選ばれる１種又は２種以上であることが好ましい。
【０００９】
また，上記クマリン類は，クマリン，クマリン−３−カルボン酸，４−メチルウンベリフェロン，３−アセチルクマリン，及び７−アミノ−４−（トリフルオロメチル）クマリンのグループから選ばれる１種又は２種以上であることが好ましい。これにより，正極集電体の劣化を更に抑制できる。
【００１０】
また，上記非水電解液は，表面保護剤としてクマリン類を用いる場合には，ＬｉＣＦ3ＳＯ3，Ｌｉ（ＣＦ3ＳＯ2）2Ｎ若しくはＬｉ（ＣＦ3ＳＯ2）3Ｃの少なくとも１種からなるリチウム塩，又は該リチウム塩の誘導体から選ばれる１種又は２種以上を含むことが好ましい。これにより，電気化学的，熱的に安定な電解質を得ることができる。
一方，表面保護剤としてトリアゾール類を用いる場合には，非水電解液は，Ｌｉ（ＣＦ 3 ＳＯ 2 ） 2 Ｎ若しくはＬｉ（ＣＦ 3 ＳＯ 2 ） 3 Ｃの少なくとも１種からなるリチウム塩，又は該リチウム塩の誘導体から選ばれる１種又は２種以上を含むことが好ましい。これにより，電気化学的，熱的に安定な電解質を得ることができる。
【００１１】
【発明の実施の形態】
実施形態例１
本発明の実施形態例に係る非水電解液二次電池について，図１を用いて説明する。
非水電解液二次電池９は，図１に示すごとく，リチウムを吸蔵，放出できる正極２１と，リチウム金属，リチウム合金若しくはリチウムを吸蔵，放出できる物質又は導電性物質からなる負極２２と，正極２１と負極２２との間に設けたセパレータ３と，該セパレータに含浸させた非水電解液１と，電池容器５とを有している。
【００１２】
正極２１は，正極活物質２１１と，正極集電体２１２とからなる。正極集電体２１２は，表面保護剤２１０により被覆されている。表面保護剤２１０は，下記の「化１」に示す１，２，４−トリアゾールである。
【００１３】
【化１】
上記表面保護剤を正極集電体の表面に被覆するに当たっては，まず，エチレンカーボネートとジメトキシエタンとの等容積混合溶媒に１，２，４−トリアゾールを０．０３ｍｏｌ・ｄｍ-3溶解して，前処理液を調製する。次いで，前処理液の中に，正極集電体に正極活物質をプレスしたものを浸漬する。正極活物質２１２としては，ＬｉＭｎ2 Ｏ4 を合剤としてシート状に成形したものを用いる。上記正極集電体としては円板状のアルミニウム箔を用いる。これにより，正極活物質から表面保護剤が浸透して，正極活物質が正極集電体の表面を被覆する。
【００１５】
負極２２は，負極活物質２２１と，円板状の負極集電体２２２とからなる。負極活物質２２１としてはリチウム箔を用い，負極集電体２２２としては銅箔を用いる。
非水電解液１は，エチレンカーボネートとジメトキシエタンとの等容積混合溶媒に，電解質としてのＬｉ（ＣＦ3 ＳＯ2 ）2 Ｎを１ｍｏｌｄｍ-3濃度となるように溶解したものである。
【００１６】
セパレータ３は，略円板状のポリエチレン製フィルムである。電池容器５は，円筒状の正極側容器５１と，円筒状の負極側容器５２と，両者を電気絶縁すると共に固定するためのリング状のガスケット５３とからなる。正極側容器５１及び負極側容器５２はステンレス鋼を，ガスケット５３はポリプロピレンを用いる。
本例の非水電解液二次電池９は，コイン型非水電解液二次電池である。
【００１７】
実施形態例２
本例の非水電解液二次電池は，表面保護剤として，下記の「化２」に示す３−アミノ−１，２，４−トリアゾールを用いる点が，上記実施形態例１と相違する。
上記表面保護剤を正極集電体の表面に被覆するに当たっては，エチレンカーボネートとジメトキシエタンとの等容積混合溶媒に３−アミノ−１，２，４−トリアゾールを０．０３ｍｏｌ・ｄｍ-3溶解して，前処理液を調製する。前処理液の中に，正極集電体に正極活物質をプレスしたものを浸漬する。これにより，正極活物質から表面保護剤が浸透して，表面保護剤が正極集電体の表面を覆う。
その他は，実施形態例１と同様である。
【００１８】
【化２】
実施形態例３
本例の非水電解液二次電池は，表面保護剤として，下記の「化３」に示す１，２，３−ベンゾトリアゾールを用いる点が，上記実施形態例１と相違する。
上記表面保護剤を正極集電体の表面に被覆するに当たっては，エチレンカーボネートとジメトキシエタンとの等容積混合溶媒に１，２，３−ベンゾトリアゾールを０．０３ｍｏｌ・ｄｍ-3溶解して，前処理液を調製する。前処理液の中に，正極集電体に正極活物質をプレスしたものを浸漬する。これにより，正極活物質から表面保護剤が浸透して，表面保護剤が正極集電体の表面を覆う。
その他は，実施形態例１と同様である。
【００２０】
【化３】
実施形態例４
本例の非水電解液二次電池は，表面保護剤として，下記の「化４」に示すクマリンを用いる点が，上記実施形態例１と相違する。
上記表面保護剤を正極集電体の表面に被覆するに当たっては，エチレンカーボネートとジメトキシエタンとの等容積混合溶媒にクマリンを０．０３ｍｏｌ・ｄｍ-3溶解して，前処理液を調製する。前処理液の中に，正極集電体に正極活物質をプレスしたものを浸漬する。これにより，正極活物質から表面保護剤が浸透して，表面保護剤が正極集電体の表面を覆う。
その他は，実施形態例１と同様である。
【００２２】
【化４】
（比較例）
本例の非水電解液二次電池は，正極集電体の表面を表面保護剤により被覆していない点が，実施形態例１と相違する。
【００２４】
（実験例）
上記実施例１〜４及び比較例の非水電解液二次電池について，充放電試験を行い，サイクル特性を評価した。
各非水電解質二次電池の充放電条件は，充電電流０．６ｍＡ・ｃｍ-2，充電上限電圧４．２Ｖ，充電時間８時間，放電電流０．６ｍＡ・ｃｍ-2，放電下限電圧３．５Ｖとした。
測定結果を表１及び図２に示した。表１には，各電池の３０サイクル後の放電容量の変化を示した。図２には，実施形態例１及び比較例の電池について，初期容量を１としたときの放電容量の変化を例示した。
【００２５】
