JP2008071559A - Lithium-ion secondary battery - Google Patents
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Abstract
Description
本発明は、リチウムイオン二次電池に関し、特に電解液に添加剤を加えることにより電池特性を向上させたリチウムイオン二次電池に関する。 The present invention relates to a lithium ion secondary battery, and more particularly to a lithium ion secondary battery whose battery characteristics are improved by adding an additive to an electrolytic solution.
リチウムイオン二次電池は小型で大容量であるという特長を有しており、携帯電話、ノート型パソコン等の携帯機器の電源として広く用いられている。従来より、リチウムイオン二次電池においては電極の表面に皮膜を形成させることにより電池特性を改善させる提案があり、特許文献１においては電解液に環状スルホン酸エステルを添加することによりサイクル寿命を改善させる記載がある。最近では、ＨＥＶ、ＥＶ等の自動車用途や電力貯蔵用途等の大型のリチウムイオン二次電池の開発が進められており、サイクル寿命に関しては１０年以上の長期の寿命が必要になり、更なる改善が必要になっている。 A lithium ion secondary battery has a feature of being small and has a large capacity, and is widely used as a power source for portable devices such as mobile phones and notebook computers. Conventionally, in lithium ion secondary batteries, there has been a proposal to improve battery characteristics by forming a film on the surface of the electrode, and Patent Document 1 improves cycle life by adding a cyclic sulfonate ester to the electrolyte. There is a description to make. Recently, development of large-sized lithium ion secondary batteries for HEV, EV, and other automobile applications and power storage applications has been promoted, and a cycle life of 10 years or longer is required, and further improvements are made. Is needed.
また、電池特性を改善させる試みの一つとして、特許文献２においては電解液にリン酸トリエステルを添加してサイクル特性を改善する記載があり、特許文献３においては電解液にフッ素を含む界面活性剤を添加して電解液のセパレータに対する濡れ性を改善する記載がある。 In addition, as one of attempts to improve battery characteristics, Patent Document 2 describes that cycle characteristics are improved by adding a phosphate triester to an electrolytic solution, and Patent Document 3 describes an interface containing fluorine in the electrolytic solution. There is a description of improving the wettability of the electrolytic solution to the separator by adding an activator.
リチウムイオン二次電池の電極活物質は、エネルギー密度の向上のために高密度充填されている。また、電解液には通常混合溶媒が用いられるが、電解液の粘度が高い。そのため、電極活物質中に電解液が充分に浸透するには、電極活物質に細孔などが存在するため時間を要していた。すなわち、初期に電解液の添加剤により電極活物質中の細孔の表面にも皮膜を形成させることが困難であり、これにより長期のサイクル寿命が劣化していた。一方、界面活性剤による濡れ性の改善のみでは電極の表面に皮膜を形成することが出来ず、サイクル寿命の改善は充分ではなかった。 The electrode active material of the lithium ion secondary battery is filled with high density in order to improve the energy density. Moreover, although a mixed solvent is normally used for electrolyte solution, the viscosity of electrolyte solution is high. Therefore, it takes time for the electrolyte to sufficiently penetrate into the electrode active material because pores and the like exist in the electrode active material. That is, it is difficult to form a film on the surface of the pores in the electrode active material at the initial stage with the additive of the electrolytic solution, thereby deteriorating the long cycle life. On the other hand, it was not possible to form a film on the surface of the electrode only by improving the wettability with the surfactant, and the cycle life was not improved sufficiently.
本発明は上記問題点に鑑みなされたものである。本発明の課題は、長期的なサイクル寿命を改善したリチウムイオン二次電池を提供することにある。 The present invention has been made in view of the above problems. An object of the present invention is to provide a lithium ion secondary battery with improved long-term cycle life.
本発明者らは上記問題点を解決するに当たり鋭意検討した結果、電解液に初期の充放電により電極活物質の表面に皮膜を形成させる添加剤を加え、さらに電解液を電極活物質の細孔部に浸透させるために界面活性剤を電解液に加えた場合に、長期的なサイクル寿命特性が向上することを見出し本発明に至ったものである。 As a result of diligent investigations to solve the above problems, the present inventors have added an additive for forming a film on the surface of the electrode active material by the initial charge / discharge to the electrolyte, and further added the electrolyte to the pores of the electrode active material. The present inventors have found that a long-term cycle life characteristic is improved when a surfactant is added to an electrolyte solution so as to penetrate into a part.
