JP5160744B2 - Nonaqueous electrolyte secondary battery - Google Patents
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Description
本発明は、リチウムを吸蔵放出する電極と電解質とを備える非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery including an electrode that occludes and releases lithium and an electrolyte.
リチウムイオン電池の充放電サイクル寿命特性を向上させるために、電解液の添加剤が数多く提案されている。例えば、負極に金属リチウムを用いた非水電解質二次電池において、リチウムと反応し難い不飽和の炭素−炭素結合を含む化合物としてビニルエチレンカーボネートを溶媒に用いることが提案されている（特許文献１参照）。また、負極に炭素材料を用いた非水電解質において、ビニルエチレンカーボネート誘導体を使用することが提案されている（特許文献２参照）。さらに、黒鉛系負極を用いたリチウム電池において、電解液の分解を抑制するために、ビニレンカーボネート及びその誘電体を含有する電解液が提案されている（特許文献３参照）。また、軽金属を用いたリチウム電池において、負極上での電解液の還元分解反応を抑制するために、電解液にフルオロエチレンカーボネートを添加することが提案されている（特許文献４参照）。
しかし、上述した環状炭酸エステル誘導体を電解液に添加した場合、充放電サイクル寿命特性は向上するが、充電状態の電池を高温で放置した際に正極上で環状炭酸エステル誘導体が酸化分解される際に炭酸ガスを発生するため、電池の内圧が上昇し、電池厚みが増大するという問題があった。さらに、環状炭酸エステル誘導体を過剰に添加した場合、正極及び負極上で環状炭酸エステル誘導体が分解される際に発生した分解物がセパレータの目詰まりを誘発したり、また、正極及び負極上にリチウムイオンの移動抵抗の高い被膜として存在するために、放電性能が低下し、充放電サイクル寿命特性（容量保持率）が低下するという問題があった。 However, when the above-mentioned cyclic carbonate derivative is added to the electrolyte, the charge / discharge cycle life characteristics are improved. However, when the charged battery is left at a high temperature, the cyclic carbonate derivative is oxidatively decomposed on the positive electrode. Since carbon dioxide gas is generated, the internal pressure of the battery rises and the battery thickness increases. Furthermore, when the cyclic carbonate derivative is added excessively, a decomposition product generated when the cyclic carbonate derivative is decomposed on the positive electrode and the negative electrode induces clogging of the separator, or lithium on the positive electrode and the negative electrode. Since it exists as a film having a high ion migration resistance, there is a problem that the discharge performance is lowered and the charge / discharge cycle life characteristic (capacity retention) is lowered.
上記問題を改善する方法として、上記環状炭酸エステル誘導体の添加量を減量することが考えられるが、環状炭酸エステル誘導体を減量した場合は負極被膜が十分に形成されず、充放電サイクルにともない負極上で電解液の分解が進行し、電解液が枯渇するため、充放電サイクル寿命特性が低下するという問題がある。逆に過剰に添加した場合は、負極の被膜抵抗が大きくなり、負極上に金属リチウムが析出したり、環状炭酸エステル誘導体の分解物によってセパレータの目詰まりが生じ易くなるので、充放電サイクル寿命特性が低下するという問題がある。 As a method for improving the above problem, it is conceivable to reduce the amount of the cyclic carbonate derivative added. However, when the amount of the cyclic carbonate derivative is reduced, the negative electrode film is not sufficiently formed, and the negative electrode film is formed on the negative electrode due to the charge / discharge cycle. However, since the decomposition of the electrolytic solution proceeds and the electrolytic solution is depleted, the charge / discharge cycle life characteristic is deteriorated. On the other hand, when added excessively, the film resistance of the negative electrode is increased, and metallic lithium is deposited on the negative electrode, or the separator is easily clogged by the decomposition product of the cyclic carbonate derivative. There is a problem that decreases.
