JP4544408B2 - Secondary battery electrolyte and secondary battery using the same - Google Patents
Secondary battery electrolyte and secondary battery using the same Download PDFInfo
- Publication number
- JP4544408B2 JP4544408B2 JP2004181106A JP2004181106A JP4544408B2 JP 4544408 B2 JP4544408 B2 JP 4544408B2 JP 2004181106 A JP2004181106 A JP 2004181106A JP 2004181106 A JP2004181106 A JP 2004181106A JP 4544408 B2 JP4544408 B2 JP 4544408B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- negative electrode
- lithium secondary
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003792 electrolyte Substances 0.000 title claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 134
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 111
- -1 hydroxy sultone compound Chemical class 0.000 claims description 67
- 239000007773 negative electrode material Substances 0.000 claims description 44
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
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- 150000001450 anions Chemical class 0.000 claims description 7
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
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- 125000001424 substituent group Chemical group 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Description
本発明は、ヒドロキシスルトン化合物を含有した二次電池用電解液や、これを用いたリチウム二次電池に関するものである。 The present invention relates to an electrolytic solution for a secondary battery containing a hydroxy sultone compound and a lithium secondary battery using the same.
負極に、リチウムを吸蔵、放出できる物質を用い、正極にリチウム含有遷移金属酸化物などを用いたリチウムを活物質とする非水系電解液二次電池は、高いエネルギー密度を実現できることから携帯電話、ノートパソコンなどの電源として注目されている。このリチウムを活物質とする二次電池において、充放電の反復に伴い負極表面に局部的に析出するデンドライトがその安全性、サイクル寿命、容量特性に大きな影響を及ぼすため、電極表面に保護膜や、あるいはＳＥＩまたは皮膜などの表面膜を形成することが行われている。かかる表面膜は充放電効率、サイクル寿命、安全性に大きな影響を及ぼすことから、電池の高性能化にはその制御が不可欠である。即ち、リチウムを吸蔵、放出できる炭素質物や酸化物を含有する材料で形成された負極においては、表面膜によりその不可逆容量の低減を抑制することが必要であり、リチウム金属やリチウム合金を含有する材料で形成された負極においては、表面膜により充放電効率の低下の抑制や安全性の問題を解決する必要がある。 A non-aqueous electrolyte secondary battery that uses lithium as a negative electrode and a lithium-containing transition metal oxide as the active material for the negative electrode can be used for mobile phones, It is attracting attention as a power source for notebook computers. In the secondary battery using lithium as an active material, the dendrite that locally deposits on the negative electrode surface with repeated charging and discharging greatly affects its safety, cycle life, and capacity characteristics. Alternatively, a surface film such as SEI or a film is formed. Such a surface film has a great influence on charge / discharge efficiency, cycle life, and safety, so that control is indispensable for improving the performance of the battery. That is, in a negative electrode formed of a material containing a carbonaceous material or an oxide capable of occluding and releasing lithium, it is necessary to suppress reduction of the irreversible capacity by the surface film, and it contains lithium metal or lithium alloy. In a negative electrode formed of a material, it is necessary to solve the problem of suppressing the reduction in charge / discharge efficiency and the safety by the surface film.
この問題を解決するためリチウム金属またはリチウム合金の表面に、化学反応を利用してフッ化リチウム等からなる皮膜層を設けることによってデンドライトの生成を抑制することが提案されている。例えば、特許文献１には、フッ化水素酸を含有する電解液にリチウム負極を曝し、負極をフッ化水素酸と反応させることによりその表面をフッ化リチウム膜で覆う技術が開示されている。電解液に含有するＬｉＰＦ6などのリチウム化合物と微量の水の反応により生成したフッ化水素を、空気中での自然酸化により水酸化リチウムや酸化リチウムの表面膜が形成されているリチウム負極表面に作用させ、これらが反応することにより、負極表面にフッ化リチウムの表面膜を生成させるのである。しかしながら、このフッ化リチウム膜は、電極界面と電解液との反応を利用して形成されるものであり、副反応成分が表面膜中に混入しやすく、均一な膜が得られにくい。また、水酸化リチウムや酸化リチウムの表面膜が均一に形成されていない場合や一部リチウムがむきだしになっている部分が存在する場合もあり、このような場合には均一な薄膜が形成されないばかりか、水やフッ化水素等とリチウムが反応することによる安全性の問題が生じる。また、反応が不十分であった場合には、フッ化物以外の不要な化合物成分が残り、イオン伝導性の低下を招く等の悪影響が考えられる。更に、このような界面での化学反応を利用してフッ化物層を形成する方法では、利用できるフッ化物や電解液の選択幅が限定され、安定な表面膜を歩留まりよく形成することは困難であった。 In order to solve this problem, it has been proposed to suppress the formation of dendrite by providing a film layer made of lithium fluoride or the like on the surface of lithium metal or lithium alloy using a chemical reaction. For example, Patent Document 1 discloses a technique in which a lithium negative electrode is exposed to an electrolytic solution containing hydrofluoric acid, and the negative electrode is reacted with hydrofluoric acid to cover the surface with a lithium fluoride film. Hydrogen fluoride generated by the reaction of a small amount of water with a lithium compound such as LiPF 6 contained in the electrolytic solution is formed on the surface of the lithium negative electrode where a surface film of lithium hydroxide or lithium oxide is formed by natural oxidation in the air. By acting and reacting these, a surface film of lithium fluoride is generated on the surface of the negative electrode. However, this lithium fluoride film is formed by utilizing the reaction between the electrode interface and the electrolytic solution, and side reaction components are likely to be mixed into the surface film, making it difficult to obtain a uniform film. Also, there may be cases where the surface film of lithium hydroxide or lithium oxide is not uniformly formed or there is a part where lithium is exposed. In such a case, a uniform thin film is not formed. In addition, there is a safety problem due to the reaction of lithium with water or hydrogen fluoride. Moreover, when reaction is inadequate, unnecessary compound components other than a fluoride remain, and bad influences, such as causing the fall of ion conductivity, are considered. Furthermore, in the method of forming a fluoride layer using such a chemical reaction at the interface, the selection range of the available fluoride and electrolyte is limited, and it is difficult to form a stable surface film with a high yield. there were.
また、特許文献２には、アルゴンとフッ化水素の混合ガスとアルミニウム−リチウム合金とを反応させ、負極表面にフッ化リチウムの表面膜を形成する方法が開示されている。しかしながら、リチウム金属表面にあらかじめ表面膜が存在する場合、特に複数種の化合物が存在する場合には反応が不均一になり易く、フッ化リチウムの膜を均一に形成することが困難である。このため、十分なサイクル特性のリチウム二次電池を得ることが困難となる。 Patent Document 2 discloses a method of forming a surface film of lithium fluoride on the negative electrode surface by reacting a mixed gas of argon and hydrogen fluoride with an aluminum-lithium alloy. However, when a surface film is present on the lithium metal surface in advance, particularly when a plurality of types of compounds are present, the reaction tends to be non-uniform, and it is difficult to form a lithium fluoride film uniformly. For this reason, it becomes difficult to obtain a lithium secondary battery having sufficient cycle characteristics.
また、特許文献３（特開平１１−２８８７０６号公報）には、均一な結晶構造すなわち（１００）結晶面が優先的に配向しているリチウムシートの表面に、岩塩型結晶構造を持つ物質を主成分とする表面皮膜構造を形成した負極が開示されている。これにより、均一な析出溶解反応すなわち電池の充放電を行うことができ、リチウム金属のデンドライト析出を抑え、電池のサイクル寿命が向上できるとされている。かかる負極の表面膜としては、ＬｉＣｌ、ＬｉＢｒ、ＬｉＩなどより選ばれる少なくとも一種と、ＬｉＦとの固溶体などのリチウムのハロゲン化物を成分とするものである。このような表面膜を有する負極を作成するには、押圧処理（圧延）により作成した（１００）結晶面が優先的に配向しているリチウムシートを、塩素分子もしくは塩素イオン、臭素分子もしくは臭素イオン、ヨウ素分子もしくはヨウ素イオンのうち少なくとも一種とフッ素分子もしくはフッ素イオンを含有している電解液に浸すことによっている。しかしながら、このような負極の形成に使用される圧延のリチウム金属シートは大気中に曝されやすく、表面に水分などに由来する皮膜が容易に形成され、活性点が不均一に存在することにより、目的とした安定な表面膜を均一に作ることが困難となり、デンドライトの抑制効果は必ずしも充分に得られない。 Patent Document 3 (Japanese Patent Laid-Open No. 11-288706) mainly discloses a substance having a rock salt type crystal structure on the surface of a lithium sheet in which a uniform crystal structure, that is, a (100) crystal plane is preferentially oriented. A negative electrode having a surface film structure as a component is disclosed. Thereby, it is said that uniform precipitation dissolution reaction, that is, charging / discharging of the battery can be performed, dendrite precipitation of lithium metal can be suppressed, and the cycle life of the battery can be improved. As the surface film of the negative electrode, at least one selected from LiCl, LiBr, LiI and the like and a lithium halide such as a solid solution with LiF are used as components. In order to create a negative electrode having such a surface film, a lithium sheet with a (100) crystal plane preferentially oriented by pressing treatment (rolling) is prepared from chlorine molecules or chlorine ions, bromine molecules or bromine ions. , By immersing in an electrolyte containing at least one of iodine molecules or iodine ions and fluorine molecules or fluorine ions. However, the rolled lithium metal sheet used for the formation of such a negative electrode is easily exposed to the atmosphere, a film derived from moisture etc. is easily formed on the surface, and the active sites are non-uniformly present. It becomes difficult to uniformly form the intended stable surface film, and the effect of suppressing dendrite is not always sufficiently obtained.