【表１】
表１及び図２に示すように，実施形態例１〜４は，放電容量の変化が少なく，サイクル特性が優れていた。この原因は，正極集電体を予め表面保護剤により被覆しておくことにより，表面保護剤が，正極集電体と電解質の分解物との反応に対する阻害剤として作用する。そのため，正極集電体表面に見かけ上安定な不導体被膜を形成し，アルミニウムの溶出が抑制されたためであると考えられる。
【００２７】
一方，比較例は，放電容量が著しく低下した。この原因は，３．５Ｖ付近で電解質であるＬｉ（ＣＦ3 ＳＯ2 ）2 Ｎの分解が生じ，この分解物と正極集電体であるアルミニウムとが反応し，アルミニウムが溶出してしまうため，正極集電体の集電性が劣化し，電気容量の低下を引き起こしたものと考えられる。
【００２８】
また，実施形態例２〜４の電池についても，上記と同様にサイクル特性を評価した（表１）。その結果，これらの電池についても，多少差はあるものの，実施形態例１と同様に高いサイクル特性が得られた。
以上より，正極集電体の表面保護剤として，１，２，４−トリアゾールが優れているとともに，３−アミノ−１，２，４−トリアゾール，１，２，３−ベンゾトリアゾール及びクマリンも有用であることがわかる。
【００２９】
なお，表面保護剤の濃度は，０．０３ｍｏｌ・ｄｍ-3で評価したが，他の濃度でも，正極集電体の表面を保護できる濃度であれば，上記各種実施形態例と同様の効果が得られると考えられる。
【００３０】
また，本発明においては，表面保護剤を正極集電体の表面に被覆するに当たっては，正極集電体を正極活物質にプレスしたプレス品を，表面保護剤を溶解させた前処理液に浸漬させているが，上記プレス品の表面に上記前処理液を塗布してもよい。また，正極集電体だけを上記前処理液に浸漬してもよいし，正極集電体の表面に上記前処理液を塗布してもよい。
また，上記プレス品又は正極集電体を，表面保護剤の存在する雰囲気中に載置してもよい。
【００３１】
また，正極集電体として，アルミニウム，チタン，ニッケル等を用いることができる。正極活物質として，Ｌｉ・Ｍｎ複合酸化物，Ｌｉ・Ｃｏ複合酸化物等のリチウム化合物等を用いることができる。負極集電体として，銅等を用いることができる。負極活物質として，リチウム金属，リチウム合金，炭素質材料等を用いることができる。
【００３２】
非水電解液の中の非水溶媒としては，エチレンカーボネート，プロピレンカーボネート等の環状エステル類，ジエチルカーボネート，ジメチルカーボネート，エチル・メチルカーボネートの鎖状エステル類，又は１，２−ジメトキシエタン等の鎖状エーテル類のグループから選ばれる１種又は２種以上を用いることができる。
【図面の簡単な説明】
【図１】実施形態例１の非水電解液二次電池の断面図。
【図２】実施形態例１及び比較例の非水電解液二次電池についての放電容量の変化を示す線図。
【符号の説明】
１．．．非水電解液，
２１．．．正極，
２１０．．．表面保護剤，
２１１．．．正極活物質，
２１２．．．正極集電体，
２２．．．負極，
３．．．セパレータ，
５．．．電池容器，
９．．．非水電解液二次電池，[0001]
【Technical field】
The present invention relates to a non-aqueous electrolyte secondary battery that can be reused by charging, for example, used as a power source in a cordless power source, an electric vehicle, or the like.
[0002]
[Prior art]
A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium and a non-aqueous electrolyte has a high voltage and a high energy density. Therefore, in recent years, it is expected to be used as a cordless power source, a small portable power source, or a power source in an electric vehicle. Therefore, the practical application of an electrochemically and thermally stable organic lithium salt electrolyte is desired as the electrolyte for non-aqueous electrolyte secondary batteries.
[0003]
[Problems to be solved]
However, in the conventional non-aqueous electrolyte secondary battery, when an organic lithium salt is used as the electrolyte, when the voltage becomes higher than 3.5 V, the elution of the positive electrode current collector occurs and the current collecting property is reduced. There is a problem that it deteriorates and the electric capacity rapidly decreases.
[0004]