本発明は斯かる事情に鑑みてなされたものであり、電解質に、ＡＬＯＭ−ＥＣ（4-(prop-2-enyloxymethyl)-1,3-dioxolan-2-one:4-(2- プロペニルオキシメチル)-1,3-ジオキソラン-2- オン）及びＰＧＯＭ−ＥＣ（4-(prop-2-ynyloxymethyl)-1,3-dioxolan-2-one：4-(2- プロピニルオキシメチル)-1,3-ジオキソラン-2- オン）のうちの少なくとも１種からなる環状炭酸エステル誘導体と、ＤＫ（ジケテン）及びＶＡ（酢酸ビニル）のうちの少なくとも１種からなるビニルエステル誘導体とを含有させることにより、充放電サイクル寿命特性を向上出来ると共に、電池を高温で保存した際の電池厚みの増大を抑制することが出来る非水電解質二次電池を提供することを目的とする。 The present invention has been made in view of such circumstances, and the electrolyte contains ALOM-EC (4- (prop-2-enyloxymethyl) -1,3-dioxolan-2-one : 4- (2-propenyloxymethyl). ) -1,3-dioxolan-2-one ) and PGOM-EC (4- (prop-2-ynyloxymethyl) -1,3-dioxolan-2-one : 4- (2-propynyloxymethyl) -1,3 A cyclic carbonate derivative consisting of at least one of ( 2-dioxolan-2-one ) and a vinyl ester derivative consisting of at least one of DK (diketene) and VA (vinyl acetate). An object of the present invention is to provide a non-aqueous electrolyte secondary battery that can improve discharge cycle life characteristics and suppress an increase in battery thickness when the battery is stored at a high temperature.
第１発明に係る非水電解質二次電池は、リチウムを吸蔵放出する電極と電解質とを備える非水電解質二次電池において、前記電解質は、下記化１で表されるＡＬＯＭ−ＥＣ（4-(2- プロペニルオキシメチル)-1,3-ジオキソラン-2- オン）、及び下記化２で表されるＰＧＯＭ−ＥＣ（4-(2- プロピニルオキシメチル)-1,3-ジオキソラン-2- オン）のうちの少なくとも１種からなる環状炭酸エステル誘導体と、下記化３で表されるＤＫ（ジケテン）、及び下記化４で表されるＶＡ（酢酸ビニル）のうちの少なくとも１種からなるビニルエステル誘導体とを含んでなることを特徴とする。
A non-aqueous electrolyte secondary battery according to a first aspect of the present invention is a non-aqueous electrolyte secondary battery comprising an electrode that occludes and releases lithium, and the electrolyte is an ALOM-EC ( 4- ( 2-propenyloxymethyl) -1,3-dioxolan-2-one ) and PGOM-EC represented by the following chemical formula ( 4- (2-propynyloxymethyl) -1,3-dioxolan-2-one ) A cyclic ester carbonate derivative comprising at least one of the above, DK (diketene) represented by the following
第２発明に係る非水電解質二次電池は、第１発明において、前記電解質の前記環状炭酸エステル誘導体の含有量は０．１質量％以上３質量％以下であることを特徴とする。 A nonaqueous electrolyte secondary battery according to a second invention is characterized in that, in the first invention, the content of the cyclic carbonate derivative of the electrolyte is 0.1 mass% or more and 3 mass% or less.
第３発明に係る非水電解質二次電池は、第１又は第２発明において、前記電解質の前記ビニルエステル誘導体の含有量は０．０１質量％以上２質量％以下であることを特徴とする。 The nonaqueous electrolyte secondary battery according to a third invention is characterized in that, in the first or second invention, the content of the vinyl ester derivative in the electrolyte is 0.01% by mass or more and 2% by mass or less.