本発明のリチウムイオン二次電池は正極、負極、電解液、およびセパレータを備えたリチウムイオン二次電池において、前記電解液が環状ジスルホン酸エステルと界面活性剤を有することを特徴とする。 The lithium ion secondary battery of the present invention is a lithium ion secondary battery comprising a positive electrode, a negative electrode, an electrolytic solution, and a separator, wherein the electrolytic solution has a cyclic disulfonic acid ester and a surfactant.
また、本発明のリチウムイオン二次電池は前記界面活性剤が、リン酸エステル、脂肪酸塩、アルカンスルホン酸塩から選択される少なくとも一種で構成されることを特徴とする。 The lithium ion secondary battery of the present invention is characterized in that the surfactant is composed of at least one selected from a phosphate ester, a fatty acid salt, and an alkane sulfonate.
また、本発明のリチウムイオン二次電池は前記界面活性剤がリン酸トリオクチルからなることを特徴とする。 The lithium ion secondary battery of the present invention is characterized in that the surfactant comprises trioctyl phosphate.
また、本発明のリチウムイオン二次電池は前記環状ジスルホン酸エステルが、下記化１（ただし、下記化１において、Ｑは酸素原子、メチレン基または単結合、Ａは置換もしくは無置換の炭素数1〜５のアルキレン基、カルボニル基、スルフィニル基、置換もしくは無置換の炭素数１〜６のフルオロアルキレン基、またはエーテル結合を介してアルキレン単位もしくはフルオロアルキレン単位結合した炭素数２〜６の２価の基を示し、Ｂは置換もしくは無置換のアルキレン基、置換もしくは無置換のフルオロアルキレン基、または酸素原子を示す）で示される化合物を含むことを特徴とする。
また、本発明のリチウムイオン二次電池は前記環状ジスルホン酸エステルが、下記化２で示される化合物または下記化３で示される化合物から選択される少なくとも一つを含むことを特徴とする。
また、本発明のリチウムイオン二次電池は前記界面活性剤が、前記電解液中に０．０１質量（以下ｗｔと表記）％以上３ｗｔ％以下含まれることを特徴とする。 In the lithium ion secondary battery of the present invention, the surfactant is contained in the electrolytic solution in an amount of 0.01 mass (hereinafter referred to as wt)% to 3 wt%.
また、本発明のリチウムイオン二次電池は前記環状ジスルホン酸エステルが、前記電解液中に０．１ｗｔ％以上５ｗｔ％以下含まれることを特徴とする。 The lithium ion secondary battery of the present invention is characterized in that the cyclic disulfonic acid ester is contained in an amount of 0.1 wt% to 5 wt% in the electrolytic solution.
本発明はリチウムイオン二次電池のサイクル寿命の改善を図ったものである。リチウムイオン二次電池に使用される電解液の溶媒は粘度が高いが、界面活性剤を添加することにより、電極活物質の細孔部へ浸透することとなり、これにより環状ジスルホン酸エステルによる初期の充電時において、電極表面に均一な皮膜が形成されることになる。その結果、充放電サイクルや高温保存時における劣化が抑制されることになる。また、皮膜の形成により界面活性剤の分解も抑制されるため、さらにサイクル寿命が改善されることとなる。 The present invention is intended to improve the cycle life of a lithium ion secondary battery. Although the solvent of the electrolyte used for the lithium ion secondary battery has a high viscosity, by adding a surfactant, it penetrates into the pores of the electrode active material. At the time of charging, a uniform film is formed on the electrode surface. As a result, deterioration during charge / discharge cycles and high temperature storage is suppressed. Moreover, since the decomposition of the surfactant is suppressed by the formation of the film, the cycle life is further improved.
本発明によれば、リチウムイオン二次電池の電解液が環状ジスルホン酸エステルと界面活性剤を有することによりサイクル寿命が改善されたリチウムイオン二次電池を提供することが出来る。 ADVANTAGE OF THE INVENTION According to this invention, the lithium ion secondary battery with improved cycle life can be provided because the electrolyte solution of a lithium ion secondary battery has cyclic disulfonic acid ester and surfactant.