In view of the conventional problems, the present invention is intended to provide a non-aqueous electrolyte secondary battery in which the current collector of the positive electrode current collector is high and the deterioration of the electric capacity can be suppressed.
[0005]
[Means for solving problems]
The first invention includes a positive electrode capable of inserting and extracting lithium, a negative electrode made of a lithium metal, a lithium alloy or a substance capable of inserting and extracting lithium or a conductive material, a separator provided between the positive electrode and the negative electrode, In a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte impregnated in the separator and a battery container,
The positive electrode comprises a positive electrode active material and a positive electrode current collector,
The positive electrode current collector is a non-aqueous electrolyte secondary battery characterized in that it is coated with a surface protective agent containing at least coumarins (Claim 1) .
According to a second aspect of the invention, a positive electrode capable of inserting and extracting lithium, a negative electrode made of lithium metal, a lithium alloy or a substance capable of inserting and extracting lithium or a conductive material, and a separator provided between the positive electrode and the negative electrode A non-aqueous electrolyte secondary battery having a non-aqueous electrolyte impregnated in the separator and a battery container,
The positive electrode comprises a positive electrode active material and a positive electrode current collector,
The non-aqueous electrolyte is one or more selected from a lithium salt composed of at least one of Li (CF 3 SO 2 ) 2 N or Li (CF 3 SO 2 ) 3 C, or a derivative of the lithium salt. Including
There is a nonaqueous electrolyte secondary battery in which the positive electrode current collector is coated with a surface protective agent containing at least triazoles (claim 4).
[0006]
In both the above inventions, the positive electrode current collector is provided with a surface protective agent containing a heterocyclic compound comprising the above-mentioned coumarins or triazoles . The coumarins or triazoles suppress the reaction between the positive electrode current collector and the electrolyte in the nonaqueous electrolytic solution. Therefore, it is possible to prevent the positive electrode current collector from being deteriorated and to increase the current collecting property of the positive electrode current collector. Further, it is possible to suppress deterioration of the electric capacity.