更に、上記従来技術は、共通する次のような課題を有している。上述のように電極表面に形成された表面膜は、その性質によって充放電効率、サイクル寿命、安全性に深く関わっているが、リチウムやその合金からなる層の上にリチウムハロゲン化物またはガラス状酸化物などからなる表面膜を形成した場合、初期使用時にはデンドライトの抑制効果が一定程度得られるものの、繰り返し使用していると、表面膜が劣化して保護膜としての機能が低下する。これは、リチウム金属やその合金からなる層は、リチウム金属などを吸蔵・放出することにより体積変化する一方、その上部に位置するリチウムハロゲン化物等からなる被膜は体積変化がほとんどないため、これらの層およびこれらの界面に内部応力が発生し、この内部応力が表面膜の一部に破損を生じさせ、デンドライト生成の抑制機能の低下の誘因となるものと考えられる。表面膜を長期に亘って確実に形成させることができる方法は未だ見出されていない。 Furthermore, the above-described prior art has the following common problems. The surface film formed on the surface of the electrode as described above is deeply related to charge / discharge efficiency, cycle life, and safety depending on its properties, but lithium halide or glassy oxide on the layer made of lithium or its alloy. When a surface film made of a material or the like is formed, a dendrite suppressing effect can be obtained to a certain degree during initial use. However, if it is repeatedly used, the surface film deteriorates and the function as a protective film is lowered. This is because a layer made of lithium metal or an alloy thereof changes in volume by occluding / releasing lithium metal or the like, while a film made of lithium halide or the like located on the upper layer hardly changes in volume. It is considered that internal stress is generated in the layer and the interface between them, and this internal stress causes a part of the surface film to be damaged, leading to a decrease in the dendrite generation suppressing function. A method capable of reliably forming the surface film over a long period of time has not yet been found.
このようなリチウム二次電池においては、電解液として常温で液体の有機溶媒にリチウム塩を溶解させた液が用いられている。かかる有機溶媒としては、エチレンカーボネートのような環状カーボネート化合物、ジメチルカーボネートのような鎖状カーボネート化合物の混合物が一般的である。しかしながら、これらの有機溶媒は揮発性が高く、且つ引火性、可燃性を有し、電池からの液漏れや安全性の確保に工夫が必要である。このため、これらの有機溶剤に代えて、実質的に蒸気圧のない常温で液体の有機常温溶融塩の利用が提案されている（例えば、特許文献４〜７参照）。かかる有機常温溶融塩としては、イミダゾリウムカチオン、ピリジニウムカチオンなどの第四級アンモニウム有機カチオンが挙げられている。しかしながら、これらの有機カチオンは負極において金属リチウムと反応し還元分解を受けるため、当該二次電池の充放電効率が低い、サイクル特性が悪いなどの問題点があった。 In such a lithium secondary battery, a liquid in which a lithium salt is dissolved in an organic solvent that is liquid at room temperature is used as an electrolytic solution. As such an organic solvent, a mixture of a cyclic carbonate compound such as ethylene carbonate and a chain carbonate compound such as dimethyl carbonate is generally used. However, these organic solvents have high volatility and are flammable and flammable, and it is necessary to devise in order to ensure liquid leakage from the battery and safety. For this reason, it has been proposed to use organic room temperature molten salts that are liquid at room temperature with substantially no vapor pressure instead of these organic solvents (see, for example, Patent Documents 4 to 7). Examples of such organic room temperature molten salts include quaternary ammonium organic cations such as imidazolium cations and pyridinium cations. However, since these organic cations react with metallic lithium in the negative electrode and undergo reductive decomposition, there are problems such as low charge / discharge efficiency of the secondary battery and poor cycle characteristics.
その他、非水電解液の溶媒として、エチレンサルファイト、ジメチルサルファイト、スルフォラン、スルフォレンなどの硫黄含有化合物を用い、電解液が接触する部分の正極集電体および外缶の材質をアルミニウム、チタンなどの弁金属とすることにより、サイクル特性を向上させた非水系電解液電池が報告されている（例えば、特許文献８）。また、４．５Ｖ以上の動作電位の二次電池としては、正極に正極活物質としてリチウム含有遷移金属複合酸化物などを用いたものが知られているが、正極上で電解液の溶媒分子の分解などが生じ、サイクル寿命の低下を招いている。 Other non-aqueous electrolyte solvents include sulfur-containing compounds such as ethylene sulfite, dimethyl sulfite, sulfolane, and sulfolene, and the positive electrode current collector and outer can that are in contact with the electrolyte are made of aluminum, titanium, etc. A non-aqueous electrolyte battery with improved cycle characteristics has been reported (for example, Patent Document 8). In addition, as a secondary battery having an operating potential of 4.5 V or more, a battery using a lithium-containing transition metal composite oxide or the like as a positive electrode active material is known for the positive electrode. Decomposition occurs and the cycle life is shortened.
このように、二次電池用電極に皮膜を形成して、充放電効率、サイクル寿命の改善などを図った研究が行われているが、未だ十分な電池が得られていない。
本発明の課題は、リチウム二次電池において、炭素質物や酸化物を含有する材料で形成された負極においては、その不可逆容量の低減を抑制し、リチウム金属やリチウム合金を含有する材料で形成された負極においては、充放電効率の低下の抑制や安全性が高いものとなるように、高いエネルギー密度や起電力など優れた電池特性を有するとともに、充放電効率の低減を抑制し、サイクル寿命の長期化を図り、電池容量の低減を抑制することができるリチウム電池用非水系電解液や、これを用いたリチウム二次電池を提供することにある。 An object of the present invention is that in a lithium secondary battery, a negative electrode formed of a material containing a carbonaceous material or an oxide is formed of a material containing lithium metal or a lithium alloy while suppressing reduction of the irreversible capacity. In addition, the negative electrode has excellent battery characteristics such as high energy density and electromotive force so as to suppress the decrease in charge / discharge efficiency and have high safety, and also suppress the decrease in charge / discharge efficiency, thereby reducing the cycle life. An object of the present invention is to provide a non-aqueous electrolyte solution for a lithium battery that can be prolonged and suppress a reduction in battery capacity, and a lithium secondary battery using the same.
本発明者らは、既に、正極にリチウムに対して４.５Ｖ以上の放電電位を示す正極活物質を含有し、非水電解液の電解質として環状スルホン酸エステルを含有することにより、充放電特性が改善された高い動作電圧を有する非水電解質二次電池を開発している。本発明者らは、更なる鋭意研究の結果、かかる環状スルホン酸エステルのうち、置換基としてヒドロキシ基を有するスルトン化合物を含有したリチウム二次電池用非水系電解液は、リチウム二次電池に顕著な充放電効率の低減抑制効果、サイクル寿命の長期化、電池容量の低減抑制効果をもたらすことの知見を得た。上記現象のメカニズムの詳細については不明であるが、これは、スルトン化合物のヒドロキシ基が負極のリチウム金属に吸着することにより、充放電前および充放電時におけるスルトン化合物の負極への吸着性を高め、負極上に緻密な安定皮膜を作ることが、このような特性改善に結びつくと考えられる。これらの知見に基づき、本発明を完成するに至った。 The present inventors have already included a positive electrode active material exhibiting a discharge potential of 4.5 V or higher with respect to lithium in the positive electrode, and a cyclic sulfonic acid ester as an electrolyte of the non-aqueous electrolyte solution. Has developed a non-aqueous electrolyte secondary battery having improved high operating voltage. As a result of further diligent research, the present inventors have found that a non-aqueous electrolyte solution for a lithium secondary battery containing a sultone compound having a hydroxy group as a substituent among such cyclic sulfonate esters is prominent in lithium secondary batteries. The present inventors have obtained knowledge that the effect of suppressing the reduction of charge / discharge efficiency, the prolongation of cycle life, and the effect of suppressing the reduction of battery capacity can be obtained. Although the details of the mechanism of the above phenomenon are unknown, this is because the hydroxy group of the sultone compound is adsorbed to the lithium metal of the negative electrode, thereby increasing the adsorptivity of the sultone compound to the negative electrode before and during charge / discharge. It is considered that the formation of a dense stable film on the negative electrode leads to such improvement in characteristics. Based on these findings, the present invention has been completed.
