JP2021144926A - Non-aqueous electrolyte for power storage device, and power storage device - Google Patents
Non-aqueous electrolyte for power storage device, and power storage device Download PDFInfo
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- JP2021144926A JP2021144926A JP2020135916A JP2020135916A JP2021144926A JP 2021144926 A JP2021144926 A JP 2021144926A JP 2020135916 A JP2020135916 A JP 2020135916A JP 2020135916 A JP2020135916 A JP 2020135916A JP 2021144926 A JP2021144926 A JP 2021144926A
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- Prior art keywords
- power storage
- storage device
- aqueous
- general formula
- aqueous electrolyte
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- 238000003860 storage Methods 0.000 title claims abstract description 68
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 44
- -1 cyclic sulfuric acid ester Chemical class 0.000 claims abstract description 72
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 55
- 239000003125 aqueous solvent Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 9
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- 238000000354 decomposition reaction Methods 0.000 abstract description 18
- 238000004040 coloring Methods 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
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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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Abstract
Description
本発明は、化学的安定性を高い水準で維持できる蓄電デバイス用非水電解液および蓄電デバイスに関する。 The present invention relates to a non-aqueous electrolyte solution for a power storage device and a power storage device capable of maintaining a high level of chemical stability.
近年、蓄電デバイス、特にリチウム二次電池は、携帯電話やノート型パソコン等の小型電子機器、電気自動車や電力貯蔵用として広く使用されている。これらの電子機器や自動車は、真夏の高温下や極寒の低温下等広い温度範囲で使用される可能性があるため、広い温度範囲でバランス良く電気化学特性を向上させることが求められている。
特に地球温暖化防止のため、ＣＯ２排出量を削減することが急務となっており、リチウム二次電池やキャパシタ等の蓄電デバイスからなる蓄電装置を搭載した環境対応車の中でも、ハイブリッド電気自動車（ＨＥＶ）、プラグインハイブリッド電気自動車（ＰＨＥＶ）、バッテリー電気自動車（ＢＥＶ）の早期普及が求められている。自動車は移動距離が長いため、熱帯の非常に暑い地域から極寒の地域まで幅広い温度範囲の地域で使用される可能性がある。特にこれらの車載用の蓄電デバイスは、高温から低温まで幅広い温度範囲で使用しても電気化学特性が低下しないことが要求されている。従って、蓄電デバイス用材料にも同様に幅広い温度範囲での化学的安定性が要求される。
尚、本明細書において、リチウム二次電池という用語は、いわゆるリチウムイオン二次電池も含む概念として用いる。
In recent years, power storage devices, particularly lithium secondary batteries, have been widely used for small electronic devices such as mobile phones and notebook personal computers, electric vehicles, and power storage. Since these electronic devices and automobiles may be used in a wide temperature range such as a high temperature in midsummer or a low temperature in extremely cold, it is required to improve the electrochemical characteristics in a well-balanced manner in a wide temperature range.
In particular, in order to prevent global warming, there is an urgent need to reduce CO 2 emissions, and among environmentally friendly vehicles equipped with power storage devices consisting of power storage devices such as lithium secondary batteries and capacitors, hybrid electric vehicles ( HEV), plug-in hybrid electric vehicles (PHEV), and battery electric vehicles (BEV) are required to be widely used at an early stage. Due to the long travel distances of automobiles, they can be used in a wide range of temperatures, from extremely hot tropical regions to extremely cold regions. In particular, these in-vehicle power storage devices are required not to deteriorate their electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature. Therefore, materials for power storage devices are also required to have chemical stability over a wide temperature range.
In this specification, the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
リチウム二次電池は、主にリチウムを吸蔵および放出可能な材料を含む正極および負極、リチウム塩と非水溶媒からなる非水電解液から構成され、非水溶媒としては、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）等のカーボネートが使用されている。
また、負極としては、金属リチウム、リチウムを吸蔵および放出可能な金属化合物（金属単体、酸化物、リチウムとの合金等）や炭素材料が知られており、特にリチウムを吸蔵および放出することが可能なコークス、人造黒鉛、天然黒鉛等の炭素材料を用いたリチウム二次電池が広く実用化されている。
The lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, a non-aqueous electrolytic solution composed of a lithium salt and a non-aqueous solvent, and examples of the non-aqueous solvent include ethylene carbonate (EC). A carbonate such as propylene carbonate (PC) is used.
Further, as the negative electrode, metallic lithium, a metal compound capable of occluding and releasing lithium (single metal, oxide, alloy with lithium, etc.) and a carbon material are known, and in particular, lithium can be occluded and released. Lithium secondary batteries using carbon materials such as occlusion, artificial graphite, and natural graphite have been widely put into practical use.
例えば、天然黒鉛や人造黒鉛等の高結晶化した炭素材料を負極材料として用いたリチウム二次電池は、非水電解液中の溶媒が充電時に負極表面で還元分解することにより発生した分解物やガスが、電池の望ましい電気化学的反応を阻害するため、サイクル特性の低下を生じることが分かっている。また、非水溶媒の分解物が蓄積すると、負極へのリチウムの吸蔵および放出がスムーズにできなくなり、広い温度範囲で使用した場合における電気化学特性が低下しやすくなる。
更に、リチウム金属やその合金、スズまたはケイ素等の金属単体やその酸化物を負極材料として用いたリチウム二次電池は、初期の容量は高いもののサイクル中に微粉化が進むため、炭素材料の負極に比べて非水溶媒の還元分解が加速的に起こり、電池容量やサイクル特性のような電池性能が大きく低下することが知られている。また、これらの負極材料の微粉化や非水溶媒の分解物が蓄積すると、負極へのリチウムの吸蔵および放出がスムーズにできなくなり、広い温度範囲で使用した場合における電気化学特性が低下しやすくなる。
For example, a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposition product generated by reduction decomposition of a solvent in a non-aqueous electrolytic solution on the negative electrode surface during charging. It has been found that the gas interferes with the desired electrochemical reaction of the battery, resulting in reduced cycle characteristics. Further, when the decomposition product of the non-aqueous solvent accumulates, it becomes impossible to smoothly occlude and release lithium to the negative electrode, and the electrochemical characteristics when used in a wide temperature range tend to deteriorate.
Further, a lithium secondary battery using a lithium metal or an alloy thereof, a single metal such as tin or silicon or an oxide thereof as a negative electrode material has a high initial capacity but becomes finer during the cycle, so that the negative electrode of a carbon material is used. It is known that the reductive decomposition of a non-aqueous solvent occurs at an accelerated rate, and the battery performance such as battery capacity and cycle characteristics is significantly reduced. In addition, if these negative electrode materials are pulverized or the decomposition products of non-aqueous solvents are accumulated, the storage and release of lithium into the negative electrode cannot be performed smoothly, and the electrochemical characteristics are likely to deteriorate when used in a wide temperature range. ..
一方、正極として、例えばＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉＯ２、ＬｉＦｅＰＯ４等を用いたリチウム二次電池は、非水電解液中の非水溶媒が充電状態で正極材料と非水電解液との界面において、局部的に一部酸化分解することにより発生した分解物やガスが電池の望ましい電気化学的反応を阻害するため、やはり広い温度範囲で使用した場合における電気化学特性の低下を生じることが分かっている。 On the other hand, in a lithium secondary battery using, for example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4, etc. as the positive electrode, the non-aqueous solvent in the non-aqueous electrolyte solution is charged and the positive electrode material and the non-aqueous electrolyte solution are used. At the interface of the battery, the decomposition products and gas generated by the partial oxidative decomposition of the battery inhibit the desirable electrochemical reaction of the battery, which also causes a decrease in the electrochemical characteristics when used in a wide temperature range. I know.
以上のように、正極上や負極上で非水電解液が分解するときの分解物やガスにより、リチウムイオンの移動が阻害されたり、電池が膨れたりすることで電池性能が低下していた。さらに、電解液の化学的安定性に関しても、幅広い温度範囲での安定性が求められている。これらの課題を改善するために、非水電解液に添加剤を添加することで、正極上や負極上で非水電解液の分解を抑制する技術が適用されている。
特許文献１には、環状硫酸エステルを非水電解液に添加することによりサイクル特性を向上させた電池が記載されている。
また、特許文献２には、特定の部位を有する環状スルホン化合物を非水電解液に添加することにより高温サイクル特性や電圧維持特性を向上させた電池が記載されている。
さらに、特許文献３には、有機シラン化合物を添加することにより非水電解液の安定性を向上させた電池が記載されている。
As described above, the decomposition products and gases when the non-aqueous electrolyte solution decomposes on the positive electrode and the negative electrode hinder the movement of lithium ions and cause the battery to swell, resulting in deterioration of battery performance. Further, the chemical stability of the electrolytic solution is also required to be stable in a wide temperature range. In order to improve these problems, a technique for suppressing the decomposition of the non-aqueous electrolytic solution on the positive electrode and the negative electrode by adding an additive to the non-aqueous electrolytic solution has been applied.