次に本発明の実施の形態について図面を参照して説明する。図１は本発明のリチウムイオン二次電池の構成を示す模式図である。 Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram showing the configuration of the lithium ion secondary battery of the present invention.
図１に示すように、アルミニウム箔等の金属からなる正極集電体１１上のリチウムイオンを吸蔵、放出し得る正極活物質を含有する層１２と、銅箔等の金属からなる負極集電体１４上のリチウムイオンを吸蔵、放出する負極活物質を含有する層１３とが、電解液１５、およびこれを含む不織布、ポリオレフィン微多孔膜などからなるセパレータ１６を介して対向して配置され構成されている。
As shown in FIG. 1, a
本発明のリチウムイオン二次電池はリチウム複合酸化物を含む正極活物質を用いた正極と、リチウムを吸蔵放出可能な負極活物質を持つ負極を主要成分とし、正極と負極の間に電気的接続を起こさないようなセパレータが挟まれ、正極と負極はリチウムイオン電導性の非水電解液に浸った状態で、非水電解液を介して対向配置され、これらが電池ケースの中に密閉された状態となっている。 The lithium ion secondary battery of the present invention is mainly composed of a positive electrode using a positive electrode active material containing a lithium composite oxide and a negative electrode having a negative electrode active material capable of occluding and releasing lithium, and is electrically connected between the positive electrode and the negative electrode. The positive electrode and the negative electrode are soaked in a lithium ion conductive non-aqueous electrolyte and are placed opposite each other through the non-aqueous electrolyte, and these are sealed in a battery case. It is in a state.
（電解液）
電解液はリチウム塩を溶解させた非プロトン性有機溶媒に環状ジスルホン酸エステルと界面活性剤を添加した物を用いることができる。電解液の溶媒としては、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、等の環状カーボネート類、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）等の鎖状カーボネート類、γ−ブチロラクトン（ＧＢＬ）等のγ−ラクトン類などの非プロトン性有機溶媒を一種又は二種以上を混合して使用できる。このうち、ＰＣ、ＥＣ、ＧＢＬ、ＤＭＣ、ＤＥＣ、ＥＭＣなどを単独もしくは混合して用いることが好ましいが、これらに限定されるものではない。
(Electrolyte)
As the electrolytic solution, a product obtained by adding a cyclic disulfonic acid ester and a surfactant to an aprotic organic solvent in which a lithium salt is dissolved can be used. As a solvent for the electrolytic solution, cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC), Aprotic organic solvents such as γ-lactones such as γ-butyrolactone (GBL) can be used singly or in combination. Of these, PC, EC, GBL, DMC, DEC, EMC, etc. are preferably used alone or in combination, but are not limited thereto.
これらの有機溶媒に支持塩としてリチウム塩を溶解させる。リチウム塩としては、例えばＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3などがあげられるが、これらに限定されるものではない。電解質濃度は、０．５ｍｏｌ／ｌから１．５ｍｏｌ／ｌが好ましい。この濃度が高すぎると密度と粘度が増加する。濃度が低すぎると電気伝導率が低下することがある。 A lithium salt is dissolved as a supporting salt in these organic solvents. Examples of the lithium salt include, but are not limited to, LiPF 6 , LiBF 4 , and LiCF 3 SO 3 . The electrolyte concentration is preferably 0.5 mol / l to 1.5 mol / l. If this concentration is too high, density and viscosity increase. If the concentration is too low, the electrical conductivity may decrease.
環状ジスルホン酸エステルとしては化合物番号１〜２２として表１に示される有機化合物が挙げられるが、これらに限定されるものではない。 Examples of the cyclic disulfonic acid ester include organic compounds shown in Table 1 as compound numbers 1 to 22, but are not limited thereto.
環状ジスルホン酸エステルの電解液への添加量は０．１ｗｔ％以上５ｗｔ％以下が好ましい。０．１ｗｔ％未満の場合には電極活物質の表面に皮膜が充分形成されず、サイクル寿命の改善効果が小さくなる恐れがあり、５ｗｔ％を超える場合には皮膜の量が増加しすぎて抵抗が上昇するなどの悪影響が出る恐れがある。 The amount of cyclic disulfonic acid ester added to the electrolytic solution is preferably 0.1 wt% or more and 5 wt% or less. If the amount is less than 0.1 wt%, a film is not sufficiently formed on the surface of the electrode active material, and the effect of improving the cycle life may be reduced. If the amount exceeds 5 wt%, the amount of the film is excessively increased and resistance is increased. There is a risk of adverse effects such as rising.