すなわち、本発明は、ヒドロキシスルトン化合物を含有するリチウム二次電池用非水系電解液であって、ヒドロキシスルトン化合物が、式（１） That is, the present invention is a non-aqueous electrolyte for a lithium secondary battery containing a hydroxy sultone compound, wherein the hydroxy sultone compound is represented by the formula (1)
で表されるヒドロキシプロパンスルトン化合物を含むことを特徴とするリチウム二次電池用非水系電解液に関する。式（１）で表されるヒドロキシプロパンスルトン化合物は、電解液中に０．５〜１００ｍＭ含まれることが好ましい。 And a non-aqueous electrolyte for a lithium secondary battery, comprising a hydroxypropane sultone compound represented by the formula: The hydroxypropane sultone compound represented by the formula (1) is preferably contained in an amount of 0.5 to 100 mM in the electrolytic solution.
上記非水系電解液は、有機溶媒として、環状カーボネートや、鎖状カーボネートなどの炭酸エステル類、脂肪族カルボン酸エステル類、ラクトン類、環状エーテルや鎖状エーテルなどのエーテル類、これらのフッ化誘導体、および有機常温溶融塩から選ばれた1または２種以上を用いることが好ましい。 The non-aqueous electrolyte includes, as an organic solvent, cyclic carbonates, carbonates such as chain carbonates, aliphatic carboxylic acid esters, lactones, ethers such as cyclic ethers and chain ethers, and fluorinated derivatives thereof. And one or more selected from organic room temperature molten salts are preferably used.
かかる有機常温溶融塩が、式（２） Such an organic room temperature molten salt has the formula (2)
（式中、Ｒ1、Ｒ3は、独立して炭素数１〜６の鎖状または分岐状アルキル基を示し、Ｒ2は水素原子または炭素数１〜６の鎖状または分岐状アルキル基を示し、Ｘ-は、アニオンを示す。）
で表されるイミダゾリウム誘導体、および／または式（３）
(Wherein R 1 and R 3 independently represent a chain or branched alkyl group having 1 to 6 carbon atoms, and R 2 represents a hydrogen atom or a chain or branched alkyl group having 1 to 6 carbon atoms. shows, X - represents an anion).
And / or the formula (3)
（式中、Ｒ4は炭素数１〜６の鎖状または分岐状アルキル基を示し、Ｒ5、Ｒ6は、独立して水素原子または炭素数１〜６の鎖状または分岐状アルキル基を示し、Ｘ-は、アニオンを示す。）
で表されるピリジニウム誘導体を含むことが好ましい。
(Wherein R 4 represents a chain or branched alkyl group having 1 to 6 carbon atoms, and R 5 and R 6 independently represent a hydrogen atom or a chain or branched alkyl group having 1 to 6 carbon atoms. shows, X - represents an anion).
It is preferable that the pyridinium derivative represented by these is included.
また、電解質として、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣｌＯ4、ＬｉＡｌＣｌ4、ＬｉＮ（ＣkＦ2k+1ＳＯ2）(ＣmＦ2m+1ＳＯ2)（ｋ，ｍは独立して１あるいは４の整数）から選ばれた１または２種以上のリチウム塩を含有することが好ましい。但し、溶媒として有機常温溶融塩を用いる場合には、電解質を構成するアニオンは有機常温溶融塩を構成するアニオンと同じであることが好ましい。 Further, as the electrolyte, LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiAlCl 4 , LiN (C k F 2k + 1 SO 2 ) (C m F 2m + 1 SO 2 ) (k and m are independent). And one or more lithium salts selected from 1 or an integer of 4). However, when an organic room temperature molten salt is used as the solvent, the anion constituting the electrolyte is preferably the same as the anion constituting the organic room temperature molten salt.
また、本発明は、上記リチウム二次電池用非水系電解液を用いたことを特徴とするリチウム二次電池に関する。 The present invention also relates to a lithium secondary battery using the non-aqueous electrolyte for a lithium secondary battery.
上記リチウム二次電池は、負極が、リチウム金属、リチウム合金、リチウムを吸蔵、放出できる炭素質物、リチウムを吸蔵、放出できる酸化物、放出できる炭素質物、リチウムを吸蔵、放出できる金属などのリチウムを吸蔵、放出できる負極活物質を含有することが好ましい。前記リチウム合金、リチウムを吸蔵、放出できる酸化物、リチウムを吸蔵、放出できる金属が、Ｓｉ、Ｇｅ、Ｉｎ、Ｓｎ、Ａｇ、Ａｌ、Ｐｂから選ばれた１または２種以上の元素を含有することが好ましい。 In the lithium secondary battery, the negative electrode is made of lithium metal, a lithium alloy, a carbonaceous material that can occlude and release lithium, an oxide that can occlude and release lithium, a carbonaceous material that can release lithium, and a metal that can occlude and release lithium. It is preferable to contain a negative electrode active material that can be occluded and released. The lithium alloy, the oxide capable of occluding and releasing lithium, and the metal capable of occluding and releasing lithium contain one or more elements selected from Si, Ge, In, Sn, Ag, Al, and Pb. Is preferred.
また、正極が、リチウム含有複合酸化物、有機イオウ化合物、導電性高分子、および有機ラジカル化合物から選ばれた１または２種以上の正極活物質を含有することが好ましく、かかる正極活物質としてのリチウム含有複合酸化物が、スピネル型リチウムマンガン複合酸化物、オリビン型リチウム含有複合酸化物、および逆スピネル型リチウム含有複合酸化物から選ばれた１または２種以上であることが好ましく、上記リチウム含有複合酸化物が、ＬｉbＣｏＯ2、ＬｉbＮｉＯ2、ＬｉbＭｎ2Ｏ4、ＬｉbＭｎＯ3、ＬｉbＮｉdＣｒ1-dＯ2（ここで、０＜ｂ、０＜ｄ＜１である。）から選ばれた１または２種以上の化合物を含有することが好ましい。また、上記スピネル型リチウムマンガン複合酸化物が、式（４）
Ｌｉa（ＡxＭｎ2-x）Ｏ4 （４）
（式中、Ａは、Ｎｉ、Ｃｏ、Ｆｅ、Ｔｉ、ＣｒまたはＣｕを示し、ｘは０＜ｘ＜２、ａは０＜ａ＜１．２の数値を示す。）
で表されることが好ましい。
The positive electrode preferably contains one or more positive electrode active materials selected from lithium-containing composite oxides, organic sulfur compounds, conductive polymers, and organic radical compounds. The lithium-containing composite oxide is preferably one or more selected from a spinel-type lithium manganese composite oxide, an olivine-type lithium-containing composite oxide, and a reverse spinel-type lithium-containing composite oxide. The composite oxide is Li b CoO 2 , Li b NiO 2 , Li b Mn 2 O 4 , Li b MnO 3 , Li b Ni d Cr 1-d O 2 (where 0 <b, 0 <d <1 It is preferable to contain 1 or 2 or more types of compounds selected from these. Further, the spinel type lithium manganese composite oxide has the formula (4)
Li a (A x Mn 2-x ) O 4 (4)
(In the formula, A represents Ni, Co, Fe, Ti, Cr or Cu, x represents a numerical value of 0 <x <2, and a represents a value of 0 <a <1.2.)
It is preferable to be represented by
本発明によれば、ヒドロキシプロパンスルトン化合物を含有するリチウム二次電池用非プロトン性電解液を用いることにより、リチウムハロゲン化膜やガラス状酸化物などであらかじめ電極表面に表面膜を形成することを不要とし、高いエネルギー密度、起電力など優れた電池特性を有するとともに、サイクル寿命、安全性に優れたリチウム二次電池用非水系電解液や、これを用いたリチウム二次電池を得ることができる。とりわけ、電解液の溶媒として常温溶融有機塩を用いた場合、これらの有機カチオンが負極において金属リチウムと反応して還元分解を受けにくくなることから、充放電効率の低下や、サイクル特性の低下を抑制し、安全性の高いリチウム二次電池用非水系電解液や、これを用いたリチウム二次電池を得ることができる。 According to the present invention, by using an aprotic electrolyte solution for a lithium secondary battery containing a hydroxypropane sultone compound, a surface film is previously formed on the electrode surface with a lithium halide film or a glassy oxide. A non-aqueous electrolyte for a lithium secondary battery having excellent battery characteristics such as high energy density and electromotive force, excellent cycle life and safety, and a lithium secondary battery using the same can be obtained. . In particular, when a room temperature molten organic salt is used as a solvent for the electrolyte, these organic cations react with metallic lithium at the negative electrode and are less susceptible to reductive decomposition, reducing charge / discharge efficiency and cycle characteristics. It is possible to obtain a highly safe non-aqueous electrolyte for a lithium secondary battery and a lithium secondary battery using the same.