Patent Document 1 describes a battery in which the cycle characteristics are improved by adding a cyclic sulfate ester to a non-aqueous electrolytic solution.
Further, Patent Document 2 describes a battery in which high temperature cycle characteristics and voltage maintenance characteristics are improved by adding a cyclic sulfone compound having a specific moiety to a non-aqueous electrolytic solution.
Further, Patent Document 3 describes a battery in which the stability of the non-aqueous electrolytic solution is improved by adding an organic silane compound.
本発明は、高温保存後の非水電解液の着色を抑制し、かつ高温保存による環状硫酸エステルや環状スルホン化合物の分解を抑制できる蓄電デバイス用非水電解液および蓄電デバイスを提供することを目的とする。 An object of the present invention is to provide a non-aqueous electrolyte solution for a power storage device and a power storage device capable of suppressing coloring of a non-aqueous electrolyte solution after high temperature storage and suppressing decomposition of a cyclic sulfate ester or a cyclic sulfone compound due to high temperature storage. And.
前述のとおり、車載用の蓄電デバイスは、高温から低温まで幅広い温度範囲で使用しても電気化学特性が低下しないことが要求されており、蓄電デバイス用材料にも同様に幅広い温度範囲での化学的安定性が要求されている。本発明者らは、上記従来技術の非水電解液の化学的安定性について詳細に検討した結果、前記特許文献１の環状硫酸エステルや前記特許文献２の特定の部位を有する環状スルホン化合物を含有する非水電解液は、一定期間の保存後に着色し、電池性能の効果を発揮できなくなることが判明した。
そこで、本発明者らは、上記課題を解決するために鋭意研究を重ね、非水溶媒に電解質塩と環状硫酸エステルおよびや環状スルホン化合物が溶解されている非水電解液において、有機シラン化合物を加えることで、非水電解液の化学的安定性が改善できることを見出し、本発明を完成した。なお、前記特許文献３には、有機シラン化合物を環状硫酸エステルまたは環状スルホン化合物と組合せた非水電解液の化学的安定性に関して記載はない。
As described above, in-vehicle power storage devices are required to have no deterioration in electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature, and materials for power storage device are also required to have chemistry in a wide temperature range. Stability is required. As a result of detailed examination of the chemical stability of the non-aqueous electrolytic solution of the prior art, the present inventors include the cyclic sulfate ester of Patent Document 1 and the cyclic sulfone compound having a specific site of Patent Document 2. It was found that the non-aqueous electrolyte solution was colored after being stored for a certain period of time, and the effect of battery performance could not be exhibited.
Therefore, the present inventors have conducted intensive studies to solve the above problems, and have found organic silane compounds in a non-aqueous electrolytic solution in which an electrolyte salt, a cyclic sulfate ester, and a cyclic sulfone compound are dissolved in a non-aqueous solvent. We have found that the chemical stability of the non-aqueous electrolyte solution can be improved by adding it, and completed the present invention. Note that Patent Document 3 does not describe the chemical stability of a non-aqueous electrolytic solution in which an organic silane compound is combined with a cyclic sulfate ester or a cyclic sulfone compound.
すなわち、本発明は、下記の（１）および（２）を提供するものである。 That is, the present invention provides the following (1) and (2).
（１）非水溶媒に電解質塩が溶解されている非水電解液において、一般式（Ｉ）で表される環状硫酸エステルおよび一般式（ＩＩ）で表される環状スルホン化合物から選ばれる１種以上と、一般式（ＩＩＩ）で表される有機シラン化合物とを含有することを特徴とする蓄電デバイス用非水電解液。
(1) One selected from a cyclic sulfate ester represented by the general formula (I) and a cyclic sulfone compound represented by the general formula (II) in a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent. A non-aqueous electrolyte solution for a power storage device, which contains the above and an organic silane compound represented by the general formula (III).
（２）正極、負極および非水溶媒に電解質塩が溶解されている非水電解液を備えた蓄電デバイスであって、該非水電解液が前記（１）に記載の非水電解液であることを特徴とする蓄電デバイス。 (2) A power storage device including a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, and a non-aqueous solvent, and the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to (1). A power storage device characterized by.
本発明によれば、高温保存後の非水電解液の着色を抑制し、かつ高温保存による環状硫酸エステルや環状スルホン化合物の分解を抑制できる蓄電デバイス用非水電解液および蓄電デバイスを提供することができる。 According to the present invention, there is provided a non-aqueous electrolyte solution for a power storage device and a power storage device capable of suppressing the coloring of the non-aqueous electrolyte solution after high temperature storage and suppressing the decomposition of cyclic sulfuric acid ester and cyclic sulfone compound due to high temperature storage. Can be done.
本発明は、蓄電デバイス用非水電解液および蓄電デバイスに関する。 The present invention relates to a non-aqueous electrolyte solution for a power storage device and a power storage device.
〔非水電解液〕
本発明の非水電解液は、非水溶媒に電解質塩が溶解されている非水電解液において、一般式（Ｉ）で表される環状硫酸エステルおよび一般式（ＩＩ）で表される環状スルホン化合物から選ばれる１種以上と、一般式（ＩＩＩ）で表される有機シラン化合物とを含有することを特徴とする蓄電デバイス用非水電解液である。
[Non-aqueous electrolyte]
The non-aqueous electrolyte solution of the present invention is a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent, and is a cyclic sulfate ester represented by the general formula (I) and a cyclic sulfone represented by the general formula (II). It is a non-aqueous electrolyte solution for a power storage device, which comprises one or more selected from compounds and an organic silane compound represented by the general formula (III).
本発明の非水電解液が、化学的な安定性を改善できる理由は必ずしも明らかではないが、以下のように考える。
非水電解液中において、一般式（Ｉ）で表される環状硫酸エステルや一般式（ＩＩ）で表される特定の部位を有する環状スルホン化合物が、一定時間経過した際に、電解質塩、特にＬｉＰＦ６と徐々に反応することで、環状構造が分解され、発生した一部の分解物が非水電解液の着色を促していると推測される。そこで、非水電解液に一般式（ＩＩＩ）で表される有機シラン化合物を更に添加することで、電解質塩と一般式（Ｉ）に記載される環状硫酸エステルや一般式（ＩＩ）で表される特定の部位を有する環状スルホン化合物との反応が抑制されると考えられる。このため、非水電解液の着色が抑えられ、更に環状硫酸エステルや環状スルホン化合物の分解を抑制できると考えられる。
The reason why the non-aqueous electrolyte solution of the present invention can improve the chemical stability is not always clear, but it is considered as follows.
In the non-aqueous electrolyte solution, when the cyclic sulfate ester represented by the general formula (I) or the cyclic sulfone compound having a specific moiety represented by the general formula (II) elapses for a certain period of time, the electrolyte salt, particularly It is presumed that the cyclic structure is decomposed by gradually reacting with LiPF 6, and some of the generated decomposition products promote the coloring of the non-aqueous electrolyte solution. Therefore, by further adding the organic silane compound represented by the general formula (III) to the non-aqueous electrolytic solution, it is represented by the electrolyte salt and the cyclic sulfate ester represented by the general formula (I) or the general formula (II). It is considered that the reaction with the cyclic sulfone compound having a specific site is suppressed. Therefore, it is considered that the coloring of the non-aqueous electrolytic solution can be suppressed, and further the decomposition of the cyclic sulfuric acid ester and the cyclic sulfone compound can be suppressed.
本発明の非水電解液は、下記一般式（Ｉ）で表される環状硫酸エステルおよび一般式（ＩＩ）で表される環状スルホン化合物から選ばれる１種以上と、一般式（ＩＩＩ）で表される有機シラン化合物とを含む。 The non-aqueous electrolytic solution of the present invention is represented by one or more selected from the cyclic sulfate ester represented by the following general formula (I) and the cyclic sulfone compound represented by the general formula (II), and the general formula (III). Includes organic silane compounds.
〔一般式（Ｉ）で表される化合物〕
前記一般式（Ｉ）において、Ｒ１およびＲ２はそれぞれ独立に、水素原子または炭素数１〜６のアルキル基を示し、Ｒ１とＲ２が互いに結合し環を形成してもよく、炭素数１〜４のアルキル基が好ましく、炭素数１または２のアルキル基がより好ましい。
[Compound represented by the general formula (I)]
In the general formula (I), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring, or carbon. Alkyl groups having the number 1 to 4 are preferable, and alkyl groups having 1 or 2 carbon atoms are more preferable.
前記Ｒ１およびＲ２の具体例としては、水素原子、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、もしくはｎ−ヘキシル基などの直鎖のアルキル基またはｉｓｏ−プロピル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基もしくはｔｅｒｔ−ブチル基などの分枝のアルキル基が好適に挙げられ、水素原子、メチル基、エチル基、ｎ−プロピル基またはｎ−ブチル基が好ましく、水素原子、メチル基またはエチル基がより好ましい。 Specific examples of R 1 and R 2 include linear alkyl groups such as hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, or n-hexyl group, or iso. Branched alkyl groups such as −propyl group, iso-butyl group, sec-butyl group or tert-butyl group are preferred, with hydrogen atom, methyl group, ethyl group, n-propyl group or n-butyl group. Preferably, a hydrogen atom, a methyl group or an ethyl group is more preferable.