界面活性剤としてはリン酸エステル、脂肪酸塩、アルカンスルホン酸塩、などを使用することができ、リン酸トリオクチル、ステアリン酸塩が好ましいがこれらに限定されるものではない。 As the surfactant, phosphate esters, fatty acid salts, alkane sulfonates, and the like can be used, and trioctyl phosphate and stearate are preferable, but not limited thereto.
界面活性剤の電解液への添加量は０．０１ｗｔ％以上３ｗｔ％以下が好ましい。０．０１ｗｔ％未満の場合には電解液の電極活物質の細孔への浸透効果が充分発揮されず、改善効果が小さくなる恐れがあり、３ｗｔ％を超える場合には、界面活性剤の分解反応が増加し電池の抵抗が増加する可能性がある。 The addition amount of the surfactant to the electrolytic solution is preferably 0.01 wt% or more and 3 wt% or less. If the amount is less than 0.01 wt%, the effect of penetration of the electrolyte into the pores of the electrode active material may not be sufficiently exerted, and the improvement effect may be reduced. If the amount exceeds 3 wt%, the surfactant is decomposed. The reaction may increase and the battery resistance may increase.
（正極）
正極活物質としては、たとえば、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2、ＬｉＮｉ0.5Ｍｎ1.5Ｏ4、ＬｉＦｅＰＯ4などのリチウム含有複合酸化物が挙げられ、これらのリチウム含有複合酸化物の遷移金属部分を他の元素で置換させたものでもよく、またこれらの混合物でもよい。これらの正極活物質とカーボンブラックなどからなる導電性付与剤およびポリフッ化ビニリデン（ＰＶＤＦ）等からなるバインダーと共に、バインダーを溶解しうるＮ−メチルピロリドン（ＮＭＰ）等の分散媒で混合（スラリー法）した上で、アルミ箔等の集電体上に塗布した後、溶剤を乾燥した後、プレス等により圧縮して正極を形成する。
(Positive electrode)
Examples of the positive electrode active material include lithium-containing composite oxides such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 1.5 O 4 , and LiFePO 4 . The transition metal portion of these lithium-containing composite oxides may be substituted with other elements, or a mixture thereof. A mixture of these positive electrode active materials, a conductivity imparting agent made of carbon black and the like and a binder made of polyvinylidene fluoride (PVDF), etc., and a dispersion medium such as N-methylpyrrolidone (NMP) capable of dissolving the binder (slurry method) Then, after coating on a current collector such as an aluminum foil, the solvent is dried and then compressed by a press or the like to form a positive electrode.
（負極）
負極活物質としては、たとえば、リチウムを吸蔵する黒鉛、非晶質炭素、Ｓｉ合金、Ｓｉ酸化物、Ｓｉ複合酸化物、Ｓｎ合金、Ｓｎ酸化物、Ｓｎ複合酸化物あるいはこれらの複合物を用いることができる。これらの負極活物質とポリフッ化ビニリデン（ＰＶＤＦ）等からなるバインダーと共に、バインダーを溶解しうるＮ−メチルピロリドン（ＮＭＰ）等の分散媒で混合（スラリー法）した上で、銅箔等の集電体上に塗布した後、溶剤を乾燥した後、プレス等により圧縮して負極を形成する。負極に用いる炭素材料としては、天然黒鉛、人造黒鉛、メソカーボンマイクロビーズなどの高結晶性の黒鉛材料や、低結晶性炭素、難黒鉛化炭素材料などの非晶質炭素を使用することができる。結晶性の高い黒鉛は電解液との反応性が高いために、表面を低結晶性または非晶質の炭素で処理した表面処理黒鉛を使用することが可能である。表面処理方法としては、固相法、液相法、気相法などの手法を使用することができる。
(Negative electrode)
As the negative electrode active material, for example, graphite that absorbs lithium, amorphous carbon, Si alloy, Si oxide, Si composite oxide, Sn alloy, Sn oxide, Sn composite oxide, or a composite thereof is used. Can do. A negative electrode active material and a binder made of polyvinylidene fluoride (PVDF) and the like, mixed with a dispersion medium such as N-methylpyrrolidone (NMP) that can dissolve the binder (slurry method), and then collected current such as copper foil After coating on the body, the solvent is dried and then compressed by a press or the like to form a negative electrode. As the carbon material used for the negative electrode, high-crystalline graphite materials such as natural graphite, artificial graphite and mesocarbon microbeads, and amorphous carbon such as low-crystalline carbon and non-graphitizable carbon material can be used. . Since highly crystalline graphite has high reactivity with the electrolytic solution, it is possible to use surface-treated graphite whose surface is treated with low crystalline or amorphous carbon. As the surface treatment method, a solid phase method, a liquid phase method, a gas phase method, or the like can be used.