本発明のリチウム二次電池用非水系電解液は、１−ヒドロキシ−１，３−プロパンスルトン、２−ヒドロキシ−１，３−プロパンスルトン、３−ヒドロキシ−１，３−プロパンスルトン、１−ヒドロキシ−１，４−ブタンスルトン、２−ヒドロキシ−１，４−ブタンスルトン、３−ヒドロキシ−１，４−ブタンスルトン、４−ヒドロキシ−１，４−ブタンスルトン、１−ヒドロキシ−１，３−ブタンスルトン、２−ヒドロキシ−１，３−ブタンスルトン、３−ヒドロキシ−１，３−ブタンスルトン、２−ヒドロキシ−２，４−ブタンスルトン、３−ヒドロキシ−２，４−ブタンスルトン、４−ヒドロキシ−２，４−ブタンスルトンなどのヒドロキシスルトン化合物を用いることができるが、このうち、式（１） The non-aqueous electrolyte for a lithium secondary battery of the present invention includes 1-hydroxy-1,3-propane sultone, 2-hydroxy-1,3-propane sultone, 3-hydroxy-1,3-propane sultone, and 1-hydroxy. -1,4-butane sultone, 2-hydroxy-1,4-butane sultone, 3-hydroxy-1,4-butane sultone, 4-hydroxy-1,4-butane sultone, 1-hydroxy-1,3-butane sultone, 2-hydroxy Hydroxy sultone such as -1,3-butane sultone, 3-hydroxy-1,3-butane sultone, 2-hydroxy-2,4-butane sultone, 3-hydroxy-2,4-butane sultone , 4-hydroxy-2,4-butane sultone Compounds can be used , of which formula (1)
で表されるヒドロキシスルトン化合物を含む。式（１）で表される化合物として、ヒドロキシ基はいずれの炭素原子に結合するものであってもよいが、特に、ヒドロキシ基が２位の炭素に結合した式（５） The hydroxy sultone compound represented by these is included . As the compound represented by the formula (1), the hydroxy group may be bonded to any carbon atom, but in particular, the formula (5) in which the hydroxy group is bonded to the carbon at the 2-position.
で表されるヒドロキシスルトン化合物が、リチウム二次電池に優れた電池特性、充放電効率、サイクル寿命を付与するため、好ましい。これらのヒドロキシスルトン化合物は公知の方法により製造することができ、例えば米国特許第３１００７７９号に記載に準じた方法などにより調製することができる。 Is preferable because it imparts excellent battery characteristics, charge / discharge efficiency, and cycle life to the lithium secondary battery. These hydroxy sultone compounds can be produced by a known method, for example, by a method according to the description in US Pat. No. 3,100,799.
このようなヒドロキシスルトン化合物の電解液中の濃度は特に限定されないが、好ましくは電解液全体に対して、０．５〜１００ｍＭの範囲である。ヒドロキシスルトン化合物の濃度が０．５ｍＭ以上であれば、電極表面全体に添加剤の効果を行き亘らせることができ、電極表面に十分な皮膜形成がなされ、１００ｍＭ以下であれば、電解質であるリチウム塩との副反応を抑制することができ、電池特性やサイクル特性が長期に亘って維持され、充放電に伴い安定な表面膜が形成される。ヒドロキシスルトン化合物の濃度は、１〜５０ｍＭの範囲であると、上記効果が顕著に得られるためより好ましく、更に顕著な効果が得られる範囲は５〜４０ｍＭである。 The concentration of such a hydroxy sultone compound in the electrolytic solution is not particularly limited, but is preferably in the range of 0.5 to 100 mM with respect to the entire electrolytic solution. If the concentration of the hydroxysultone compound is 0.5 mM or more, the effect of the additive can be spread over the entire electrode surface, and a sufficient film is formed on the electrode surface. Side reactions with the lithium salt can be suppressed, battery characteristics and cycle characteristics are maintained over a long period of time, and a stable surface film is formed with charge and discharge. The concentration of the hydroxy sultone compound is more preferably in the range of 1 to 50 mM because the above effect is remarkably obtained, and the range in which a further remarkable effect is obtained is 5 to 40 mM.
本発明のリチウム二次電池用非水系電解液に用いる溶媒は、常温で液体のものであれば使用することができるが、具体的には、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ブチレンカーボネート（ＢＣ）、ビニレンカーボネート（ＶＣ）などの環状カーボネート類や、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭＣ）、ジプロピルカーボネート（ＤＰＣ）などの鎖状カーボネート類等の炭酸エステル類；ギ酸メチル、酢酸メチル、プロピオン酸エチルなどの脂肪族カルボン酸エステル類；ブチロラクトンなどのラクトン類；エチルエーテル、１，２−エトキシエタン（ＤＥＥ）、エトキシメトキシエタン（ＥＭＥ）、トリメトキシメタン、エチルモノグライムなどの鎖状エーテル類や、テトラヒドロフラン、２−メチルテトラヒドロフランなどの環状エーテル類等のエーテル類；フッ素化カルボン酸エステルなどこれらのフッ化誘導体等；ジメチルスルホキシド、１，３−ジオキソラン、ホルムアミド、アセトアミド、ジメチルホルムアミド、ジオキソラン、アセトニトリル、プロピルニトリル、ニトロメタン、リン酸トリエステル、ジオキソラン誘導体、スルホラン、メチルスルホラン、１，３−ジメチル−２−イミダゾリジノン、３−メチル−２−オキサゾリジノン、プロピレンカーボネート誘導体、テトラヒドロフラン誘導体、アニソール、Ｎ−メチルピロリドンなどや、後述する有機常温溶融塩を挙げることができる。これらは単独で用いてもよく、また、電解質の種類や、電極の種類などに応じて適宜組み合わせて使用することができる。 The solvent used in the non-aqueous electrolyte for a lithium secondary battery of the present invention can be used as long as it is liquid at room temperature. Specifically, propylene carbonate (PC), ethylene carbonate (EC), butylene. Cyclic carbonates such as carbonate (BC) and vinylene carbonate (VC), and chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC). Carbonic acid esters; aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate; lactones such as butyrolactone; ethyl ether, 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), trimethoxy Methane, ethyl monogly Chain ethers such as tetrahydrofuran, cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran; fluorinated derivatives such as fluorinated carboxylates; dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, Dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, phosphate triester, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran Derivatives, anisole, N-methylpyrrolidone and the like, and organic room temperature molten salts described later can be mentioned. These may be used alone, or may be used in appropriate combination depending on the type of electrolyte, the type of electrode, and the like.
上記有機常温溶融塩としては、常温で液状の有機塩であればよく、具体的には、イミダゾリウムイオン、ピラゾリウムイオン、ピロリジニウムイオン、ピペリジニウムイオンなどの第四級有機アンンモニウムイオンを有するものを挙げることができ、これら第四級有機アンモニウムイオンを有する有機常温溶融塩のうちでは、イミダゾリウムイオンを有する式（２） The organic room temperature molten salt may be an organic salt that is liquid at room temperature, and specifically includes a quaternary organic ammonium ion such as an imidazolium ion, a pyrazolium ion, a pyrrolidinium ion, or a piperidinium ion. Among these organic room temperature molten salts having quaternary organic ammonium ions, those having formula (2) having imidazolium ions
で表されるイミダゾリウム誘導体や、ピリジニウムイオンを有する式（３） Or an imidazolium derivative represented by the formula (3) having a pyridinium ion
で表されるピリジニウム誘導体を好ましいものとして挙げることができる。 The pyridinium derivative represented by these can be mentioned as a preferable thing.
かかるイミダゾリウム誘導体を表す式（２）におけるＲ1、Ｒ3は、独立して炭素数１〜６の鎖状または分岐状アルキル基を示し、Ｒ2は水素原子または炭素数１〜６の鎖状もしくは分岐状アルキル基を示し、Ｒ1、Ｒ2、Ｒ3が示す炭素数１〜６の鎖状または分岐状アルキル基としては、上記に例示した炭素数１〜６の鎖状または分岐状アルキル基と同様のものを具体的に挙げることができる。式（２）におけるイミダゾリウムイオンとしては、具体的に、Ｎ，Ｎ−ジメチルイミダゾリウムイオン、Ｎ，Ｎ−ジエチルイミダゾリウムイオンなどのＮ，Ｎ−ジアルキルイミダゾリウムイオンや、Ｎ，Ｎ−２−トリメチルイミダゾリウムイオン、Ｎ，Ｎ−ジメチル−２−エチルイミダゾリウムイオンなどのＮ，Ｎ−２−トリアルキルイミダゾリウムイオンなどのイミダゾリウムイオンを例示することができる。 R 1 and R 3 in formula (2) representing such an imidazolium derivative independently represent a chain or branched alkyl group having 1 to 6 carbon atoms, and R 2 represents a hydrogen atom or a chain having 1 to 6 carbon atoms. Or a branched or branched alkyl group having 1 to 6 carbon atoms represented by R 1 , R 2 , or R 3 is a linear or branched chain having 1 to 6 carbon atoms as exemplified above. The thing similar to an alkyl group can be mentioned concretely. Specific examples of the imidazolium ion in formula (2) include N, N-dialkylimidazolium ions such as N, N-dimethylimidazolium ion and N, N-diethylimidazolium ion, and N, N-2- Examples thereof include imidazolium ions such as N, N-2-trialkylimidazolium ions such as trimethylimidazolium ion and N, N-dimethyl-2-ethylimidazolium ion.