また、Ｒ１およびＲ２が互いに結合し環を形成する場合の具体例としては、シクロブチル構造、シクロペンチル構造、シクロヘキシル構造、シクロヘプチル構造またはシクロオクチル構造を有するものが好適に挙げられ、シクロペンチル構造またはシクロヘキシル構造を有するものがより好ましい。 Further, specific examples of the case where R 1 and R 2 are bonded to each other to form a ring include those having a cyclobutyl structure, a cyclopentyl structure, a cyclohexyl structure, a cycloheptyl structure or a cyclooctyl structure, and a cyclopentyl structure or a cyclopentyl structure or Those having a cyclopentyl structure are more preferable.
前記一般式（Ｉ）で表される環状硫酸エステルとしては、具体的に以下の化合物が好適に挙げられる。 Specific preferred examples of the cyclic sulfuric acid ester represented by the general formula (I) include the following compounds.
上記好適例の中でも化合物Ａ１〜Ａ３、Ａ１２、Ａ１３、Ａ１４、Ａ１６またはＡ１７が好ましく、１，３，２−ジオキサチオラン−２，２−ジオキシド（化合物Ａ１）、４，５−ジメチル−１，３，２−ジオキサチオラン−２，２−ジオキシド（化合物Ａ１２）またはテトラヒドロ−４Ｈ−シクロペンタ［ｄ］［１，３，２］ジオキサチオール２，２−ジオキシド（化合物Ａ１６）がより好ましい。 Among the above preferred examples, compounds A1-A3, A12, A13, A14, A16 or A17 are preferable, 1,3,2-dioxathiolane-2,2-dioxide (Compound A1), 4,5-dimethyl-1,3. 2-Dioxathiolane-2,2-dioxide (Compound A12) or tetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol 2,2-dioxide (Compound A16) is more preferred.
前記一般式（ＩＩ）で表される環状スルホン化合物としては、具体的に以下の化合物が好適に挙げられる。 Specific preferred examples of the cyclic sulfone compound represented by the general formula (II) include the following compounds.
上記好適例の中でも化合物Ｃ１〜Ｃ３、Ｃ１１、またはＣ１６が好ましく、１，２，５−オキサジチラン ２，２，５，５−テトラオキシド（Ｃ１）、１，２，６−オキサジチアン ２，２，６，６−テトラオキシド（Ｃ２）、または１，２，７−オキサジチエパン ２，２，７，７−テトラオキシド（Ｃ３）がより好ましく、１，２，６−オキサジチアン ２，２，６，６−テトラオキシド（Ｃ２）がさらに好ましい。 Among the above preferred examples, compounds C1 to C3, C11, or C16 are preferable, and 1,2,5-oxaditilane 2,2,5,5-tetraoxide (C1), 1,2,6-oxadithian 2,2,6 , 6-Tetraoxide (C2), or 1,2,7-oxadithiepan 2,2,7,7-tetraoxide (C3) is more preferred, 1,2,6-oxadithian 2,2,6,6-tetra Oxide (C2) is more preferred.
本発明の非水電解液において、非水電解液に含有される前記一般式（Ｉ）で表される環状硫酸エステルおよび前記一般式（ＩＩ）で表される環状スルホン化合物の含有量はそれぞれ、非水電解液中に、非水電解液全量に対して、０．００１〜５質量％であることが好ましい。該含有量が５質量％以下であれば、電極上に過度に被膜が形成されるおそれが少なく、また０．００１質量％以上であれば被膜の強度が高まるので上記範囲であることが好ましい。該含有量は、非水電解液中に０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましい。また、３質量％以下がより好ましく、２質量％以下が更に好ましい。 In the non-aqueous electrolytic solution of the present invention, the contents of the cyclic sulfate ester represented by the general formula (I) and the cyclic sulfone compound represented by the general formula (II) contained in the non-aqueous electrolytic solution are respectively. It is preferably 0.001 to 5% by mass in the non-aqueous electrolytic solution with respect to the total amount of the non-aqueous electrolytic solution. If the content is 5% by mass or less, there is little possibility that an excessive film is formed on the electrode, and if it is 0.001% by mass or more, the strength of the film is increased, so the above range is preferable. The content is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more in the non-aqueous electrolytic solution. Further, 3% by mass or less is more preferable, and 2% by mass or less is further preferable.
〔一般式（ＩＩＩ）で表される化合物〕
前記一般式（ＩＩＩ）において、Ｒ３およびＲ４はそれぞれ独立に、炭素数１〜３のアルキル基を示し、炭素数１または２のアルキル基がより好ましい。
[Compound represented by the general formula (III)]
In the general formula (III), R 3 and R 4 independently represent an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 or 2 carbon atoms is more preferable.
前記Ｒ３およびＲ４の具体例としては、メチル基、エチル基、ｎ−プロピル基またはｉｓｏ−プロピル基が好適に挙げられ、メチル基またはエチル基がより好ましい。 Specific examples of R 3 and R 4 are preferably a methyl group, an ethyl group, an n-propyl group or an iso-propyl group, and a methyl group or an ethyl group is more preferable.
前記一般式（ＩＩＩ）において、Ｒ５およびＲ６はそれぞれ独立に、炭素数１〜３のアルキル基または置換基を有していてもよいアリール基を示す。 In the general formula (III), R 5 and R 6 each independently represent an aryl group which may have an alkyl group or a substituent having 1 to 3 carbon atoms.
前記Ｒ５およびＲ６の具体例としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、フェニル基、トリル基またはキシリル基が好適に挙げられ、メチル基またはフェニル基がより好ましい。 Specific examples of the R 5 and R 6 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a phenyl group, a tolyl group or a xsilyl group, and a methyl group or a phenyl group is more preferable. ..
前記一般式（ＩＩＩ）で表される有機シラン化合物としては、具体的に以下の化合物が好適に挙げられる。 Specific preferred examples of the organic silane compound represented by the general formula (III) include the following compounds.
上記好適例の中でも化合物Ｂ１、Ｂ２またはＢ１０が好ましく、ジメトキシジメチルシラン（化合物B１）またはジフェニルジメトキシシラン（化合物Ｂ１０）がより好ましい。 Among the above preferred examples, compound B1, B2 or B10 is preferable, and dimethoxydimethylsilane (compound B1) or diphenyldimethoxysilane (compound B10) is more preferable.
本発明の非水電解液において、非水電解液に含有される前記一般式（ＩＩ）で表される有機シラン化合物の含有量は、非水電解液中に、非水電解液全量に対して、０．０１〜０．５質量％であることが好ましい。該含有量は、高温保存後の一般式（Ｉ）の化合物残存量の点から、０．３質量％以下がより好ましい。また、非水電解液の着色抑制の点から、０．０１質量％以上であることが好ましく、０．０５質量％以上であることがより好ましい。 In the non-aqueous electrolytic solution of the present invention, the content of the organic silane compound represented by the general formula (II) contained in the non-aqueous electrolytic solution is the total amount of the non-aqueous electrolytic solution in the non-aqueous electrolytic solution. , 0.01 to 0.5% by mass is preferable. The content is more preferably 0.3% by mass or less from the viewpoint of the residual amount of the compound of the general formula (I) after storage at high temperature. Further, from the viewpoint of suppressing coloration of the non-aqueous electrolytic solution, it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.
本発明の非水電解液において、前記一般式（Ｉ）で表される化合物および一般式（ＩＩ）で表される環状スルホン化合物から選ばれる１種以上と一般式（ＩＩＩ）で表される化合物とを、以下に述べる非水溶媒と電解質塩とを組合せることにより、高温保存後の非水電解液の着色と環状硫酸エステルや環状スルホン化合物の分解をより抑制できる。 In the non-aqueous electrolyte solution of the present invention, one or more selected from the compound represented by the general formula (I) and the cyclic sulfone compound represented by the general formula (II) and the compound represented by the general formula (III). By combining the above-mentioned non-aqueous solvent and the electrolyte salt, it is possible to further suppress the coloring of the non-aqueous electrolytic solution after high-temperature storage and the decomposition of the cyclic sulfate ester and the cyclic sulfone compound.
〔非水溶媒〕
本発明の非水電解液に使用される非水溶媒としては、環状カーボネート、鎖状エステル、ラクトン、エーテルおよびアミドから選ばれる１種または２種以上が好適に挙げられる。
[Non-aqueous solvent]
As the non-aqueous solvent used in the non-aqueous electrolytic solution of the present invention, one or more selected from cyclic carbonates, chain esters, lactones, ethers and amides are preferably used.
なお、「鎖状エステル」なる用語は、鎖状カーボネートおよび鎖状カルボン酸エステルを含む概念として用いる。 The term "chain ester" is used as a concept including a chain carbonate and a chain carboxylic acid ester.