セパレーターとして、ポリプロピレン、ポリエチレン等のポリオレフィン、フッ素樹脂等の多孔性フィルムなどが使用できるが、これに限定されるものではない。 As the separator, polyolefin such as polypropylene and polyethylene, porous film such as fluororesin, and the like can be used, but the separator is not limited thereto.
以下に本発明の実施例について詳細に説明するが、本発明は以下の実施例のみに限定されるものではない。 Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples.
（実施例１）
（電池の作製）
本発明の実施例１のリチウムイオン電池の作製について説明する。正極は、正極集電体として厚さ２０μｍのアルミニウム箔を用い、正極活物質としてＬｉ（Ｌｉ0.1Ｍｎ1.9）Ｏ4、とＬｉＮｉ0.8Ｃｏ0.15Ａｌ0.05Ｏ2を質量比で８０：２０に混合したものを用いた。また負極は、負極集電体として厚さ１０μｍの銅箔を用い、負極活物質として黒鉛を用いた。電解液は溶媒としてＥＣとＤＥＣの混合溶媒（体積比：３０／７０）を用い、電解質としてＬｉＰＦ6を１ｍｏｌ／ｌ溶解し、さらにリン酸トリオクチル０．５ｗｔ％、および表１に記載の化合物Ｎｏ．１（メチレンメタンジスルホン酸エステル：以下ＭＭＤＳと記載）１．５ｗｔ％を加えた。次に正極と負極をポリエチレンからなるセパレータを介して積層し、ラミネート外装型リチウムイオン二次電池を作製した。
(Example 1)
(Production of battery)
The production of the lithium ion battery of Example 1 of the present invention will be described. As the positive electrode, an aluminum foil having a thickness of 20 μm was used as the positive electrode current collector, and Li (Li 0.1 Mn 1.9 ) O 4 and LiNi 0.8 Co 0.15 Al 0.05 O 2 were mixed at a mass ratio of 80:20 as the positive electrode active material. A thing was used. Moreover, the negative electrode used the 10-micrometer-thick copper foil as a negative electrode electrical power collector, and used graphite as the negative electrode active material. As the electrolyte, a mixed solvent of EC and DEC (volume ratio: 30/70) was used as a solvent, 1 mol / l of LiPF 6 was dissolved as an electrolyte, 0.5 wt% of trioctyl phosphate, and the compound No. described in Table 1 . 1 (methylenemethane disulfonic acid ester: hereinafter referred to as MMDS) 1.5 wt% was added. Next, the positive electrode and the negative electrode were laminated via a separator made of polyethylene, to produce a laminated exterior type lithium ion secondary battery.
（充放電サイクル試験）
温度６０℃において、充電条件：充電終止電圧４．２Ｖ、充電レート１Ｃ、２．５時間、放電条件：放電終止電圧３．０Ｖ、放電レート０．２Ｃで充放電を行なった。容量維持率（％）は、５００サイクル後の放電容量（ｍＡｈ）の、１０サイクル目の放電容量（ｍＡｈ）に対する割合である。サイクル試験の結果を表２に示す。
(Charge / discharge cycle test)
At a temperature of 60 ° C., charging / discharging was performed under the following conditions: charging condition: end-of-charge voltage of 4.2 V, charging rate of 1 C, 2.5 hours, discharging condition: end-of-discharge voltage of 3.0 V, and discharging rate of 0.2 C. The capacity retention rate (%) is the ratio of the discharge capacity (mAh) after 500 cycles to the discharge capacity (mAh) at the 10th cycle. The results of the cycle test are shown in Table 2.