上記ピリジニウム誘導体を表す式（３）におけるＲ4は炭素数１〜６の鎖状または分岐状アルキル基を示し、Ｒ5、Ｒ6は、独立して水素原子または炭素数１〜６の鎖状もしくは分岐状アルキル基を示し、Ｒ4、Ｒ5、Ｒ6が示す炭素数１〜６の鎖状または分岐状アルキル基としては、上記例示の炭素数１〜６の鎖状または分岐状アルキル基と同様のものを具体的に挙げることができる。式（３）におけるピリジニウムイオンとしては、Ｎ−メチルピリジニウムイオン、Ｎ−エチルピリジニウムイオンなどのＮ−アルキルピリジニウムイオンを例示することができる。 R 4 in the formula (3) representing the pyridinium derivative represents a chain or branched alkyl group having 1 to 6 carbon atoms, and R 5 and R 6 are independently a hydrogen atom or a chain structure having 1 to 6 carbon atoms. Or, it represents a branched alkyl group, and the chain or branched alkyl group having 1 to 6 carbon atoms represented by R 4 , R 5 , and R 6 includes the above-exemplified chain or branched alkyl group having 1 to 6 carbon atoms. The same thing can be specifically mentioned. Examples of the pyridinium ion in formula (3) include N-alkylpyridinium ions such as N-methylpyridinium ion and N-ethylpyridinium ion.
また、上記式（２）または式（３）におけるＸ-は、本発明の非水系電解液に含有される電解質に含まれるアニオンと同じものであることが好ましいが、ＢＦ4 -，ＰＦ6 -，ＣＦ3ＳＯ3 -、またはＮ（ＣkＦ2k+1ＳＯ2）(ＣmＦ2m+1ＳＯ2) -（ｋ，ｍは独立して１または４の整数）を示すものであってもよい。 X − in the above formula (2) or formula (3) is preferably the same as the anion contained in the electrolyte contained in the non-aqueous electrolyte of the present invention, but BF 4 − , PF 6 −. , CF 3 SO 3 − , or N (C k F 2k + 1 SO 2 ) (C m F 2m + 1 SO 2 ) − (k and m are each independently an integer of 1 or 4) Also good.
上記有機常温溶融塩は単独で用いてもよく、また、任意のものを組み合わせて使用することができ、有機常温溶融塩以外の他種の溶媒と適宜組み合わせて用いることができる。 The organic room temperature molten salt may be used alone, or may be used in combination with any other, and may be used in appropriate combination with other types of solvents other than the organic room temperature molten salt.
本発明のリチウム二次電池用非水系電解液の電解質としては、リチウム塩が好ましく、具体的には、リチウムイミド塩、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＡｌＣｌ4、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＳｂＦ6などは安全性などの点で好ましいものとして挙げることができる。これらの電解質は溶媒、負極、正極の材質などとの関係において適宜選択することができ、単独で用いることも、また、２種以上を組み合わせて用いることもできる。電解質の濃度としては、例えば、０.５〜１．５ｍｏｌ／Ｌであることが好ましく、この範囲であれば適切な電気伝導率を得ることができるため好ましく、１．０Ｍ前後であることがかかる効果をより顕著に得ることができ、好ましい。 As an electrolyte of the nonaqueous electrolytic solution for lithium secondary battery of the present invention, lithium salts are preferred, specifically, a lithium imide salt, LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6 , etc. It can be mentioned as preferable in terms of safety. These electrolytes can be appropriately selected in relation to the material of the solvent, the negative electrode, the positive electrode, etc., and can be used alone or in combination of two or more. The concentration of the electrolyte is preferably 0.5 to 1.5 mol / L, for example, and within this range, an appropriate electrical conductivity can be obtained, which is preferably about 1.0M. The effect can be obtained more remarkably, which is preferable.
本発明のリチウム二次電池用非水系電解液は、ヒドロキシスルトン化合物およびリチウム化合物などの電解質をあらかじめ溶媒に添加・溶解することにより調製することができる。 The nonaqueous electrolytic solution for a lithium secondary battery of the present invention can be prepared by previously adding and dissolving an electrolyte such as a hydroxy sultone compound and a lithium compound in a solvent.
本発明のリチウム二次電池は、本発明のリチウム二次電池用非水系電解液を用いたものであれば、特に制限されるものではなく、リチウム含有酸化物を正極活物質として含む正極と、リチウムを吸蔵、放出可能な負極活物質を含む負極と、正極と負極の間に配置された絶縁体としてのセパレータとを備え、正極と負極が本発明のリチウム二次電池用非水系電解液に浸った状態となるように、これらが電池ケースの中に密閉された形態をとることができる。正極と負極に電圧を印加することにより、正極活物質がリチウムイオンを放出し負極活物質がリチウムイオンを吸蔵し、電池は充電状態となり、充電状態と逆反応が進行して放電状態となる。 The lithium secondary battery of the present invention is not particularly limited as long as it uses the non-aqueous electrolyte for lithium secondary battery of the present invention, and a positive electrode containing a lithium-containing oxide as a positive electrode active material; A negative electrode containing a negative electrode active material capable of occluding and releasing lithium, and a separator as an insulator disposed between the positive electrode and the negative electrode, the positive electrode and the negative electrode being a non-aqueous electrolyte for a lithium secondary battery of the present invention These can take the form of being sealed in the battery case so as to be immersed. By applying a voltage to the positive electrode and the negative electrode, the positive electrode active material releases lithium ions, the negative electrode active material absorbs lithium ions, the battery enters a charged state, and a reverse reaction proceeds from the charged state to a discharged state.
本発明のリチウム二次電池の負極は、リチウムを吸蔵、放出可能な負極活物質を含み、かかるリチウムを吸蔵、放出可能な負極活物質としては、充電時にリチウムイオンを吸蔵でき、放電時にリチウムイオンを放出できるものであればよく、具体的には、リチウム金属、リチウム合金、リチウムを吸蔵、放出可能な炭素質物、リチウムを吸蔵、放出可能な酸化物、リチウムを吸蔵、放出可能な金属またはこれらの複合物を挙げることができる。リチウムを吸蔵、放出可能な炭素質物としては、例えば、黒鉛、非晶質炭素、ダイヤモンド状炭素、カーボンナノチューブ、カーボンナノホーンなどを挙げることができ、リチウムを吸蔵、放出可能な酸化物としては、酸化シリコン、酸化スズ、酸化インジウム、酸化亜鉛、酸化リチウム、リン酸、ホウ酸や、これらの複合酸化物を挙げることができる。これら酸化物のうち特に、酸化シリコンは安定で他の化合物との反応を引き起こさないため、好ましい。またリチウム合金としては、リチウムと合金形成可能な金属の１種または２種以上とリチウムとの２元または３元以上の合金を用いることができ、リチウムと合金形成可能な金属としては、例えば、Ａｌ、Ｓｉ、Ｐｂ、Ｓｎ、Ｉｎ、Ｂｉ、Ａｇ、Ｂａ、Ｃａ、Ｈｇ、Ｐｄ、Ｐｔ、Ｔｅ、Ｚｎ、Ｌａなどを挙げることができる。リチウムを吸蔵、放出可能な金属としては、Ａｌ、Ｓｉ、Ｐｂ、Ｓｎ、Ｉｎ、Ｂｉ、Ａｇ、Ｂａ、Ｃａ、Ｈｇ、Ｐｄ、Ｐｔ、Ｔｅ、Ｚｎ、Ｌａなどから選ばれる元素の１種または２種以上を含む混合物または合金を用いることができる。これらの金属のうち、Ｓｉ、Ｇｅ、Ｉｎ、Ｓｎ、Ａｇ、Ａｌ、Ｐｂなどから選ばれる１種または２種以上を含む混合物または合金が特に好ましい。 The negative electrode of the lithium secondary battery of the present invention includes a negative electrode active material capable of occluding and releasing lithium. As the negative electrode active material capable of occluding and releasing lithium, lithium ions can be occluded during charging and lithium ions during discharging. Specifically, lithium metal, lithium alloy, carbonaceous material that can occlude and release lithium, oxide that can occlude and release lithium, metal that can occlude and release lithium, or these can be used. Can be mentioned. Examples of carbonaceous materials that can occlude and release lithium include graphite, amorphous carbon, diamond-like carbon, carbon nanotubes, and carbon nanohorns. Examples of oxides that can occlude and release lithium include oxidation. Examples thereof include silicon, tin oxide, indium oxide, zinc oxide, lithium oxide, phosphoric acid, boric acid, and complex oxides thereof. Among these oxides, silicon oxide is particularly preferable because it is stable and does not cause a reaction with other compounds. In addition, as the lithium alloy, a binary or ternary alloy of one or more metals capable of forming an alloy with lithium and lithium can be used. As a metal capable of forming an alloy with lithium, for example, Examples thereof include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, and La. As a metal capable of inserting and extracting lithium, one or two elements selected from Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, etc. Mixtures or alloys containing more than one species can be used. Of these metals, a mixture or alloy containing one or more selected from Si, Ge, In, Sn, Ag, Al, Pb, and the like is particularly preferable.