環状カーボネートとしては、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、１，２−ブチレンカーボネート、２，３−ブチレンカーボネート、４−フルオロ−１，３−ジオキソラン−２−オン（ＦＥＣ）、トランスもしくはシス−４，５−ジフルオロ−１，３−ジオキソラン−２−オン（以下、両者を総称して「ＤＦＥＣ」という）、ビニレンカーボネート（ＶＣ）、ビニルエチレンカーボネート（ＶＥＣ）および４−エチニル−１，３−ジオキソラン−２−オン（ＥＥＣ）から選ばれる一種または二種以上が挙げられ、エチレンカーボネート、プロピレンカーボネート、４−フルオロ−１，３−ジオキソラン−２−オン、ビニレンカーボネートおよび４−エチニル−１，３−ジオキソラン−２−オンから選ばれる一種または二種以上がより好適である。 Cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1,3-dioxolane-2-one (FEC), trans or Sis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter, both are collectively referred to as "DFEC"), vinylene carbonate (VC), vinylethylene carbonate (VEC) and 4-ethynyl-1, One or more selected from 3-dioxolane-2-one (EEC) can be mentioned, including ethylene carbonate, propylene carbonate, 4-fluoro-1,3-dioxolan-2-one, vinylene carbonate and 4-ethynyl-1. , 3-Dioxolane-2-one selected from one or more is more preferred.
これらの溶媒は一種類で使用してもよく、また二種類以上を組合せて使用した場合は、広い温度範囲での電気化学特性の改善効果が更に向上するので好ましく、３種類以上を組合せて使用することが特に好ましい。これらの環状カーボネートの好適な組合せとしては、ＥＣとＰＣ、ＥＣとＶＣ、ＰＣとＶＣ、ＶＣとＦＥＣ、ＥＣとＦＥＣ、ＰＣとＦＥＣ、ＦＥＣとＤＦＥＣ、ＥＣとＤＦＥＣ、ＰＣとＤＦＥＣ、ＶＣとＤＦＥＣ、ＶＥＣとＤＦＥＣ、ＶＣとＥＥＣ、ＥＣとＥＥＣ、ＥＣとＰＣとＶＣ、ＥＣとＰＣとＦＥＣ、ＥＣとＶＣとＦＥＣ、ＥＣとＶＣとＶＥＣ、ＥＣとＶＣとＥＥＣ、ＥＣとＥＥＣとＦＥＣ、ＰＣとＶＣとＦＥＣ、ＥＣとＶＣとＤＦＥＣ、ＰＣとＶＣとＤＦＥＣ、ＥＣとＰＣとＶＣとＦＥＣまたはＥＣとＰＣとＶＣとＤＦＥＣ等が好ましい。前記の組合せのうち、ＥＣとＶＣ、ＥＣとＦＥＣ、ＰＣとＦＥＣ、ＥＣとＰＣとＶＣ、ＥＣとＰＣとＦＥＣ、ＥＣとＶＣとＦＥＣ、ＥＣとＶＣとＥＥＣ、ＥＣとＥＥＣとＦＥＣ、ＰＣとＶＣとＦＥＣまたはＥＣとＰＣとＶＣとＦＥＣ等の組合せがより好ましい。 One type of these solvents may be used, and when two or more types are used in combination, the effect of improving the electrochemical properties in a wide temperature range is further improved, so that it is preferable to use three or more types in combination. It is particularly preferable to do so. Suitable combinations of these cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC. , VEC and DFEC, VC and EEC, EC and EEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and EEC and FEC, PC And VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC and PC and VC and FEC or EC and PC and VC and DFEC and the like are preferable. Of the above combinations, EC and VC, EC and FEC, PC and FEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and EEC, EC and EEC and FEC, PC and A combination of VC and FEC or EC and PC and VC and FEC is more preferable.
鎖状エステルとしては、メチルエチルカーボネート（ＭＥＣ）、メチルプロピルカーボネート（ＭＰＣ）、メチルイソプロピルカーボネート（ＭＩＰＣ）、メチルブチルカーボネートおよびエチルプロピルカーボネートから選ばれる１種または２種以上の非対称鎖状カーボネート、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、ジプロピルカーボネートおよびジブチルカーボネートから選ばれる１種または２種以上の対称鎖状カーボネート、ピバリン酸メチル、ピバリン酸エチル、ピバリン酸プロピル等のピバリン酸エステル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、酢酸メチルおよび酢酸エチルから選ばれる１種または２種以上の鎖状カルボン酸エステルが好適に挙げられる。 As the chain ester, one or more asymmetric chain carbonates selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate and ethyl propyl carbonate, dimethyl One or more symmetric chain carbonates selected from carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate and dibutyl carbonate, pivalic acid esters such as methyl pivalate, ethyl pivalate, propyl pivalate, propion Preferable examples thereof include one or more chain carboxylic acid esters selected from methyl acid, ethyl propionate, propyl propionate, methyl acetate and ethyl acetate.
前記鎖状エステルの中でも、ジメチルカーボネート、メチルエチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート、メチルブチルカーボネート、プロピオン酸メチル、酢酸メチルおよび酢酸エチルから選ばれるメチル基を有する鎖状エステルが好ましく、特にメチル基を有する鎖状カーボネートが好ましい。 Among the chain esters, a chain ester having a methyl group selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate is preferable, and methyl is particularly preferable. A chain carbonate having a group is preferable.
また、鎖状カーボネートを用いる場合には、２種以上を用いることが好ましい。さらに対称鎖状カーボネートと非対称鎖状カーボネートの両方が含まれるとより好ましく、対称鎖状カーボネートの含有量が非対称鎖状カーボネートより多く含まれると更に好ましい。 When chain carbonate is used, it is preferable to use two or more kinds. Further, it is more preferable that both the symmetric chain carbonate and the asymmetric chain carbonate are contained, and it is further preferable that the content of the symmetric chain carbonate is higher than that of the asymmetric chain carbonate.
本発明の非水電解液に用いる非水溶媒における鎖状エステルの含有量は、特に制限されないが、非水電解液全量に対して、５〜９０質量％の範囲で用いるのが好ましい。該含有量が５質量％以上であれば非水電解液の粘度が高くなりすぎず、より好ましくは１０質量％以上であり、さらに好ましくは３０質量％以上であり、特に好ましくは５０質量％以上である。また、９０質量％以下であれば非水電解液の電気伝導度が低下するおそれが少ないので、上記範囲であることが好ましい。 The content of the chain ester in the non-aqueous solvent used in the non-aqueous electrolytic solution of the present invention is not particularly limited, but it is preferably used in the range of 5 to 90% by mass with respect to the total amount of the non-aqueous electrolytic solution. When the content is 5% by mass or more, the viscosity of the non-aqueous electrolytic solution does not become too high, more preferably 10% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. Is. Further, if it is 90% by mass or less, there is little possibility that the electric conductivity of the non-aqueous electrolytic solution is lowered, so that it is preferably in the above range.
〔電解質塩〕
本発明に使用される電解質塩としては、下記のリチウム塩が好適に挙げられる。
リチウム塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４等の無機リチウム塩、ＬｉＮ（ＳＯ２Ｆ）２〔ＬｉＦＳＩ〕、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２、ＬｉＣＦ３ＳＯ３、ＬｉＣ（ＳＯ２ＣＦ３）３、ＬｉＰＦ４（ＣＦ３）２、ＬｉＰＦ３（Ｃ２Ｆ５）３、ＬｉＰＦ３（ＣＦ３）３、ＬｉＰＦ３（ｉｓｏ−Ｃ３Ｆ７）３、ＬｉＰＦ５（ｉｓｏ−Ｃ３Ｆ７）等の鎖状のフッ化アルキル基を含有するリチウム塩や、（ＣＦ２）２（ＳＯ２）２ＮＬｉ、（ＣＦ２）３（ＳＯ２）２ＮＬｉ等の環状のフッ化アルキレン鎖を有するリチウム塩等が好適に挙げられ、これらの中から選ばれる少なくとも１種のリチウム塩を含むことが好ましく、これらの１種または２種以上を混合して使用することができる。
これらの中でも、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２およびＬｉＮ（ＳＯ２Ｆ）２〔ＬｉＦＳＩ〕から選ばれる１種または２種以上を含むことがより好ましく、ＬｉＰＦ６を含むことがもっとも好ましい。
電解質塩のそれぞれの濃度は、前記の非水電解液全量に対して、４質量％以上であることが好ましく、９質量％以上がより好ましく、１３質量％以上が更に好ましく、また、２８質量％以下であることが好ましく、２３質量％以下がより好ましく、２０質量％以下が更に好ましい。
[Electrolyte salt]
Preferred examples of the electrolyte salt used in the present invention include the following lithium salts.