[0007]
That is, triazoles or click Marin class can more effectively suppress the deterioration of the positive electrode current collector, it is possible to exhibit excellent current collecting property. In addition, the deterioration of electric capacity can be further suppressed.
[0008]
The upper SL triazoles, 1,2,4-triazole, 3-amino-1,2,4 Toriazo Le, one or more selected 1,2,3- benzotriazole Le whether et al Preferably there is.
[0009]
The upper SL coumarins, coumarin, coumarin-3-carboxylic acid, 4-methylumbelliferone, 3-acetyl coumarin, and 7-amino-4-one selected from the group of (trifluoromethyl) coumarin, or Two or more are preferable. Thereby, deterioration of the positive electrode current collector can be further suppressed.
[0010]
The upper KiHisui electrolyte, in the case of using coumarins as a surface protective agent, LiCF 3 SO 3, Li ( CF 3 SO 2) 2 N or Li (CF 3 SO 2) 3 C at least one It is preferable that 1 type, or 2 or more types chosen from the lithium salt which consists of, or the derivative | guide_body of this lithium salt is included. Thereby, an electrochemically and thermally stable electrolyte can be obtained.
On the other hand, when triazoles are used as the surface protective agent, the non-aqueous electrolyte is a lithium salt composed of at least one of Li (CF 3 SO 2 ) 2 N or Li (CF 3 SO 2 ) 3 C, or It is preferable to include one or more selected from lithium salt derivatives. Thereby, an electrochemically and thermally stable electrolyte can be obtained.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Embodiment 1
A nonaqueous electrolyte secondary battery according to an embodiment of the present invention will be described with reference to FIG.
As shown in FIG. 1, the non-aqueous electrolyte secondary battery 9 includes a
[0012]
The
[0013]
[Chemical 1]
In coating the surface protective agent on the surface of the positive electrode current collector, first, 0.03 mol · dm −3 of 1,2,4-triazole was dissolved in an equal volume mixed solvent of ethylene carbonate and dimethoxyethane, Prepare a pretreatment solution. Next, a positive electrode current collector pressed with a positive electrode active material is immersed in the pretreatment liquid. As the positive electrode
[0015]
The
The nonaqueous electrolytic solution 1 is obtained by dissolving Li (CF 3 SO 2 ) 2 N as an electrolyte in an equal volume mixed solvent of ethylene carbonate and dimethoxyethane so as to have a concentration of 1 moldm −3 .
[0016]
The separator 3 is a substantially disc-shaped polyethylene film. The
The nonaqueous electrolyte secondary battery 9 of this example is a coin-type nonaqueous electrolyte secondary battery.
[0017]
Embodiment 2
The non-aqueous electrolyte secondary battery of this example is different from the first embodiment in that 3-amino-1,2,4-triazole shown in the following “Chemical Formula 2” is used as a surface protective agent.
In coating the surface protective agent on the surface of the positive electrode current collector, 0.03 mol · dm −3 of 3-amino-1,2,4-triazole was dissolved in an equal volume mixed solvent of ethylene carbonate and dimethoxyethane. Prepare the pretreatment solution. In the pretreatment liquid, a positive electrode current collector pressed with a positive electrode active material is immersed. Thereby, the surface protective agent penetrates from the positive electrode active material, and the surface protective agent covers the surface of the positive electrode current collector.
Others are the same as in the first embodiment.
[0018]
[Chemical formula 2]
Embodiment 3
The nonaqueous electrolyte secondary battery of this example is different from the first embodiment in that 1,2,3-benzotriazole shown in the following “Chemical Formula 3” is used as a surface protective agent.
In coating the surface of the positive electrode current collector with the above surface protective agent, 0.03 mol · dm −3 of 1,2,3-benzotriazole was dissolved in an equal volume mixed solvent of ethylene carbonate and dimethoxyethane. Prepare a treatment solution. In the pretreatment liquid, a positive electrode current collector pressed with a positive electrode active material is immersed. Thereby, the surface protective agent penetrates from the positive electrode active material, and the surface protective agent covers the surface of the positive electrode current collector.
Others are the same as in the first embodiment.
[0020]
[Chemical 3]
Embodiment 4
The nonaqueous electrolyte secondary battery of this example is different from the first embodiment in that a coumarin represented by the following “Chemical Formula 4” is used as a surface protective agent.