上記リチウム金属、リチウム合金、リチウムを吸蔵、放出可能な酸化物、リチウムを吸蔵、放出可能な金属の構造としてはアモルファス状態であることが好ましい。アモルファス構造であれば、結晶粒界、欠陥といった結晶構造に特有の不均一性に起因する劣化が起きにくいためである。 The structure of the lithium metal, lithium alloy, oxide capable of inserting and extracting lithium, and metal capable of inserting and extracting lithium is preferably in an amorphous state. This is because an amorphous structure is less likely to deteriorate due to non-uniformity peculiar to the crystal structure such as crystal grain boundaries and defects.
上記負極活物質が、リチウム金属、リチウム合金、リチウムを吸蔵、放出可能な金属酸化物や、その複合物を含有する材質で形成する場合は、融液冷却方式、液体急冷方式、アトマイズ方式、ゾル−ゲル方式などの方式により形成することができる。 When the negative electrode active material is formed of a material containing lithium metal, a lithium alloy, a metal oxide capable of inserting and extracting lithium, or a composite thereof, a melt cooling method, a liquid quenching method, an atomizing method, a sol -It can be formed by a method such as a gel method.
本発明のリチウム二次電池の負極には、負極活物質の他、必要に応じて負極活物質の作用を促進させる導電材や、またその作用を抑制しない範囲で結着材などを含有してもよい。かかる結着材としては、ポリフッ化ビニリデンなどのフッ素系樹脂バインダーを用いることができ、結着材の含有量は負極全体の１〜１０質量％などとすることができる。また、導電材としては、カーボンブラックなどの炭素材料や、導電性酸化物の粉末などを用いることができ、導電材の含有量は負極全体の１〜１０質量％などとすることができる。 The negative electrode of the lithium secondary battery of the present invention contains, in addition to the negative electrode active material, a conductive material that promotes the action of the negative electrode active material as necessary, and a binder as long as the action is not suppressed. Also good. As the binder, a fluorine-based resin binder such as polyvinylidene fluoride can be used, and the content of the binder can be 1 to 10% by mass of the whole negative electrode. In addition, as the conductive material, a carbon material such as carbon black, a conductive oxide powder, or the like can be used, and the content of the conductive material can be 1 to 10% by mass or the like of the whole negative electrode.
本発明のリチウム二次電池の負極は、上記方法により形成された負極活物質と、必要ならば結合材や導電材とを、Ｎ−メチル−２−ピロリドン（ＮＭＰ）溶媒などに分散させ、混練した混合物を用いて、基体上に成膜した膜状構造体としたり、また、粒子状やペレット状に成形したものの集合体としたものを用いることができる。かかる負極活物質を含む混合物を膜状構造体に形成するには、基体である銅などの金属箔を用いた集電体上に上記混合物を塗布したり、真空蒸着、スパッタリング、プラズマＣＶＤ、光ＣＶＤ、熱ＣＶＤ等の方法によることができる。また、負極活物質を含む混合物を粒子状に成形するには、上記負極活物質を含む混合物を膜状構造体に成形した後、粉砕または分級を行うことにより成形することができ、また、これらを結合剤などと混練し、圧縮成形してペレット状に成形することができる。 The negative electrode of the lithium secondary battery of the present invention is prepared by dispersing the negative electrode active material formed by the above method and, if necessary, a binder or conductive material in an N-methyl-2-pyrrolidone (NMP) solvent or the like, and kneading. Using the mixture, a film-like structure formed on a substrate or an aggregate of those formed into particles or pellets can be used. In order to form a mixture containing such a negative electrode active material into a film-like structure, the mixture is applied to a current collector using a metal foil such as copper as a base, vacuum deposition, sputtering, plasma CVD, light It can be performed by a method such as CVD or thermal CVD. Further, in order to form a mixture containing a negative electrode active material into particles, the mixture containing a negative electrode active material can be formed into a film-like structure, and then pulverized or classified. Can be kneaded with a binder or the like and compression molded to form a pellet.
本発明のリチウム二次電池の正極は、特に制限されるものではないが、リチウム含有複合酸化物、有機イオウ化合物、導電性高分子、および有機ラジカル化合物から選ばれた１または２種以上の正極活物質を含むものとすることができる。かかるリチウム含有複合酸化物としては、ＬｉbＺＯ2（ただしＺは、少なくとも１種の遷移金属を表す。）で表され、例えば、ＬｉbＣｏＯ2、ＬｉbＮｉＯ2、ＬｉbＭｎ2Ｏ4、ＬｉbＭｎＯ3、ＬｉbＮｉdＣｒ1-dＯ2（ここで、０＜ｂ、０＜ｄ＜１である。）を挙げることができる。また、高い動作電圧を有する高電位の二次電池に対しては、正極活物質として、リチウム対極電位で４．５Ｖ以上にプラトーを有するリチウム含有複合酸化物を用いることもできる。かかるリチウム含有複合酸化物としては、スピネル型リチウムマンガン複合酸化物、オリビン型リチウム含有複合酸化物、逆スピネル型リチウム含有複合酸化物等を用いることができ、リチウム含有複合酸化物としては、例えば、Ｌｉa（ＡxＭｎ2-x）Ｏ4（ここで、Ａは、Ｎｉ、Ｃｏ、Ｆｅ、Ｔｉ、ＣｒまたはＣｕを示し、ｘは０＜ｘ＜２、ａは０＜ａ＜１．２の数値を示す。）で表される化合物を例示することができる。このようなリチウム含有複合酸化物を正極活物質に用いることにより、正極の活性な界面が減少して電解液溶媒の分解が抑制され、充放電特性が改善されると考えられる。その際、電解液に含有されるヒドロキシスルトン化合物が、これらの正極活物質の作用と相俟って、充放電特性、特に保存特性が大きく改善されるものと考えられる。正極活物質としての有機イオウ化合物としては、例えば、有機ジスルフィド化合物、有機ポリスルフィド化合物などを挙げることができ、正極活物質としての導電性高分子としては、ポリアセチレン、ポリアニリン、ポリアセンなどを挙げることができ、正極活物質としての有機ラジカル化合物としては、２，２，６，６−テトラメチルピペリノジノキシメタクリレート（ＰＴＭＡ）などを挙げることができる。 The positive electrode of the lithium secondary battery of the present invention is not particularly limited, but one or more positive electrodes selected from lithium-containing composite oxides, organic sulfur compounds, conductive polymers, and organic radical compounds. An active material can be included. Such a lithium-containing composite oxide is represented by Li b ZO 2 (where Z represents at least one transition metal), for example, Li b CoO 2 , Li b NiO 2 , Li b Mn 2 O 4. , Li b MnO 3 , Li b Ni d Cr 1-d O 2 (where 0 <b and 0 <d <1). In addition, for a high potential secondary battery having a high operating voltage, a lithium-containing composite oxide having a plateau at 4.5 V or more at the lithium counter electrode potential can be used as the positive electrode active material. As such a lithium-containing composite oxide, spinel-type lithium manganese composite oxide, olivine-type lithium-containing composite oxide, reverse spinel-type lithium-containing composite oxide, and the like can be used. Li a (A x Mn 2-x ) O 4 (where A represents Ni, Co, Fe, Ti, Cr or Cu, x is 0 <x <2, a is 0 <a <1.2 The compound represented by these can be illustrated. By using such a lithium-containing composite oxide as the positive electrode active material, it is considered that the active interface of the positive electrode is reduced, decomposition of the electrolyte solution is suppressed, and charge / discharge characteristics are improved. At that time, it is considered that the charge and discharge characteristics, particularly the storage characteristics, are greatly improved by the hydroxysultone compound contained in the electrolytic solution in combination with the action of these positive electrode active materials. Examples of the organic sulfur compound as the positive electrode active material include organic disulfide compounds and organic polysulfide compounds. Examples of the conductive polymer as the positive electrode active material include polyacetylene, polyaniline, and polyacene. Examples of the organic radical compound as the positive electrode active material include 2,2,6,6-tetramethylpiperinodinoxy methacrylate (PTMA).
本発明のリチウム二次電池の正極には、正極活物質の他、必要に応じて正極活物質の作用を促進する導電材や、その作用を抑制しない範囲で結着材などを含有してもよい。かかる結着材としては、ポリビニリデンフルオライド（ＰＶＤＦ）などの樹脂バインダーを用いることができ、結着材の含有量は正極全体の１〜１０質量％などとすることができる。また、導電材としては、カーボンブラックなどの炭素材料や、導電性酸化物の粉末などを用いることができ、導電材の含有量は正極全体の１〜１０質量％などとすることができる。 The positive electrode of the lithium secondary battery of the present invention may contain, in addition to the positive electrode active material, a conductive material that accelerates the action of the positive electrode active material as necessary, or a binder or the like as long as the action is not suppressed. Good. As such a binder, a resin binder such as polyvinylidene fluoride (PVDF) can be used, and the content of the binder can be 1 to 10% by mass of the whole positive electrode. In addition, as the conductive material, a carbon material such as carbon black, a conductive oxide powder, or the like can be used, and the content of the conductive material can be 1 to 10% by mass or the like of the entire positive electrode.