第１発明においては、電解質に、ＡＬＯＭ−ＥＣ及びＰＧＯＭ−ＥＣのうちの少なくとも１種からなる環状炭酸エステル誘導体と、ＤＫ及びＶＡのうちの少なくとも１種からなるビニルエステル誘導体とを含有させた場合、前記環状炭酸エステル誘導体及び前記ビニルエステル誘導体を混合した添加剤が還元分解することによって形成される負極被膜が電解液の分解を抑制し、初期充放電効率が高くなる。そのため、初期容量の低減を抑制することができ、初期容量の大きい電池が得られる。また、負極の被膜抵抗が大きく上がらないため、負極上の金属リチウムデンドライトが発生し難くなる。 In the first invention, when the electrolyte contains a cyclic carbonate derivative comprising at least one of ALOM-EC and PGOM-EC and a vinyl ester derivative comprising at least one of DK and VA The negative electrode film formed by the reductive decomposition of the additive in which the cyclic carbonate derivative and the vinyl ester derivative are mixed suppresses the decomposition of the electrolytic solution, thereby increasing the initial charge / discharge efficiency. Therefore, a reduction in initial capacity can be suppressed, and a battery having a large initial capacity can be obtained. Moreover, since the film resistance of the negative electrode does not increase greatly, it is difficult to generate metallic lithium dendrite on the negative electrode.
また、前記ビニルエステル誘導体は前記環状炭酸エステル誘導体よりも酸化分解を受け難く、また酸化分解物が気体でないため分解の際にガスの発生が少なく、高温放置時のガス発生を抑制することが出来る。さらに、前記ビニルエステル誘導体が負極表面に被膜を形成し、電解液成分が負極上で還元され、ガスを発生する反応を抑制することが出来る。また、前記ビニルエステル誘導体は、負極上の環状炭酸エステル誘導体の分解反応や、正負極上での電解液の分解反応を抑制するため、高温放置時のガス発生が少なく、電池厚みの増加を抑制でき、また充放電サイクル寿命特性も高くなる。 In addition, the vinyl ester derivative is less susceptible to oxidative degradation than the cyclic carbonate derivative, and since the oxidative decomposition product is not a gas, the generation of gas is small during decomposition, and the generation of gas when left at high temperature can be suppressed. . Furthermore, the vinyl ester derivative forms a film on the surface of the negative electrode, and the electrolyte component is reduced on the negative electrode, thereby suppressing a reaction that generates gas. In addition, the vinyl ester derivative suppresses the decomposition reaction of the cyclic carbonate derivative on the negative electrode and the decomposition reaction of the electrolyte solution on the positive and negative electrodes, so that there is little gas generation when left at high temperature and the increase in battery thickness can be suppressed. Also, the charge / discharge cycle life characteristics are improved.
また、前記ビニルエステル誘導体は、前記環状炭酸エステル誘導体と同様に負極上に被膜を形成し、負極上での電解液の分解を抑制するが、前記ビニルエステル誘導体単独又は前記環状炭酸エステル誘導体単独がそれぞれ形成する負極被膜よりも、前記ビニルエステル誘導体及び前記環状炭酸エステル誘導体を混合した場合に形成される負極被膜の方が安定であり、相乗効果によって充放電サイクル寿命特性がさらに向上する。 The vinyl ester derivative forms a film on the negative electrode in the same manner as the cyclic carbonate derivative and suppresses the decomposition of the electrolytic solution on the negative electrode, but the vinyl ester derivative alone or the cyclic carbonate derivative alone The negative electrode film formed when the vinyl ester derivative and the cyclic carbonate derivative are mixed is more stable than the negative electrode film to be formed, and the charge / discharge cycle life characteristics are further improved by a synergistic effect.
第２発明においては、電解質の環状炭酸エステル誘導体の含有量を０．１質量％以上３質量％以下にすると、充放電サイクル寿命特性を向上させ、高温放置時の電池厚みの増加を抑制することが出来ると共に、初期容量の低下を抑制することが出来る。環状炭酸エステル誘導体の含有量が０．１質量％未満の場合は、充放電サイクル寿命特性が向上せず、３質量％を超える場合は、初期容量が低下し、電池厚みが増加し、放電性能が低下する。 In the second invention, when the content of the cyclic carbonate derivative of the electrolyte is 0.1% by mass or more and 3% by mass or less, the charge / discharge cycle life characteristics are improved, and an increase in the battery thickness when left at high temperature is suppressed. And a decrease in the initial capacity can be suppressed. When the content of the cyclic carbonate derivative is less than 0.1% by mass, the charge / discharge cycle life characteristics are not improved. When the content exceeds 3% by mass, the initial capacity decreases, the battery thickness increases, and the discharge performance. Decreases.