（実施例２〜６）
リン酸トリオクチルの添加量を３．０ｗｔ％、２．０ｗｔ％、０．２ｗｔ％、０．０５ｗｔ％、０．０１ｗｔ％とした他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Examples 2 to 6)
A lithium ion secondary battery was fabricated in the same manner as in Example 1 except that the amount of trioctyl phosphate added was 3.0 wt%, 2.0 wt%, 0.2 wt%, 0.05 wt%, 0.01 wt%, A charge / discharge cycle test was conducted. The results are shown in Table 2.
（実施例７〜１１）
ＭＭＤＳの添加量を０．５ｗｔ％、１．０ｗｔ％、２．０ｗｔ％、３．０ｗｔ％、５．０ｗｔ％とした他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Examples 7 to 11)
A lithium ion secondary battery was fabricated in the same manner as in Example 1 except that the amount of MMDS added was 0.5 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, and 5.0 wt%. A cycle test was performed. The results are shown in Table 2.
（実施例１２〜１３）
リン酸トリオクチルに代えてステアリン酸ナトリウムまたはＣ12Ｈ25−ＯＳＯ3Ｌｉとした他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Examples 12 to 13)
A lithium ion secondary battery was prepared in the same manner as in Example 1 except that sodium stearate or C 12 H 25 —OSO 3 Li was used instead of trioctyl phosphate, and a charge / discharge cycle test was performed. The results are shown in Table 2.
（実施例１４）
ＭＭＤＳに代えて表１に記載の化合物Ｎｏ．２（エチレンメタンジスルホン酸エステル：以下ＥＭＤＳと記載）とした他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Example 14)
In place of MMDS, the compound Nos. A lithium ion secondary battery was prepared in the same manner as in Example 1 except that it was changed to 2 (ethylene methanedisulfonate ester: hereinafter referred to as EMDS), and a charge / discharge cycle test was performed. The results are shown in Table 2.
（比較例１）
リン酸トリオクチルおよびＭＭＤＳを添加しない他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Comparative Example 1)
A lithium ion secondary battery was prepared in the same manner as in Example 1 except that trioctyl phosphate and MMDS were not added, and a charge / discharge cycle test was performed. The results are shown in Table 2.
（比較例２）
ＭＭＤＳを添加しない他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Comparative Example 2)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that MMDS was not added, and a charge / discharge cycle test was performed. The results are shown in Table 2.
（比較例３）
リン酸トリオクチルを添加しない他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表２に示す。
(Comparative Example 3)
A lithium ion secondary battery was prepared in the same manner as in Example 1 except that trioctyl phosphate was not added, and a charge / discharge cycle test was performed. The results are shown in Table 2.
実施例１〜実施例１４の電池は比較例１〜比較例３の電池と比較してサイクル試験後の容量維持率が改善されていることが確認された。 The batteries of Examples 1 to 14 were confirmed to have improved capacity retention after the cycle test as compared with the batteries of Comparative Examples 1 to 3.
（実施例１５）
正極活物質をＬｉＮｉ0.8Ｃｏ0.15Ａｌ0.05Ｏ2１００％とし、負極活物質を表面処理黒鉛とした他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表３に示す。
(Example 15)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the positive electrode active material was LiNi 0.8 Co 0.15 Al 0.05 O 2 100% and the negative electrode active material was surface-treated graphite, and a charge / discharge cycle test was performed. The results are shown in Table 3.
（比較例４）
リン酸トリオクチルおよびＭＭＤＳを添加しない他は実施例１５と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表３に示す。
(Comparative Example 4)
A lithium ion secondary battery was produced in the same manner as in Example 15 except that trioctyl phosphate and MMDS were not added, and a charge / discharge cycle test was performed. The results are shown in Table 3.
（比較例５）
ＭＭＤＳを添加しない他は実施例１５と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表３に示す。
(Comparative Example 5)
A lithium ion secondary battery was produced in the same manner as in Example 15 except that MMDS was not added, and a charge / discharge cycle test was performed. The results are shown in Table 3.
（比較例６）
リン酸トリオクチルを添加しない他は実施例１５と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表３に示す。
(Comparative Example 6)
A lithium ion secondary battery was prepared in the same manner as in Example 15 except that trioctyl phosphate was not added, and a charge / discharge cycle test was performed. The results are shown in Table 3.