In coating the surface protective agent on the surface of the positive electrode current collector, 0.03 mol · dm −3 of coumarin is dissolved in an equal volume mixed solvent of ethylene carbonate and dimethoxyethane to prepare a pretreatment liquid. In the pretreatment liquid, a positive electrode current collector pressed with a positive electrode active material is immersed. Thereby, the surface protective agent penetrates from the positive electrode active material, and the surface protective agent covers the surface of the positive electrode current collector.
Others are the same as in the first embodiment.
[0022]
[Formula 4]
(Comparative example)
The non-aqueous electrolyte secondary battery of this example is different from Embodiment 1 in that the surface of the positive electrode current collector is not covered with a surface protective agent.
[0024]
(Experimental example)
About the non-aqueous electrolyte secondary battery of the said Examples 1-4 and the comparative example, the charge / discharge test was done and cycling characteristics were evaluated.
The charge / discharge conditions of each non-aqueous electrolyte secondary battery are as follows: charge current 0.6 mA · cm −2 , charge upper limit voltage 4.2 V, charge time 8 hours, discharge current 0.6 mA · cm −2 , discharge lower limit voltage 3. The voltage was 5V.
The measurement results are shown in Table 1 and FIG. Table 1 shows the change in discharge capacity after 30 cycles of each battery. FIG. 2 illustrates the change in discharge capacity when the initial capacity is set to 1 for the batteries of Example 1 and the comparative example.
[0025]
[Table 1]
As shown in Table 1 and FIG. 2, Embodiment Examples 1 to 4 had little change in discharge capacity and excellent cycle characteristics. This is because the positive electrode current collector is previously coated with a surface protective agent, so that the surface protective agent acts as an inhibitor for the reaction between the positive electrode current collector and the decomposition product of the electrolyte. Therefore, it is considered that an apparently stable non-conductive film was formed on the surface of the positive electrode current collector, and the elution of aluminum was suppressed.
[0027]
On the other hand, the discharge capacity of the comparative example was significantly reduced. The cause is that decomposition of Li (CF 3 SO 2 ) 2 N as an electrolyte occurs near 3.5 V, and this decomposition product reacts with aluminum as a positive electrode current collector, so that aluminum is eluted. It is considered that the current collecting property of the positive electrode current collector deteriorated and the electric capacity was reduced.
[0028]
Further, the cycle characteristics of the batteries of Embodiment Examples 2 to 4 were also evaluated in the same manner as described above (Table 1). As a result, high cycle characteristics were obtained for these batteries as well as the first embodiment, although there were some differences.
As described above, 1,2,4-triazole is excellent as a surface protecting agent for the positive electrode current collector, and 3-amino-1,2,4-triazole, 1,2,3-benzotriazole and coumarin are also useful. It can be seen that it is.
[0029]
Although the concentration of the surface protective agent was evaluated at 0.03 mol · dm −3 , the same effects as those of the above-described various embodiments can be obtained at other concentrations as long as the concentration can protect the surface of the positive electrode current collector. It is thought that it is obtained.
[0030]
In the present invention, in order to coat the surface of the positive electrode current collector with the surface protective agent, a press product obtained by pressing the positive electrode current collector into the positive electrode active material is immersed in a pretreatment solution in which the surface protective agent is dissolved. However, the pretreatment liquid may be applied to the surface of the pressed product. Further, only the positive electrode current collector may be immersed in the pretreatment liquid, or the pretreatment liquid may be applied to the surface of the positive electrode current collector.
Further, the press product or the positive electrode current collector may be placed in an atmosphere in which a surface protective agent is present.
[0031]
In addition, aluminum, titanium, nickel, or the like can be used as the positive electrode current collector. As the positive electrode active material, lithium compounds such as Li / Mn composite oxide and Li / Co composite oxide can be used. Copper or the like can be used as the negative electrode current collector. As the negative electrode active material, lithium metal, lithium alloy, carbonaceous material, or the like can be used.
[0032]
Nonaqueous solvents in the nonaqueous electrolyte include cyclic esters such as ethylene carbonate and propylene carbonate, chain esters such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and chains such as 1,2-dimethoxyethane. 1 type (s) or 2 or more types selected from the group of the shape ethers can be used.