第３発明においては、電解質のビニルエステル誘導体の含有量が０．０１質量％以上２質量％以下であるため、充放電サイクル寿命特性を向上させ、高温放置時の電池厚みの増加を抑制することが出来ると共に、初期容量の低下を抑制することが出来る。ビニルエステル誘導体の含有量が０．０１質量％未満の場合は、電池厚みが増加、放電性能が低下し、２質量％を超える場合は、初期容量が低下する。 In the third invention, since the content of the vinyl ester derivative of the electrolyte is 0.01% by mass or more and 2% by mass or less, the charge / discharge cycle life characteristics are improved, and the increase in battery thickness when left at high temperature is suppressed. And a decrease in the initial capacity can be suppressed. When the content of the vinyl ester derivative is less than 0.01% by mass, the battery thickness increases and the discharge performance decreases, and when it exceeds 2% by mass, the initial capacity decreases.
本発明によれば、充放電サイクル寿命特性（容量保持率）を向上出来ると共に、電池を高温で保存した際の電池厚みの増加を抑制することが出来る。 ADVANTAGE OF THE INVENTION According to this invention, while being able to improve a charge / discharge cycle life characteristic (capacity retention), the increase in battery thickness at the time of storing a battery at high temperature can be suppressed.
以下、好適な参考例を用いて本発明を説明するが、本発明は本参考例により何ら制限されるものではなく、その主旨を変更しない範囲において、適宜変更して実施することが出来る。 Hereinafter, the present invention will be described with reference to preferred reference examples. However, the present invention is not limited to the present reference examples, and can be appropriately modified and implemented without departing from the spirit of the present invention.
（実施例１）
図１は本発明に係る非水電解質二次電池の例を示す概略断面図である。図１において、１は非水電解質二次電池（以下、電池という）、２は電極群、３は負極、４は正極、５はセパレータ、６は電池ケース、７は電池蓋、８は安全弁、９は負極端子、１０は負極リードである。電極群２は、負極３と正極４とをセパレータ５を介して扁平状に巻回したものである。電極群２は電池ケース６に収納してあり、電池ケース６の開口部は、安全弁８及び負極端子９が設けられた電池蓋７をレーザ溶接して密閉している。負極端子９は負極リード１０と接続され、正極４は電池ケース６内面と接続されている。電池１は角型であり、厚みは４．２ｍｍである。
Example 1
FIG. 1 is a schematic cross-sectional view showing an example of a nonaqueous electrolyte secondary battery according to the present invention. In FIG. 1, 1 is a non-aqueous electrolyte secondary battery (hereinafter referred to as a battery), 2 is an electrode group, 3 is a negative electrode, 4 is a positive electrode, 5 is a separator, 6 is a battery case, 7 is a battery lid, 8 is a safety valve, 9 is a negative electrode terminal, and 10 is a negative electrode lead. The
正極４については、活物質としてＬｉＣｏＯ2 ９４質量％と、導電助剤としてアセチレンブラック３質量％と、結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）３質量％とを混合した正極合剤を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に分散させることによりペーストを調製した。このペーストを厚さ２０μｍのアルミニウム集電体に均一に塗布し、乾燥させた後、ロールプレスで圧縮形成することにより正極４を作製した。
For the
負極３については、活物質として黒鉛９５質量％と、結着剤としてカルボキシメチルセルロース３質量％、スチレンブタジエンゴム２質量％とを混合し、蒸留水を適宜加えて分散させ、スラリーを調製した。このスラリーを厚さ１５μｍの銅集電体に均一に塗布、乾燥させた後、１００℃で５時間乾燥させ、ロールプレスで圧縮形成することにより負極３を作製した。
Regarding the
セパレータ５は、厚さ２０μｍの微多孔性ポリエチレンフィルムを用いた。電解質は、エチレンカーボネート（ＥＣ）とエチルメチルカーボネート（ＥＭＣ）とジエチルカーボネート（ＤＥＣ）との体積比３：２：５混合溶媒にＬｉＰＦ6 を１．１ｍｏｌ／Ｌ溶解させた電解質に、さらに電解質の総量に対して前記ＡＬＯＭ−ＥＣを０．５質量％、前記ＤＫを０．５質量％添加したものを用いた。
As the
（実施例２）
電解質の総量に対してＡＬＯＭ−ＥＣを０．５質量％、前記ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Example 2)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of ALOM-EC and 0.5% by mass of the VA were added to the total amount of the electrolyte.