本発明のリチウム二次電池の正極は、上記の正極活物質と、必要ならば結合材や導電材とを、Ｎ−メチル−２−ピロリドン（ＮＭＰ）溶媒などに分散させ、今練した混合物を用いて、基体上に成膜した膜状構造体としたり、また、粒子状やペレット状に成形したものの集合体としたものを用いることができる。かかる負極活物質を含む混合物を膜状構造体に形成するには、基体である銅などの金属箔を用いた集電体上に上記混合物を塗布するなどの方法によることができる。 The positive electrode of the lithium secondary battery of the present invention is prepared by dispersing the positive electrode active material and, if necessary, a binder or a conductive material in an N-methyl-2-pyrrolidone (NMP) solvent or the like, It is possible to use a film-like structure formed on a substrate, or an aggregate of those formed into particles or pellets. In order to form the mixture containing the negative electrode active material in the film-like structure, a method of applying the mixture on a current collector using a metal foil such as copper as a base can be used.
本発明のリチウム二次電池におけるセパレーターとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィンや、フッ素樹脂などの微多孔性フィルムを用いることができる。 As a separator in the lithium secondary battery of the present invention, for example, a polyolefin such as polyethylene or polypropylene, or a microporous film such as a fluororesin can be used.
本発明に係る非水電解質リチウム二次電池は、乾燥空気または不活性ガス雰囲気において、負極および正極を、セパレーターを介して積層、あるいは積層したものを捲回した後に、電池缶に収容したり、合成樹脂と金属箔との積層体からなる可撓性フィルム等によって封口することによって電池を製造することができる。本発明のリチウム二次電池の形状としては、特に制限はないが、例えば、円筒型、角型、コイン型、ラミネート型などを挙げることができる。 The nonaqueous electrolyte lithium secondary battery according to the present invention is laminated in a dry air or an inert gas atmosphere with a negative electrode and a positive electrode laminated via a separator, or wound in a laminated battery can, A battery can be manufactured by sealing with a flexible film made of a laminate of a synthetic resin and a metal foil. The shape of the lithium secondary battery of the present invention is not particularly limited, and examples thereof include a cylindrical shape, a square shape, a coin shape, and a laminate shape.
本発明のリチウム二次電池の一実施例について図面を参照して説明する。図１に本発明のリチウム二次電池のコインタイプのセルの概略構造図を示す。図１に示すように、本発明のリチウム二次電池の一実施例のコインタイプのセルは、正極活物質を含有する正極活物質層１２が設けられた正極集電体１１と、負極活物質を含有する負極活物質層１３が設けられた負極集電体１４と、正極と負極を分ける多孔質のセパレータ１５と、正極活物質層の１２表面、負極活物質１３の表面および多孔質セパレータ１５を浸漬する電解液（図示せず）と、これらを収納する外缶（図示せず）で構成される。
An embodiment of the lithium secondary battery of the present invention will be described with reference to the drawings. FIG. 1 shows a schematic structural diagram of a coin-type cell of the lithium secondary battery of the present invention. As shown in FIG. 1, a coin-type cell of an embodiment of the lithium secondary battery of the present invention includes a positive electrode
[電池の作製]
正極集電体１１として２０μｍのアルミニウム箔を用い、この上に正極活物質としてＬｉＭｎ2Ｏ4を用いて調製した塗布液を塗布し正極活物質層１２を成形し正極を作成した。負極集電体１４として１０μｍの銅箔を用い、この上に負極活物質としてリチウム金属を用いて蒸着して２０μｍの負極活物質層１３を成形し負極を作成した。電解液は、溶媒としてエチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）の体積比：３０／７０の混合溶媒を用い、この溶媒中に１ｍｏｌ／ＬのＬｉＢＦ4を溶解させた。更に種々の濃度の３−ヒドロキシ−１，３−プロパンスルトンを加え溶解した。そして、負極と正極とをポリエチレンからなるセパレーター１５を介して積層し、コイン型二次電池を作製した。
[実施例１−６]：充放電サイクル試験
温度２０℃において、充電レート０．０５Ｃ、放電レート０．１Ｃ、充電終止電圧４．２Ｖ、放電終止電圧３．０Ｖ、リチウム金属負極の利用率（放電深度）は３３％とした。容量維持率（％）は１００サイクル後の放電容量（ｍＡｈ）を、１０サイクル目の放電容量（ｍＡｈ）で割った値である。サイクル試験で得られた結果を下記表１に示す。
（比較例１、２）
比較例１ではヒドロキシプロパンスルトンを添加しないこと、比較例２ではヒドロキシプロパンスルトンに代えて１−ヘキサノール２５ｍＭを添加した以外は、実施例と全く同様にしてコイン型二次電池を作製し、充放電サイクル試験を実施した。結果を表１に併せて記載する。
[Battery fabrication]
A 20 μm aluminum foil was used as the positive electrode
[Example 1-6]: Charge / discharge cycle test At a temperature of 20 ° C., a charge rate of 0.05 C, a discharge rate of 0.1 C, a charge end voltage of 4.2 V, a discharge end voltage of 3.0 V, a utilization rate of a lithium metal negative electrode ( The depth of discharge) was 33%. The capacity retention rate (%) is a value obtained by dividing the discharge capacity (mAh) after 100 cycles by the discharge capacity (mAh) at the 10th cycle. The results obtained in the cycle test are shown in Table 1 below.
(Comparative Examples 1 and 2)
A coin-type secondary battery was prepared and charged / discharged in the same manner as in Example 1 except that hydroxypropane sultone was not added in Comparative Example 1 and that 1-hexanol 25 mM was added instead of hydroxypropane sultone in Comparative Example 2. A cycle test was performed. The results are also shown in Table 1.
結果から、添加剤としてヒドロキシプロパンスルトンを用いた場合、比較例と比べてサイクル時に於ける容量維持率が高いことが分かる。特に、ヒドロキシプロパンスルトン濃度が１〜５０ｍＭの場合に効果が大きいことが分かる。比較例２から、単なる脂肪族アルコールの添加では効果がないことが分かる。従って、ヒドロキシプロパンスルトンの効果は、ヒドロキシ基と負極表面の金属リチウムの反応が起こった後にプロパンスルトンが充放電により還元され開環し、Ｌｉ2ＣＯ3、ＬｉＦなどとともに有効な表面薄膜を負極表面上に形成できたためと推定される。 From the results, it can be seen that when hydroxypropane sultone is used as an additive, the capacity retention rate in the cycle is higher than in the comparative example. In particular, it can be seen that the effect is large when the hydroxypropane sultone concentration is 1 to 50 mM. From Comparative Example 2, it can be seen that simply adding an aliphatic alcohol has no effect. Therefore, the effect of hydroxypropane sultone is that after the reaction between the hydroxy group and metallic lithium on the negative electrode surface occurs, the propane sultone is reduced by charge / discharge and ring-opened, and an effective surface thin film with Li 2 CO 3 , LiF, etc. is formed on the negative electrode surface. It is estimated that it was formed above.
[実施例７]
負極活物質としてＳｉＯを用い、真空蒸着法にて膜厚２０μｍの負極活物質層を成形した。負極活物質をＳｉＯに代えた以外は実施例４と同様にして電池を調製した。当該電池について実施例１と同様な評価を行った。結果を表２に示す。
[実施例８]
負極活物質としてＳｎＯを用いた。ＳｎＯ：導電剤（カーボンブラック）：ＰＶＤＦ（ポリビニリデンフルオライド）＝８５：５：１０の重量比となるようにＰＶＤＦのＮ−メチルピロリドン溶液とＳｎＯ、導電剤を混錬し、厚さ１０μｍの銅箔に塗布した。これを１００℃で１２時間乾燥後、ローラープレスにより加圧成型し、負極活物質層を成形し負極を調製した。負極の厚みは５０μｍとした。負極活物質をＳｎＯとし、塗布法にて負極を作製した以外は実施例４と同様にして電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表２に示す。
[実施例９]
負極活物質としてＬｉxＳｉ（３≦ｘ≦４）を用い、真空蒸着法にて膜厚２０μｍの負極活物質層を成形した。負極活物質をＬｉxＳｉに代えた以外は実施例４と同様にして電池を調製した。当該電池について実施例１と同様な評価を行った。結果を表２に示す。
[実施例１０]
負極活物質としてＬｉyＳｎ（３≦ｙ≦４）を用い、真空蒸着法にて膜厚２０μｍの負極活物質層を成形した。負極活物質をＬｉyＳｎに代えた以外は実施例４と同様にして電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表２に示す。
（比較例３）
実施例７において、ヒドロキシプロパンスルトンを添加しないこと以外は全く同様にしてコイン型二次電池を作製し、充放電サイクル試験を実施した。結果を表２に併せて記載する。
[Example 7]
SiO was used as the negative electrode active material, and a negative electrode active material layer having a thickness of 20 μm was formed by vacuum deposition. A battery was prepared in the same manner as in Example 4 except that the negative electrode active material was changed to SiO. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[Example 8]
SnO was used as the negative electrode active material. SnO: Conductive agent (carbon black): PVDF (polyvinylidene fluoride) = 85: 5: 10 A PVDF N-methylpyrrolidone solution, SnO, and a conductive agent were mixed so as to have a weight ratio of 10 μm in thickness. It applied to copper foil. This was dried at 100 ° C. for 12 hours and then pressure-molded by a roller press to form a negative electrode active material layer to prepare a negative electrode. The thickness of the negative electrode was 50 μm. A battery was produced in the same manner as in Example 4 except that the negative electrode active material was SnO and a negative electrode was produced by a coating method. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[Example 9]
Li x Si (3 ≦ x ≦ 4) was used as the negative electrode active material, and a negative electrode active material layer having a thickness of 20 μm was formed by vacuum deposition. A battery was prepared in the same manner as in Example 4 except that the negative electrode active material was changed to Li x Si. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[Example 10]
Li y Sn (3 ≦ y ≦ 4) was used as the negative electrode active material, and a negative electrode active material layer having a thickness of 20 μm was formed by vacuum deposition. A battery was fabricated in the same manner as in Example 4 except that the negative electrode active material was changed to Li y Sn. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 2.