Lithium salts include inorganic lithium salts such as LiPF 6 , LiBF 4 , and LiClO 4 , LiN (SO 2 F) 2 [LiFS I], LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiCF 3 SO 3 , LiC (SO 2 CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , Lithium salt containing a chain-like alkyl fluoride group such as LiPF 5 (iso-C 3 F 7 ), (CF 2 ) 2 (SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 ) 2 Lithium salts having a cyclic fluorinated alkylene chain such as NLi are preferably mentioned, and it is preferable to contain at least one lithium salt selected from these, and one or two or more of these are mixed. Can be used.
Among these, one or more selected from LiPF 6 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 F) 2 [LiFSI] It is more preferable to contain LiPF 6, and it is most preferable to contain LiPF 6.
The concentration of each of the electrolyte salts is preferably 4% by mass or more, more preferably 9% by mass or more, further preferably 13% by mass or more, and 28% by mass, based on the total amount of the non-aqueous electrolyte solution. It is preferably 23% by mass or less, more preferably 20% by mass or less.
〔非水電解液の製造〕
本発明の非水電解液は、例えば、前記の非水溶媒を混合し、これに前記の電解質塩および該非水電解液に対して前記一般式（Ｉ）および前記一般式（ＩＩ）で表される化合物から選ばれる１種以上と一般式（ＩＩＩ）で表される化合物とを添加することにより得ることができる。
この際、用いる非水溶媒および非水電解液に加える化合物は、生産性を著しく低下させない範囲内で、予め精製して、不純物が極力少ないものを用いることが好ましい。
[Manufacturing of non-aqueous electrolyte solution]
The non-aqueous electrolyte solution of the present invention is, for example, mixed with the non-aqueous solvent, and is represented by the general formula (I) and the general formula (II) with respect to the electrolyte salt and the non-aqueous electrolyte solution. It can be obtained by adding one or more selected from the above compounds and the compound represented by the general formula (III).
At this time, it is preferable that the compounds to be added to the non-aqueous solvent and the non-aqueous electrolytic solution to be used are those that have been purified in advance and contain as few impurities as possible within a range that does not significantly reduce the productivity.
本発明の非水電解液は、下記の第１〜第４の蓄電デバイスに使用することができ、非水電解質として、液体状のものだけでなくゲル化されているものも使用し得る。更に本発明の非水電解液は固体高分子電解質用としても使用できる。中でも電解質塩にリチウム塩を使用する第１の蓄電デバイス用（即ち、リチウム電池用）または第４の蓄電デバイス用（即ち、リチウムイオンキャパシタ用）として用いることが好ましく、リチウム電池用として用いることが更に好ましく、リチウム二次電池用として用いることが最も適している。 The non-aqueous electrolyte solution of the present invention can be used in the following first to fourth power storage devices, and as the non-aqueous electrolyte solution, not only a liquid one but also a gelled one can be used. Further, the non-aqueous electrolyte solution of the present invention can also be used for a solid polymer electrolyte. Of these, it is preferably used for a first power storage device (that is, for a lithium battery) or a fourth power storage device (that is, for a lithium ion capacitor) that uses a lithium salt as an electrolyte salt, and is preferably used for a lithium battery. More preferably, it is most suitable for use in a lithium secondary battery.
〔第１の蓄電デバイス（リチウム電池）〕
本発明の第１の蓄電デバイスであるリチウム二次電池は、正極、負極および非水溶媒に電解質塩が溶解されている前記非水電解液からなる。非水電解液以外の正極、負極等の構成部材は特に制限なく使用できる。
例えば、リチウム二次電池用正極活物質としては、コバルト、マンガンおよびニッケルからなる群より選ばれる１種または２種以上を含有するリチウムとの複合金属酸化物が使用される。これらの正極活物質は、１種単独で用いるかまたは２種以上を組合せて用いることができる。
このようなリチウム複合金属酸化物としては、例えば、ＬｉＣｏＯ２、ＬｉＣｏ１−ｘＭｘＯ２（但し、ＭはＳｎ、Ｍｇ、Ｆｅ、Ｔｉ、Ａｌ、Ｚｒ、Ｃｒ、Ｖ、Ｇａ、ＺｎおよびＣｕから選ばれる１種または２種以上の元素、０．００１≦ｘ≦０．０５）、ＬｉＭｎ２Ｏ４、ＬｉＮｉＯ２、ＬｉＣｏ１−ｘＮｉｘＯ２（０．０１＜ｘ＜１）、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ０．５Ｍｎ０．３Ｃｏ０．２Ｏ２、ＬｉＮｉ０．８Ｍｎ０．１Ｃｏ０．１Ｏ２、ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２、Ｌｉ２ＭｎＯ３とＬｉＭＯ２（Ｍは、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ等の遷移金属）との固溶体およびＬｉＮｉ１／２Ｍｎ３／２Ｏ４から選ばれる１種以上が好適に挙げられ、２種以上がより好適である。また、ＬｉＣｏＯ２とＬｉＭｎ２Ｏ４、ＬｉＣｏＯ２とＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４とＬｉＮｉＯ２のように併用してもよい。
[First power storage device (lithium battery)]
The lithium secondary battery, which is the first power storage device of the present invention, comprises the positive electrode, the negative electrode, and the non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent. Constituent members such as a positive electrode and a negative electrode other than the non-aqueous electrolytic solution can be used without particular limitation.
For example, as the positive electrode active material for a lithium secondary battery, a composite metal oxide containing one or more selected from the group consisting of cobalt, manganese and nickel is used. These positive electrode active materials can be used alone or in combination of two or more.
Examples of such lithium composite metal oxides include LiCoO 2 , LiCo 1-x M x O 2 (where M is Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn and Cu. One or more elements selected from, 0.001 ≤ x ≤ 0.05), LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 <x <1), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , LiNi 0.8 Co 0 .15 Al 0.05 O 2 , Li 2 MnO 3 and LiMO 2 (M is a transition metal such as Co, Ni, Mn, Fe) solid solution and LiNi 1/2 Mn 3/2 O 4 selected 1 More than one species is preferred, and two or more species are more preferred. Further, LiCoO 2 and LiMn 2 O 4 , LiCoO 2 and LiNiO 2 , and LiMn 2 O 4 and LiNiO 2 may be used in combination.
高充電電圧で動作するリチウム複合金属酸化物を使用すると、充電時における電解液との反応によりサイクル特性が低下しやすいが、本発明に係るリチウム二次電池ではこれらの電気化学特性の低下を抑制することができる。
特にＮｉを含む正極活物質の場合にＮｉの触媒作用により正極表面での非水溶媒の分解が起き、電池の抵抗が増加しやすい傾向にある。特に高温環境下での電気化学特性が低下しやすい傾向にあるが、本発明に係るリチウム二次電池ではこれらの電気化学特性の低下を抑制することができるので好ましい。特に、正極活物質中の全遷移金属元素の原子濃度に対するＮｉの原子濃度の割合が、３０ａｔｏｍｉｃ％を超える正極活物質を用いた場合に上記効果が顕著になるので好ましく、５０ａｔｏｍｉｃ％以上が更に好ましく、７５％以上が特に好ましい。具体的には、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ０．５Ｍｎ０．３Ｃｏ０．２Ｏ２、ＬｉＮｉ０．８Ｍｎ０．１Ｃｏ０．１Ｏ２、ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２等が好適に挙げられる。
When a lithium composite metal oxide that operates at a high charging voltage is used, the cycle characteristics tend to deteriorate due to the reaction with the electrolytic solution during charging, but the lithium secondary battery according to the present invention suppresses the deterioration of these electrochemical characteristics. can do.
In particular, in the case of a positive electrode active material containing Ni, the catalytic action of Ni causes decomposition of the non-aqueous solvent on the surface of the positive electrode, and the resistance of the battery tends to increase. In particular, the electrochemical characteristics tend to deteriorate in a high temperature environment, but the lithium secondary battery according to the present invention is preferable because the deterioration of these electrochemical characteristics can be suppressed. In particular, when the ratio of the atomic concentration of Ni to the atomic concentration of all transition metal elements in the positive electrode active material exceeds 30 atomic%, the above effect becomes remarkable, and 50 atomic% or more is more preferable. , 75% or more is particularly preferable. Specifically, LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 and the like are preferably mentioned.
更に、正極活物質として、リチウム含有オリビン型リン酸塩を用いることもできる。特に鉄、コバルト、ニッケルおよびマンガンから選ばれる少なくとも１種以上含むリチウム含有オリビン型リン酸塩が好ましい。その具体例としては、ＬｉＦｅＰＯ４、ＬｉＣｏＰＯ４、ＬｉＮｉＰＯ４、ＬｉＭｎＰＯ４等が挙げられる。
これらのリチウム含有オリビン型リン酸塩の一部は他元素で置換してもよく、鉄、コバルト、ニッケル、マンガンの一部をＣｏ、Ｍｎ、Ｎｉ、Ｍｇ、Ａｌ、Ｂ、Ｔｉ、Ｖ、Ｎｂ、Ｃｕ、Ｚｎ、Ｍｏ、Ｃａ、Ｓｒ、ＷおよびＺｒ等から選ばれる１種以上の元素で置換する、またはこれらの他元素を含有する化合物や炭素材料で被覆することもできる。これらの中では、ＬｉＦｅＰＯ４またはＬｉＭｎＰＯ４が好ましい。
また、リチウム含有オリビン型リン酸塩は、例えば前記の正極活物質と混合して用いることもできる。
Further, a lithium-containing olivine-type phosphate can be used as the positive electrode active material. In particular, a lithium-containing olivine-type phosphate containing at least one selected from iron, cobalt, nickel and manganese is preferable. Specific examples thereof include LiFePO 4 , LiCoPO 4 , LiNiPO 4 , and LiMnPO 4 .