（実施例３）
電解質の総量に対して前記ＰＧＯＭ−ＥＣを０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（実施例４）
電解質の総量に対してＰＧＯＭ−ＥＣを０．５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Example 3)
A battery was fabricated in the same manner as in Example 1 except that 0.5% by mass of PGOM-EC and 0.5% by mass of DK were added to the total amount of the electrolyte.
Example 4
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of PGOM-EC and 0.5% by mass of VA were added to the total amount of the electrolyte.
（参考例１）
電解質の総量に対してビニレンカーボネート（ＶＣ(1,3-dioxolen-2-one)、化５参照）を０．１質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 1)
0.1% by weight of vinylene carbonate (VC (1,3-dioxolen-2-one), refer to Chemical Formula 5) and 0.01% by weight of DK are added to the total amount of the electrolyte, and the rest is the same as in Example 1. A similar battery was produced.
（参考例２）
電解質の総量に対してＶＣを０．５質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３）
電解質の総量に対してＶＣを１質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４）
電解質の総量に対してＶＣを２質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 2)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 3)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 4)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 0.01% by mass of DK were added to the total amount of the electrolyte.
（参考例５）
電解質の総量に対してＶＣを３質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６）
電解質の総量に対してＶＣを５質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 5)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 6)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 0.01% by mass of DK were added to the total amount of the electrolyte.
（参考例７）
電解質の総量に対してＶＣを０．１質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８）
電解質の総量に対してＶＣを０．５質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９）
電解質の総量に対してＶＣを１質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０）
電解質の総量に対してＶＣを２質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１）
電解質の総量に対してＶＣを３質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２）
電解質の総量に対してＶＣを５質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 7)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 8)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 9)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 10)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 11)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 12)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 0.1% by mass of DK were added to the total amount of the electrolyte.
（参考例１３）
電解質の総量に対してＶＣを０．１質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１４）
電解質の総量に対してＶＣを０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１５）
電解質の総量に対してＶＣを１質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１６）
電解質の総量に対してＶＣを２質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１７）
電解質の総量に対してＶＣを３質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１８）
電解質の総量に対してＶＣを５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 13)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 14)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 15)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 16)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 17)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 18)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 0.5% by mass of DK were added to the total amount of the electrolyte.
（参考例１９）
電解質の総量に対してＶＣを０．１質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２０）
電解質の総量に対してＶＣを０．５質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２１）
電解質の総量に対してＶＣを１質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２２）
電解質の総量に対してＶＣを２質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２３）
電解質の総量に対してＶＣを３質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２４）
電解質の総量に対してＶＣを５質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 19)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 20)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 21)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 22)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 23)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 24)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 1% by mass of DK were added to the total amount of the electrolyte.
（参考例２５）
電解質の総量に対してＶＣを０．１質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２６）
電解質の総量に対してＶＣを０．５質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２７）
電解質の総量に対してＶＣを１質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２８）
電解質の総量に対してＶＣを２質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例２９）
電解質の総量に対してＶＣを３質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３０）
電解質の総量に対してＶＣを５質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 25)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by weight of VC and 2% by weight of DK were added to the total amount of the electrolyte.