[Brief description of the drawings]
1 is a cross-sectional view of a nonaqueous electrolyte secondary battery according to Embodiment 1;
FIG. 2 is a diagram showing a change in discharge capacity for the nonaqueous electrolyte secondary batteries of Embodiment 1 and Comparative Example.
[Explanation of symbols]
1. . . Non-aqueous electrolyte,
21. . . Positive electrode,
210. . . Surface protection agent,
211. . . Cathode active material,
212. . . Positive electrode current collector,
22. . . Negative electrode,
3. . . Separator,
5. . . Battery container,
9. . . Non-aqueous electrolyte secondary battery,
Claims (5)
上記正極は，正極活物質と，正極集電体とからなり，
上記正極集電体は，クマリン類を少なくとも含有する表面保護剤により被覆されていることを特徴とする非水電解液二次電池。A positive electrode capable of inserting and extracting lithium, a negative electrode made of a lithium metal, a lithium alloy or a substance capable of inserting and extracting lithium or a conductive material, a separator provided between the positive electrode and the negative electrode, and the separator impregnated In a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte and a battery container,
The positive electrode comprises a positive electrode active material and a positive electrode current collector,
The non-aqueous electrolyte secondary battery, wherein the positive electrode current collector is coated with a surface protective agent containing at least coumarins .
上記正極は，正極活物質と，正極集電体とからなり，
上記非水電解液は，Ｌｉ（ＣＦ 3 ＳＯ 2 ） 2 Ｎ若しくはＬｉ（ＣＦ 3 ＳＯ 2 ） 3 Ｃの少なくとも１種からなるリチウム塩，又は該リチウム塩の誘導体から選ばれる１種又は２種以上を含み，
上記正極集電体は，トリアゾール類を少なくとも含有する表面保護剤により被覆されていることを特徴とする非水電解液二次電池。 A positive electrode capable of inserting and extracting lithium, a negative electrode made of a lithium metal, a lithium alloy or a substance capable of inserting and extracting lithium or a conductive material, a separator provided between the positive electrode and the negative electrode, and the separator impregnated In a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte and a battery container,
The positive electrode comprises a positive electrode active material and a positive electrode current collector,
The non-aqueous electrolyte is one or more selected from a lithium salt composed of at least one of Li (CF 3 SO 2 ) 2 N or Li (CF 3 SO 2 ) 3 C, or a derivative of the lithium salt. Including
The non-aqueous electrolyte secondary battery , wherein the positive electrode current collector is coated with a surface protective agent containing at least triazoles .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33513096A JP3721678B2 (en) | 1996-11-29 | 1996-11-29 | Non-aqueous electrolyte secondary battery |
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| JP33513096A JP3721678B2 (en) | 1996-11-29 | 1996-11-29 | Non-aqueous electrolyte secondary battery |
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| JPH10162833A JPH10162833A (en) | 1998-06-19 |
| JP3721678B2 true JP3721678B2 (en) | 2005-11-30 |
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| JP33513096A Expired - Fee Related JP3721678B2 (en) | 1996-11-29 | 1996-11-29 | Non-aqueous electrolyte secondary battery |
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| JP4590682B2 (en) * | 2000-04-26 | 2010-12-01 | 三菱化学株式会社 | Positive electrode material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery |
| JP5066805B2 (en) * | 2005-12-12 | 2012-11-07 | 日本電気株式会社 | Electricity storage device |
| JP4893000B2 (en) * | 2006-02-03 | 2012-03-07 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery and manufacturing method thereof |
| JP5168395B2 (en) | 2010-09-17 | 2013-03-21 | ダイキン工業株式会社 | Conductive protective layer forming paste for current collecting laminates such as non-aqueous secondary batteries |
| WO2013031045A1 (en) * | 2011-08-26 | 2013-03-07 | 三洋化成工業株式会社 | Additive for electrode, and electrode |
| JP5784819B2 (en) | 2012-03-15 | 2015-09-24 | 株式会社東芝 | Electrode for solid electrolyte secondary battery, solid electrolyte secondary battery, and battery pack |
| JP5715298B2 (en) * | 2012-03-23 | 2015-05-07 | 株式会社東芝 | Anode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery and battery pack |
| CN112216869B (en) * | 2020-10-13 | 2022-08-09 | 中国科学院成都有机化学有限公司 | High-voltage electrolyte additive, high-voltage electrolyte and lithium ion battery |
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| JPH10162833A (en) | 1998-06-19 |
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