(Comparative Example 3)
In Example 7, a coin-type secondary battery was produced in the same manner except that hydroxypropane sultone was not added, and a charge / discharge cycle test was performed. The results are also shown in Table 2.
結果から、負極活物質として酸化物やリチウム合金を用いた系でも、添加剤としてヒドロキシプロパンスルトンを用いるとサイクル時に於ける容量維持率が高いことが分かる。
[実施例１１、１２]
電解液溶剤を有機常温溶融塩系に代えた以外は実施例４と同様にして電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表３に示す。
（比較例４）
実施例１１において、ヒドロキシプロパンスルトンを添加しないこと以外は全く同様にしてコイン型二次電池を作製し、充放電サイクル試験を実施した。結果を表２に併せて記載する。
From the results, it can be seen that even in a system using an oxide or a lithium alloy as the negative electrode active material, when hydroxypropane sultone is used as an additive, the capacity retention rate during cycling is high.
[Examples 11 and 12]
A battery was produced in the same manner as in Example 4 except that the electrolyte solvent was changed to an organic room temperature molten salt system. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 3.
(Comparative Example 4)
In Example 11, a coin-type secondary battery was produced in the same manner except that hydroxypropane sultone was not added, and a charge / discharge cycle test was performed. The results are also shown in Table 2.
表３の結果を比較すると、有機常温溶融塩を溶媒として用いた系においても、添加剤としてヒドロキシプロパンスルトンを用いるとサイクル時に於ける容量維持率が高いことが分かる。また、有機常温溶融塩とカーボネート溶剤の混合溶媒を用いた系でもヒドロキシプロパンスルトンが有用であることが分かる。 Comparing the results shown in Table 3, it can be seen that even in a system using an organic room temperature molten salt as a solvent, the capacity maintenance rate during the cycle is high when hydroxypropane sultone is used as an additive. It can also be seen that hydroxypropane sultone is useful even in a system using a mixed solvent of an organic room temperature molten salt and a carbonate solvent.
[実施例１３]
負極活物質としてＬｉ2ＳｉＯ3を用いた。Ｌｉ2ＳｉＯ3：導電剤（カーボンブラック）：ＰＶＤＦ（ポリビニリデンフルオライド）＝８５：５：１０の重量比となるようにＰＶＤＦのＮ−メチルピロリドン溶液とＬｉ2ＳｉＯ3、導電剤を混錬し、厚さ10μｍのＣｕ箔に塗布した。これを１００℃で１２時間乾燥後、ローラープレスにより加圧成型し、負極活物質層を成形し、負極を調製した。負極の厚みは５０μｍとした。負極活物質をＬｉ2ＳｉＯ3とし、塗布法にて負極を作製した以外は実施例１１と同様にして電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表４に示す。
[実施例１４]
負極活物質としてＬｉzＡｌ（０≦ｘ≦１）を用い、真空蒸着法にて膜厚２０μｍの負極活物質層を成形し負極を調製した。負極活物質をＬｉzＡｌに代えた以外は実施例１１と同様にして電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表４に示す。
[実施例１５]
負極活物質としてＧｅＯとＰｂとＬｉの混合物（重量比ＧｅＯ：Ｐｂ：Ｌｉ＝３：２：２）を用いた。負極活物質をＧｅＯとＰｂとＬｉの混合物に代えた以外は実施例１３と同様にして塗布法にて厚さ５０μｍの負極活物質層を成形し、負極を調製し電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表４に示す。
[実施例１６]
負極活物質としてＡｇとＩｎの混合物（重量比Ａｇ：Ｉｎ＝１：２）を用いた。負極活物質をＡｇとＩｎの混合物に代えた以外は実施例１３と同様にして塗布法にて厚さ５０μｍの負極活物質層を成形し負極を調製し、電池を作製した。当該電池について実施例１と同様な評価を行った。結果を表４に示す。
（比較例５）
実施例１３において、ヒドロキシプロパンスルトンを添加しないこと以外は全く同様にしてコイン型二次電池を作製し、充放電サイクル試験を実施した。結果を表４に併せて記載する。
[Example 13]
Li 2 SiO 3 was used as the negative electrode active material. Li 2 SiO 3 : Conductive agent (carbon black): PVDF (polyvinylidene fluoride) = kneaded PVDF N-methylpyrrolidone solution with Li 2 SiO 3 and conductive agent so that the weight ratio is 85: 5: 10. And applied to a Cu foil having a thickness of 10 μm. This was dried at 100 ° C. for 12 hours, and then pressure-molded with a roller press to form a negative electrode active material layer to prepare a negative electrode. The thickness of the negative electrode was 50 μm. A battery was fabricated in the same manner as in Example 11 except that the negative electrode active material was Li 2 SiO 3 and the negative electrode was fabricated by a coating method. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 4.
[Example 14]
Li z with Al (0 ≦ x ≦ 1) as an anode active material, and the molded negative electrode active material layer having a thickness of 20μm anode prepared by vacuum deposition. A battery was fabricated in the same manner as in Example 11 except that the negative electrode active material was changed to Li z Al. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 4.
[Example 15]
A mixture of GeO, Pb, and Li (weight ratio GeO: Pb: Li = 3: 2: 2) was used as the negative electrode active material. A negative electrode active material layer having a thickness of 50 μm was formed by a coating method in the same manner as in Example 13 except that the negative electrode active material was changed to a mixture of GeO, Pb, and Li, and a negative electrode was prepared to prepare a battery. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 4.
[Example 16]
A mixture of Ag and In (weight ratio Ag: In = 1: 2) was used as the negative electrode active material. A negative electrode was prepared by forming a negative electrode active material layer having a thickness of 50 μm by a coating method in the same manner as in Example 13 except that the negative electrode active material was changed to a mixture of Ag and In, and a battery was produced. The battery was evaluated in the same manner as in Example 1. The results are shown in Table 4.
(Comparative Example 5)
In Example 13, a coin-type secondary battery was produced in the same manner except that hydroxypropane sultone was not added, and a charge / discharge cycle test was performed. The results are also shown in Table 4.
表４の結果を比較すると、有機常温溶融塩を溶媒として用いた系でも、負極に酸化物やリチウム合金を用いた場合に、添加剤としてヒドロキシプロパンスルトンを用いるとサイクル時に於ける容量維持率が高いことが分かる。 Comparing the results shown in Table 4, even in a system using an organic room temperature molten salt as a solvent, when an oxide or a lithium alloy is used for the negative electrode, if hydroxypropane sultone is used as an additive, the capacity retention rate at the time of cycling is increased. I understand that it is expensive.
１１ 正極集電体
１２ 正極活物質層
１３ 負極活物質層
１４ 負極集電体
１５ 多孔質セパレータ
DESCRIPTION OF
Claims (13)
で表されるイミダゾリウム誘導体、および／または式（３）And / or the formula (3)
で表されるピリジニウム誘導体を含むことを特徴とする請求項３記載のリチウム二次電池用非水系電解液。The non-aqueous electrolyte for lithium secondary batteries of Claim 3 characterized by including the pyridinium derivative represented by these.
Ｌｉ Li aa （Ａ(A xx ＭｎMn 2-x2-x ）Ｏ) O 4Four （４） (4)
（式中、Ａは、Ｎｉ、Ｃｏ、Ｆｅ、Ｔｉ、ＣｒまたはＣｕを示し、ｘは０＜ｘ＜２、ａは０＜ａ＜１．２の数値を示す。）(In the formula, A represents Ni, Co, Fe, Ti, Cr or Cu, x represents a numerical value of 0 <x <2, and a represents 0 <a <1.2.)
で表されることを特徴とする請求項１１記載のリチウム二次電池。The lithium secondary battery according to claim 11, represented by:
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| KR20200105233A (en) | 2019-02-28 | 2020-09-07 | 동우 화인켐 주식회사 | A compound, and an electrolyte solution and a secondary battery comprising the compound |
| KR20200105242A (en) | 2019-02-28 | 2020-09-07 | 동우 화인켐 주식회사 | A compound, and an electrolyte solution and a secondary battery comprising the compound |
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