Some of these lithium-containing olivine-type phosphates may be replaced with other elements, and some of iron, cobalt, nickel and manganese may be replaced with Co, Mn, Ni, Mg, Al, B, Ti, V and Nb. , Cu, Zn, Mo, Ca, Sr, W, Zr and the like, or can be coated with a compound or carbon material containing one or more of these other elements. Of these, LiFePO 4 or LiMnPO 4 is preferred.
Further, the lithium-containing olivine-type phosphate can also be used, for example, by mixing with the above-mentioned positive electrode active material.
また、リチウム一次電池用正極としては、ＣｕＯ、Ｃｕ２Ｏ、Ａｇ２Ｏ、Ａｇ２ＣｒＯ４、ＣｕＳ、ＣｕＳＯ４、ＴｉＯ２、ＴｉＳ２、ＳｉＯ２、ＳｎＯ、Ｖ２Ｏ５、Ｖ６Ｏ１２、ＶＯｘ、Ｎｂ２Ｏ５、Ｂｉ２Ｏ３、Ｂｉ２Ｐｂ２Ｏ５，Ｓｂ２Ｏ３、ＣｒＯ３、Ｃｒ２Ｏ３、ＭｏＯ３、ＷＯ３、ＳｅＯ２、ＭｎＯ２、Ｍｎ２Ｏ３、Ｆｅ２Ｏ３、ＦｅＯ、Ｆｅ３Ｏ４、Ｎｉ２Ｏ３、ＮｉＯ、ＣｏＯ３、ＣｏＯなどの、１種もしくは２種以上の金属元素の酸化物あるいはカルコゲン化合物、ＳＯ２、ＳＯＣｌ２などの硫黄化合物、一般式（ＣＦｘ）ｎで表されるフッ化炭素（フッ化黒鉛）などが挙げられる。中でも、ＭｎＯ２、Ｖ２Ｏ５、フッ化黒鉛などが好ましい。 Further, as the positive electrode for the lithium primary battery, CuO, Cu 2 O, Ag 2 O, Ag 2 CrO 4 , CuS, CuSO 4 , TiO 2 , TiS 2 , SiO 2 , SnO, V 2 O 5 , V 6 O 12 , VO x , Nb 2 O 5 , Bi 2 O 3 , Bi 2 Pb 2 O 5 , Sb 2 O 3 , CrO 3 , Cr 2 O 3 , MoO 3 , WO 3 , SeO 2 , MnO 2 , Mn 2 O 3 , Fe 2 O 3 , FeO, Fe 3 O 4 , Ni 2 O 3 , NiO, CoO 3 , CoO, and other oxides or chalcogen compounds of one or more metal elements, SO 2 , SOCl 2, etc. Examples thereof include sulfur compounds and fluorocarbon (fluorinated graphite) represented by the general formula (CF x ) n. Of these, MnO 2 , V 2 O 5 , and graphite fluoride are preferable.
正極の導電剤は、化学変化を起こさない電子伝導材料であれば特に制限はない。例えば、天然黒鉛（鱗片状黒鉛等）、人造黒鉛等のグラファイト、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等のカーボンブラック等が挙げられる。また、グラファイトとカーボンブラックを適宜混合して用いてもよい。導電剤の正極合剤への添加量は、１〜１０質量％が好ましく、特に２〜５質量％が好ましい。 The conductive agent for the positive electrode is not particularly limited as long as it is an electron conductive material that does not cause a chemical change. For example, natural graphite (scaly graphite or the like), graphite such as artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and the like can be mentioned. Further, graphite and carbon black may be appropriately mixed and used. The amount of the conductive agent added to the positive electrode mixture is preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
正極は、前記の正極活物質をアセチレンブラック、カーボンブラック等の導電剤、およびポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、スチレンとブタジエンの共重合体（ＳＢＲ）、アクリロニトリルとブタジエンの共重合体（ＮＢＲ）、カルボキシメチルセルロース（ＣＭＣ）、エチレンプロピレンジエンターポリマー等の結着剤と混合し、これに１−メチル−２−ピロリドン等の高沸点溶剤を加えて混練して正極合剤とした後、この正極合剤を集電体のアルミニウム箔やステンレス製のラス板等に塗布して、乾燥、加圧成型した後、５０℃〜２５０℃程度の温度で、２時間程度真空下で加熱処理することにより作製することができる。
正極の集電体を除く部分の密度は、通常は１．５ｇ／ｃｍ３以上であり、電池の容量をさらに高めるため、好ましくは２ｇ／ｃｍ３以上であり、より好ましくは、３ｇ／ｃｍ３以上であり、更に好ましくは、３．６ｇ／ｃｍ３以上である。また、４ｇ／ｃｍ３以下が好ましい。
For the positive electrode, the positive electrode active material is made of a conductive agent such as acetylene black or carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a styrene-butadiene copolymer (SBR), acrylonitrile and butadiene. Mix with a binder such as copolymer (NBR), carboxymethyl cellulose (CMC), ethylene propylene dienter polymer, etc., add a high boiling point solvent such as 1-methyl-2-pyrrolidone, and knead to make a positive mixture. After that, this positive electrode mixture is applied to an aluminum foil of a current collector, a lath plate made of stainless steel, etc., dried and pressure-molded, and then vacuumed at a temperature of about 50 ° C to 250 ° C for about 2 hours. It can be produced by heat-treating with.
The density of the part except the collector of the positive electrode is usually at 1.5 g / cm 3 or more, for further increasing the capacity of the battery, it is preferably 2 g / cm 3 or more, more preferably, 3 g / cm 3 The above is more preferably 3.6 g / cm 3 or more. Further, 4 g / cm 3 or less is preferable.
リチウム二次電池用負極活物質としては、リチウム金属やリチウム合金、およびリチウムを吸蔵および放出することが可能な炭素材料〔易黒鉛化炭素や、（００２）面の面間隔が０．３７ｎｍ（ナノメータ）以上の難黒鉛化炭素や、（００２）面の面間隔が０．３４ｎｍ以下の黒鉛など〕、スズ（単体）、スズ化合物、ケイ素（単体）、ケイ素化合物、Ｌｉ４Ｔｉ５Ｏ１２などのチタン酸リチウム化合物等を１種単独または２種以上を組合せて用いることができる。
これらの中では、リチウムイオンの吸蔵および放出能力において、人造黒鉛や天然黒鉛等の高結晶性の炭素材料を使用することが更に好ましく、格子面（００２）の面間隔（ｄ００２）が０．３４０ｎｍ以下、特に０．３３５〜０．３３７ｎｍである黒鉛型結晶構造を有する炭素材料を使用することが特に好ましい。
複数の扁平状の黒鉛質微粒子が互いに非平行に集合或いは結合した塊状構造を有する人造黒鉛粒子や、例えば鱗片状天然黒鉛粒子に圧縮力、摩擦力、剪断力等の機械的作用を繰り返し与え、球形化処理を施した黒鉛粒子を用いることにより、負極の集電体を除く部分の密度を１．５ｇ／ｃｍ３以上の密度に加圧成形したときの負極シートのＸ線回折測定から得られる黒鉛結晶の（１１０）面のピーク強度Ｉ（１１０）と（００４）面のピーク強度Ｉ（００４）の比Ｉ（１１０）／Ｉ（００４）が０．０１以上となると一段と正極活物質からの金属溶出量の改善と、充電保存特性が向上するので好ましく、０．０５以上となることがより好ましく、０．１以上となることが更に好ましい。また、過度に処理し過ぎて結晶性が低下し電池の放電容量が低下する場合があるので、０．５以下が好ましく、０．３以下がより好ましい。
また、高結晶性の炭素材料（コア材）はコア材よりも低結晶性の炭素材料によって被膜されていると、サイクル特性が一段と良好となるので好ましい。被覆の炭素材料の結晶性は、ＴＥＭにより確認することができる。
高結晶性の炭素材料を使用すると、充電時において非水電解液と反応し、界面抵抗の増加によってサイクル特性を低下させる傾向があるが、本発明に係るリチウム二次電池ではサイクル特性が良好となる。
As the negative electrode active material for lithium secondary batteries, lithium metal, lithium alloy, and carbon material capable of occluding and releasing lithium [graphitized carbon and (002) plane spacing of 0.37 nm (nanometer) ) Or more difficult-to-graphite carbon, or graphite with a (002) plane spacing of 0.34 nm or less], tin (elemental substance), tin compound, silicon (elemental substance), silicon compound, Li 4 Ti 5 O 12, etc. A lithium titanate compound or the like can be used alone or in combination of two or more.