実施例１５の電池は比較例４〜比較例６の電池に比較しサイクル試験後の容量維持率が高く、サイクル寿命特性が改善されたことが確認された。 It was confirmed that the battery of Example 15 had a higher capacity retention rate after the cycle test as compared with the batteries of Comparative Examples 4 to 6, and the cycle life characteristics were improved.
（実施例１６）
正極活物質をＬｉＣｏＯ2とし、電解液の溶媒としてＥＣとＧＢＬの混合溶媒（体積比：２０／８０）を用いた他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表４に示す。
(Example 16)
A lithium ion secondary battery was prepared in the same manner as in Example 1 except that the positive electrode active material was LiCoO 2 and a mixed solvent of EC and GBL (volume ratio: 20/80) was used as the solvent of the electrolytic solution. A test was conducted. The results are shown in Table 4.
（比較例７）
リン酸トリオクチルおよびＭＭＤＳを添加しない他は実施例１６と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表４に示す。
(Comparative Example 7)
A lithium ion secondary battery was produced in the same manner as in Example 16 except that trioctyl phosphate and MMDS were not added, and a charge / discharge cycle test was performed. The results are shown in Table 4.
（比較例８）
ＭＭＤＳを添加しない他は実施例１６と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表４に示す。
(Comparative Example 8)
A lithium ion secondary battery was produced in the same manner as in Example 16 except that MMDS was not added, and a charge / discharge cycle test was performed. The results are shown in Table 4.
（比較例９）
リン酸トリオクチルを添加しない他は実施例１６と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表４に示す。
(Comparative Example 9)
A lithium ion secondary battery was produced in the same manner as in Example 16 except that trioctyl phosphate was not added, and a charge / discharge cycle test was performed. The results are shown in Table 4.
実施例１６の電池は比較例７〜比較例９の電池に比較しサイクル試験後の容量維持率が高く、サイクル寿命特性が改善されたことが確認された。 It was confirmed that the battery of Example 16 had a higher capacity retention rate after the cycle test as compared with the batteries of Comparative Examples 7 to 9, and the cycle life characteristics were improved.
（実施例１７）
正極活物質をＬｉ（Ｍｎ1.9Ｌｉ0.1）Ｏ4とし、負極活物質を非晶質炭素とし電解液の溶媒としてＥＣとＰＣＬの混合溶媒（体積比：１０／９０）を用いた他は実施例１と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。充放電サイクル試験は放電終止電圧を２．５Vとした以外は実施例１と同じ方法で行った。結果を表５に示す。
(Example 17)
Example except that the positive electrode active material is Li (Mn 1.9 Li 0.1 ) O 4 , the negative electrode active material is amorphous carbon, and a mixed solvent of EC and PCL (volume ratio: 10/90) is used as a solvent for the electrolytic solution. A lithium ion secondary battery was prepared in the same manner as in Example 1, and a charge / discharge cycle test was performed. The charge / discharge cycle test was performed in the same manner as in Example 1 except that the final discharge voltage was 2.5V. The results are shown in Table 5.
（比較例１０）
リン酸トリオクチルおよびＭＭＤＳを添加しない他は実施例１７と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表５に示す。
(Comparative Example 10)
A lithium ion secondary battery was produced in the same manner as in Example 17 except that trioctyl phosphate and MMDS were not added, and a charge / discharge cycle test was performed. The results are shown in Table 5.
（比較例１１）
ＭＭＤＳを添加しない他は実施例１７と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表５に示す。
(Comparative Example 11)
A lithium ion secondary battery was produced in the same manner as in Example 17 except that MMDS was not added, and a charge / discharge cycle test was performed. The results are shown in Table 5.
（比較例１２）
リン酸トリオクチルを添加しない他は実施例１７と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表５に示す。
(Comparative Example 12)
A lithium ion secondary battery was produced in the same manner as in Example 17 except that trioctyl phosphate was not added, and a charge / discharge cycle test was performed. The results are shown in Table 5.
実施例１７の電池は比較例１０〜比較例１２の電池に比較しサイクル試験後の容量維持率が高く、サイクル寿命特性が改善されたことが確認された。 It was confirmed that the battery of Example 17 had a higher capacity retention rate after the cycle test than the batteries of Comparative Examples 10 to 12, and the cycle life characteristics were improved.