Among these, it is more preferable to use a highly crystalline carbon material such as artificial graphite or natural graphite in terms of the ability to occlude and release lithium ions, and the interplanar spacing (d 002 ) of the lattice plane (002) is 0. It is particularly preferable to use a carbon material having a graphite-type crystal structure having a graphite-type crystal structure of 340 nm or less, particularly 0.335 to 0.337 nm.
Mechanical actions such as compressive force, frictional force, and shearing force are repeatedly applied to artificial graphite particles having a massive structure in which a plurality of flat graphite fine particles are aggregated or bonded to each other in a non-parallel manner, for example, scaly natural graphite particles. It can be obtained from the X-ray diffraction measurement of the negative electrode sheet when the density of the portion of the negative electrode excluding the current collector is pressure-molded to a density of 1.5 g / cm 3 or more by using the spheroidized graphite particles. When the ratio I (110) / I (004) of the peak intensity I (110) on the (110) plane and the peak intensity I (004) on the (004) plane of the graphite crystal is 0.01 or more, it is further from the positive electrode active material. It is preferable because the amount of metal elution is improved and the charge storage characteristics are improved, and it is more preferably 0.05 or more, and further preferably 0.1 or more. In addition, excessive treatment may reduce the crystallinity and the discharge capacity of the battery. Therefore, 0.5 or less is preferable, and 0.3 or less is more preferable.
Further, it is preferable that the highly crystalline carbon material (core material) is coated with a carbon material having a lower crystallinity than the core material because the cycle characteristics are further improved. The crystallinity of the coated carbon material can be confirmed by TEM.
When a highly crystalline carbon material is used, it reacts with a non-aqueous electrolytic solution during charging and tends to reduce the cycle characteristics due to an increase in interfacial resistance. However, the lithium secondary battery according to the present invention has good cycle characteristics. Become.
また、負極活物質としてのリチウムを吸蔵および放出可能な金属化合物としては、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｐ、Ｓｂ、Ｂｉ、Ａｌ、Ｇａ、Ｉｎ、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｇ、Ｍｇ、Ｓｒ、Ｂａ等の金属元素を少なくとも１種含有する化合物が挙げられる。これらの金属化合物は単体、合金、酸化物、窒化物、硫化物、硼化物、リチウムとの合金等、何れの形態で用いてもよいが、単体、合金、酸化物、リチウムとの合金の何れかが高容量化できるので好ましい。中でも、Ｓｉ、ＧｅおよびＳｎから選ばれる少なくとも１種の元素を含有するものが好ましく、ＳｉおよびＳｎから選ばれる少なくとも１種の元素を含むものが電池を高容量化できるので特に好ましい。 Examples of the metal compound capable of occluding and releasing lithium as a negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni and Cu. , Zn, Ag, Mg, Sr, Ba and other compounds containing at least one metal element. These metal compounds may be used in any form such as elemental substances, alloys, oxides, nitrides, sulfides, borides, alloys with lithium, etc., but any of elemental substances, alloys, oxides, alloys with lithium, etc. It is preferable because the capacity can be increased. Among them, those containing at least one element selected from Si, Ge and Sn are preferable, and those containing at least one element selected from Si and Sn are particularly preferable because the capacity of the battery can be increased.
負極は、上記の正極の作製と同様な導電剤、結着剤、高沸点溶剤を用いて混練して負極合剤とした後、この負極合剤を集電体の銅箔等に塗布して、乾燥、加圧成型した後、５０℃〜２５０℃程度の温度で２時間程度真空下加熱処理することにより作製することができる。
負極の集電体を除く部分の密度は、通常は１．１ｇ／ｃｍ３以上であり、電池の容量をさらに高めるため、好ましくは１．５ｇ／ｃｍ３以上であり、特に好ましくは１．７ｇ／ｃｍ３以上である。また、２ｇ／ｃｍ３以下が好ましい。
The negative electrode is kneaded with a conductive agent, a binder, and a high boiling point solvent similar to those for producing the positive electrode to obtain a negative electrode mixture, and then this negative electrode mixture is applied to a copper foil or the like of a current collector. After drying and pressure molding, it can be produced by heat treatment under vacuum for about 2 hours at a temperature of about 50 ° C. to 250 ° C.
The density of the portion of the negative electrode excluding the current collector is usually 1.1 g / cm 3 or more, and is preferably 1.5 g / cm 3 or more, particularly preferably 1.7 g, in order to further increase the capacity of the battery. / Cm 3 or more. Further, it is preferably 2 g / cm 3 or less.
また、リチウム一次電池用の負極活物質としては、リチウム金属またはリチウム合金が挙げられる。 Moreover, as a negative electrode active material for a lithium primary battery, a lithium metal or a lithium alloy can be mentioned.
リチウム電池の構造には特に限定はなく、単層または複層のセパレータを有するコイン型電池、円筒型電池、角型電池、ラミネート電池等を適用できる。
電池用セパレータとしては、特に制限はされないが、ポリプロピレン、ポリエチレン等のポリオレフィンの単層または積層の微多孔性フィルム、織布、不織布等を使用できる。
The structure of the lithium battery is not particularly limited, and a coin-type battery having a single-layer or multi-layer separator, a cylindrical battery, a square battery, a laminated battery, or the like can be applied.
The battery separator is not particularly limited, but a monolayer or laminated microporous film of polyolefin such as polypropylene or polyethylene, a woven fabric, a non-woven fabric or the like can be used.
本発明におけるリチウム二次電池は、充電終止電圧が４．２Ｖ以上、特に４．３Ｖ以上の場合にもサイクル特性に優れ、更に、４．４Ｖ以上においても特性は良好である。放電終止電圧は、通常２．８Ｖ以上、更には２．５Ｖ以上とすることができるが、本願発明におけるリチウム二次電池は、２．０Ｖ以上とすることができる。電流値については特に限定されないが、通常０．１〜３０Ｃの範囲で使用される。また、本発明におけるリチウム電池は、−４０〜１００℃、好ましくは−１０〜８０℃で充放電することができる。 The lithium secondary battery in the present invention has excellent cycle characteristics even when the charge termination voltage is 4.2 V or more, particularly 4.3 V or more, and further, the characteristics are also good when the charge termination voltage is 4.4 V or more. The discharge end voltage can usually be 2.8 V or higher, further 2.5 V or higher, but the lithium secondary battery in the present invention can be 2.0 V or higher. The current value is not particularly limited, but is usually used in the range of 0.1 to 30C. Further, the lithium battery in the present invention can be charged and discharged at −40 to 100 ° C., preferably −10 to 80 ° C.
本発明においては、リチウム電池の内圧上昇の対策として、電池蓋に安全弁を設けたり、電池缶やガスケット等の部材に切り込みを入れる方法も採用することができる。また、過充電防止の安全対策として、電池の内圧を感知して電流を遮断する電流遮断機構を電池蓋に設けることができる。 In the present invention, as a countermeasure against an increase in the internal pressure of the lithium battery, a method of providing a safety valve on the battery lid or making a notch in a member such as a battery can or a gasket can also be adopted. Further, as a safety measure for preventing overcharging, a current cutoff mechanism that senses the internal pressure of the battery and cuts off the current can be provided on the battery lid.
〔第２の蓄電デバイス（電気二重層キャパシタ）〕
第２の蓄電デバイスは、電解液と電極界面の電気二重層容量を利用してエネルギーを貯蔵する蓄電デバイスである。本発明の一例は、電気二重層キャパシタである。この蓄電デバイスに用いられる最も典型的な電極活物質は、活性炭である。二重層容量は概ね表面積に比例して増加する。
[Second power storage device (electric double layer capacitor)]
The second power storage device is a power storage device that stores energy by utilizing the electric double layer capacity at the interface between the electrolytic solution and the electrode. An example of the present invention is an electric double layer capacitor. The most typical electrode active material used in this power storage device is activated carbon. The double layer capacity increases approximately in proportion to the surface area.
〔第３の蓄電デバイス〕
第３の蓄電デバイスは、電極のドープ／脱ドープ反応を利用してエネルギーを貯蔵する蓄電デバイスである。この蓄電デバイスに用いられる電極活物質として、酸化ルテニウム、酸化イリジウム、酸化タングステン、酸化モリブデン、酸化銅等の金属酸化物や、ポリアセン、ポリチオフェン誘導体等のπ共役高分子が挙げられる。これらの電極活物質を用いたキャパシタは、電極のドープ／脱ドープ反応にともなうエネルギー貯蔵が可能である。
[Third power storage device]
The third storage device is a storage device that stores energy by utilizing the doping / dedoping reaction of the electrodes. Examples of the electrode active material used in this power storage device include metal oxides such as ruthenium oxide, iridium oxide, tungsten oxide, molybdenum oxide and copper oxide, and π-conjugated polymers such as polyacene and polythiophene derivatives. Capacitors using these electrode active materials can store energy associated with the doping / dedoping reaction of the electrodes.
〔第４の蓄電デバイス（リチウムイオンキャパシタ）〕
第４の蓄電デバイスは、負極であるグラファイト等の炭素材料へのリチウムイオンのインターカレーションを利用してエネルギーを貯蔵する蓄電デバイスである。リチウムイオンキャパシタ（ＬＩＣ）と呼ばれる。正極は、例えば活性炭電極と電解液との間の電気ニ重層を利用したものや、π共役高分子電極のドープ／脱ドープ反応を利用したもの等が挙げられる。電解液には少なくともＬｉＰＦ６などのリチウム塩が含まれる。
[Fourth power storage device (lithium ion capacitor)]
The fourth power storage device is a power storage device that stores energy by utilizing the intercalation of lithium ions with a carbon material such as graphite, which is a negative electrode. It is called a lithium ion capacitor (LIC). Examples of the positive electrode include those using an electric double layer between the activated carbon electrode and the electrolytic solution, those using the doping / dedoping reaction of the π-conjugated polymer electrode, and the like. The electrolytic solution contains at least a lithium salt such as LiPF 6.
以下、本発明の化合物を用いた電解液の実施例を示すが、本発明は、これらの実施例に限定されるものではない。 Hereinafter, examples of the electrolytic solution using the compound of the present invention will be shown, but the present invention is not limited to these examples.
実施例１〜４、参考例１、比較例１〜２
〔非水電解液の調製〕
表１に記載の溶媒および電解質塩を一定量で混合し、調製した基準電解液に対して、表１に記載の一般式（Ｉ）の環状硫酸エステル、一般式（ＩＩ）の環状スルホン化合物および一般式（ＩＩＩ）の有機シラン化合物をそれぞれ加えて、非水電解液を調製した。
Examples 1-4, Reference Example 1, Comparative Examples 1-2
[Preparation of non-aqueous electrolyte solution]
The cyclic sulfate ester of the general formula (I), the cyclic sulfone compound of the general formula (II), and the cyclic sulfone compound of the general formula (II) shown in Table 1 are mixed with the reference electrolytic solution prepared by mixing the solvent and the electrolyte salt shown in Table 1 in a fixed amount. A non-aqueous electrolyte solution was prepared by adding each of the organic silane compounds of the general formula (III).
〔非水電解液の化学的安定性評価〕
＜高温保存試験＞
上記の方法で作製した非水電解液を用いて４０℃の恒温槽中、２８日間保存を行った。保存後、これらの電解液を２５℃に冷却した後、電解液の化学的安定性を測定するため、以下の評価を行った。
[Chemical stability evaluation of non-aqueous electrolyte solution]
<High temperature storage test>
The non-aqueous electrolytic solution prepared by the above method was stored in a constant temperature bath at 40 ° C. for 28 days. After storage, these electrolytic solutions were cooled to 25 ° C., and then the following evaluations were performed in order to measure the chemical stability of the electrolytic solutions.
＜高温保存後における着色度合の測定＞
電解液の着色度合であるＡＰＨＡ（ハーゼン色数）を測定した（日本電色工業製測色色差計ＺＥ６０００）。
<Measurement of degree of coloring after high temperature storage>
APHA (Hazen color number), which is the degree of coloring of the electrolytic solution, was measured (color difference meter ZE6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.).
＜高温保存後における電解液中の環状硫酸エステル残存量の測定＞
電解液中の環状硫酸エステルや環状スルホン化合物の残存量は、１Ｈ−ＮＭＲの内標定量法により算出した（４００ＭＨｚ；重溶媒なし、内標：（トリフルオロメトキシ）ベンゼン、日本電子製ＪＮＭ−ＥＣＺ４００Ｒ）。
電解液の化学的安定性評価結果を表１に示す。
<Measurement of residual cyclic sulfate ester in electrolyte after high temperature storage>
The residual amount of cyclic sulfate ester and cyclic sulfone compound in the electrolytic solution was calculated by 1 H-NMR internal standard quantification method (400 MHz; no deuterated solvent, internal standard: (trifluoromethoxy) benzene, JNM-manufactured by JEOL Ltd. ECZ400R).
Table 1 shows the results of the chemical stability evaluation of the electrolytic solution.
なお、表１に示す実施例および比較例においては、非水電解液全体に対する表中記載の化合物の含有量が、表１に示す量となるように、非水電解液を調製した。 In the examples and comparative examples shown in Table 1, the non-aqueous electrolytic solution was prepared so that the content of the compound shown in the table with respect to the entire non-aqueous electrolytic solution was the amount shown in Table 1.
上記表１において、環状硫酸エステルのみを添加した比較例１や環状スルホン化合物のみを添加した比較例２では、高温保存後に電解液の着色に伴うＡＰＨＡ値の上昇および環状硫酸エステルや環状スルホン化合物の分解が確認された。一方で、本発明の一般式（ＩＩＩ）で表される有機シラン化合物を含む実施例１〜実施例４では、ＡＰＨＡ値の上昇および環状硫酸エステルや環状スルホン化合物の分解の両方が抑制されている。また、有機シラン化合物の含有量としては、０.３質量％以下の場合、特に好ましい効果を発揮する。これらの結果から、本発明の非水電解液は、高温保存後の非水電解液の着色を抑制し、かつ高温保存による環状硫酸エステルや環状スルホン化合物の分解を抑制できる蓄電デバイス用非水電解液を提供することが出来る。 In Table 1 above, in Comparative Example 1 in which only the cyclic sulfate ester was added and Comparative Example 2 in which only the cyclic sulfone compound was added, the APHA value increased with the coloring of the electrolytic solution after storage at a high temperature, and the cyclic sulfate ester and the cyclic sulfone compound were added. Disassembly was confirmed. On the other hand, in Examples 1 to 4 containing the organic silane compound represented by the general formula (III) of the present invention, both the increase in APHA value and the decomposition of the cyclic sulfate ester and the cyclic sulfone compound are suppressed. .. Further, when the content of the organic silane compound is 0.3% by mass or less, a particularly preferable effect is exhibited. From these results, the non-aqueous electrolytic solution of the present invention can suppress the coloring of the non-aqueous electrolytic solution after high-temperature storage, and can also suppress the decomposition of cyclic sulfate ester and cyclic sulfone compound due to high-temperature storage. The liquid can be provided.
本発明の非水電解液を使用すれば、高温保存後の非水電解液の着色を抑制し、かつ高温保存による環状硫酸エステルや環状スルホン化合物の分解を抑制できる蓄電デバイス用非水電解液を提供することができ、広い温度範囲における電気化学特性に優れた蓄電デバイスを得ることができる。特にハイブリッド電気自動車、プラグインハイブリッド電気自動車、バッテリー電気自動車等に搭載されるリチウム二次電池等の蓄電デバイス用の非水電解液として使用すると、広い温度範囲で電気化学特性が低下しにくい蓄電デバイスを得ることができる。 By using the non-aqueous electrolyte solution of the present invention, a non-aqueous electrolyte solution for a power storage device capable of suppressing coloring of the non-aqueous electrolyte solution after high temperature storage and suppressing decomposition of cyclic sulfate ester and cyclic sulfone compound by high temperature storage can be obtained. It is possible to provide a power storage device having excellent electrochemical characteristics in a wide temperature range. In particular, when used as a non-aqueous electrolyte solution for power storage devices such as lithium secondary batteries installed in hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, etc., storage devices whose electrochemical characteristics do not easily deteriorate over a wide temperature range. Can be obtained.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003242991A (en) * | 2002-02-04 | 2003-08-29 | Lithdyne Internatl Inc | Stabilized lithium electrochemical cell containing alkoxysilane |
| JP2010232117A (en) * | 2009-03-30 | 2010-10-14 | Hitachi Vehicle Energy Ltd | Lithium secondary battery |
| JP2011124047A (en) * | 2009-12-09 | 2011-06-23 | Sony Corp | Lithium ion secondary battery, anode for lithium ion secondary battery, power tool, electric vehicle, and power storage system |
| CN104241688A (en) * | 2013-06-24 | 2014-12-24 | 微宏动力系统（湖州）有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| WO2019073831A1 (en) * | 2017-10-11 | 2019-04-18 | 株式会社Adeka | Method for preventing decomposition of silyl ester compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003242991A (en) * | 2002-02-04 | 2003-08-29 | Lithdyne Internatl Inc | Stabilized lithium electrochemical cell containing alkoxysilane |
| JP2010232117A (en) * | 2009-03-30 | 2010-10-14 | Hitachi Vehicle Energy Ltd | Lithium secondary battery |
| JP2011124047A (en) * | 2009-12-09 | 2011-06-23 | Sony Corp | Lithium ion secondary battery, anode for lithium ion secondary battery, power tool, electric vehicle, and power storage system |
| CN104241688A (en) * | 2013-06-24 | 2014-12-24 | 微宏动力系统（湖州）有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| WO2019073831A1 (en) * | 2017-10-11 | 2019-04-18 | 株式会社Adeka | Method for preventing decomposition of silyl ester compound |
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