（実施例１８）
正極活物質をＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2とした他は実施例１５と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表６に示す。
(Example 18)
A lithium ion secondary battery was prepared in the same manner as in Example 15 except that the positive electrode active material was LiNi 1/3 Co 1/3 Mn 1/3 O 2 , and a charge / discharge cycle test was performed. The results are shown in Table 6.
（比較例１３）
リン酸トリオクチルおよびＭＭＤＳを添加しない他は実施例１８と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表６に示す。
(Comparative Example 13)
A lithium ion secondary battery was produced in the same manner as in Example 18 except that trioctyl phosphate and MMDS were not added, and a charge / discharge cycle test was performed. The results are shown in Table 6.
（比較例１４）
ＭＭＤＳを添加しない他は実施例１８と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表６に示す。
(Comparative Example 14)
A lithium ion secondary battery was produced in the same manner as in Example 18 except that MMDS was not added, and a charge / discharge cycle test was performed. The results are shown in Table 6.
（比較例１５）
リン酸トリオクチルを添加しない他は実施例１８と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表５に示す。
(Comparative Example 15)
A lithium ion secondary battery was produced in the same manner as in Example 18 except that trioctyl phosphate was not added, and a charge / discharge cycle test was performed. The results are shown in Table 5.
実施例１８の電池は比較例１３〜比較例１５の電池に比較しサイクル試験後の容量維持率が高く、サイクル寿命特性が改善されたことが確認された。 It was confirmed that the battery of Example 18 had a higher capacity retention rate after the cycle test than the batteries of Comparative Examples 13 to 15, and the cycle life characteristics were improved.
（実施例１９）
正極活物質をＬｉＮｉ0.5Ｍｎ1.35Ｔｉ0.15Ｏ4とし、電解液の溶媒としてＥＣとＤＭＣ.の混合溶媒（体積比：４０／６０）を用いた他は実施例１と同様にリチウムイオン二次電池を作製した。充放電サイクルにおける充電終止電圧を４．７５Ｖとし、放電終止電圧を３Ｖとした他は、実施例１と同じ条件でサイクル試験を行った。結果を表７に示す。
(Example 19)
A lithium ion secondary battery as in Example 1 except that the positive electrode active material was LiNi 0.5 Mn 1.35 Ti 0.15 O 4 and a mixed solvent of EC and DMC. (Volume ratio: 40/60) was used as the solvent of the electrolytic solution. Was made. A cycle test was performed under the same conditions as in Example 1 except that the charge end voltage in the charge / discharge cycle was 4.75 V and the discharge end voltage was 3 V. The results are shown in Table 7.
（比較例１６）
リン酸トリオクチルおよびＭＭＤＳを添加しない他は実施例１９と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表７に示す。
(Comparative Example 16)
A lithium ion secondary battery was produced in the same manner as in Example 19 except that trioctyl phosphate and MMDS were not added, and a charge / discharge cycle test was performed. The results are shown in Table 7.
（比較例１７）
ＭＭＤＳを添加しない他は実施例１９と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表７に示す。
(Comparative Example 17)
A lithium ion secondary battery was produced in the same manner as in Example 19 except that MMDS was not added, and a charge / discharge cycle test was performed. The results are shown in Table 7.
（比較例１８）
リン酸トリオクチルを添加しない他は実施例１９と同様にリチウムイオン二次電池を作製し、充放電サイクル試験を行なった。結果を表７に示す。
(Comparative Example 18)
A lithium ion secondary battery was produced in the same manner as in Example 19 except that trioctyl phosphate was not added, and a charge / discharge cycle test was performed. The results are shown in Table 7.
実施例１９の電池は比較例１６〜１８の電池に比較しサイクル試験後の容量維持率が高く、サイクル寿命特性が改善されたことが確認された。 It was confirmed that the battery of Example 19 had a higher capacity retention rate after the cycle test as compared with the batteries of Comparative Examples 16 to 18, and the cycle life characteristics were improved.
１１正極集電体
１２正極活物質を含有する層
１３負極活物質を含有する層
１４負極集電体
１５電解液
１６セパレータ
11 positive electrode
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