(Reference Example 26)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 27)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 28)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 29)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 30)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 2% by mass of DK were added to the total amount of the electrolyte.
（参考例３１）
電解質の総量に対してＶＣを０．１質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３２）
電解質の総量に対してＶＣを０．５質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３３）
電解質の総量に対してＶＣを１質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３４）
電解質の総量に対してＶＣを２質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３５）
電解質の総量に対してＶＣを３質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３６）
電解質の総量に対してＶＣを５質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 31)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 32)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 33)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 34)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 35)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 36)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 3% by mass of DK were added to the total amount of the electrolyte.
（参考例３７）
電解質の総量に対してＶＣを０．１質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３８）
電解質の総量に対してＶＣを０．５質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例３９）
電解質の総量に対してＶＣを１質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４０）
電解質の総量に対してＶＣを２質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４１）
電解質の総量に対してＶＣを３質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４２）
電解質の総量に対してＶＣを５質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 37)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 38)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 39)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 40)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 41)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 42)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 0.01% by mass of VA were added to the total amount of the electrolyte.
（参考例４３）
電解質の総量に対してＶＣを０．１質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４４）
電解質の総量に対してＶＣを０．５質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４５）
電解質の総量に対してＶＣを１質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４６）
電解質の総量に対してＶＣを２質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４７）
電解質の総量に対してＶＣを３質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例４８）
電解質の総量に対してＶＣを５質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 43)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 44)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 45)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 46)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 47)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 48)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 0.1% by mass of VA were added to the total amount of the electrolyte.
（参考例４９）
電解質の総量に対してＶＣを０．１質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５０）
電解質の総量に対してＶＣを０．５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５１）
電解質の総量に対してＶＣを１質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５２）
電解質の総量に対してＶＣを２質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５３）
電解質の総量に対してＶＣを３質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５４）
電解質の総量に対してＶＣを５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 49)
A battery was manufactured in the same manner as in Example 1 except that 0.1 mass% of VC and 0.5 mass% of VA were added to the total amount of the electrolyte.
(Reference Example 50)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 51)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 52)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 53)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 54)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 0.5% by mass of VA were added to the total amount of the electrolyte.
（参考例５５）
電解質の総量に対してＶＣを０．１質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５６）
電解質の総量に対してＶＣを０．５質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５７）
電解質の総量に対してＶＣを１質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５８）
電解質の総量に対してＶＣを２質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例５９）
電解質の総量に対してＶＣを３質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６０）
電解質の総量に対してＶＣを５質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 55)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by weight of VC and 1% by weight of VA were added to the total amount of the electrolyte.
(Reference Example 56)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 57)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 58)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 59)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 60)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 1% by mass of VA were added to the total amount of the electrolyte.
（参考例６１）
電解質の総量に対してＶＣを０．１質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６２）
電解質の総量に対してＶＣを０．５質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６３）
電解質の総量に対してＶＣを１質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６４）
電解質の総量に対してＶＣを２質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６５）
電解質の総量に対してＶＣを３質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６６）
電解質の総量に対してＶＣを５質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 61)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by weight of VC and 2% by weight of VA were added to the total amount of the electrolyte.
(Reference Example 62)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 63)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 64)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 65)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 66)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 2% by mass of VA were added to the total amount of the electrolyte.
（参考例６７）
電解質の総量に対してＶＣを０．１質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６８）
電解質の総量に対してＶＣを０．５質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例６９）
電解質の総量に対してＶＣを１質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７０）
電解質の総量に対してＶＣを２質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７１）
電解質の総量に対してＶＣを３質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７２）
電解質の総量に対してＶＣを５質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 67)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 68)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 69)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 70)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 71)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 72)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC and 3% by mass of VA were added to the total amount of the electrolyte.
（参考例７３）
電解質の総量に対してモノフルオロエチレンカーボネート（ＦＥＣ（4-fluoro-1,3-dioxolan-2-one）、化６参照）を０．１質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 73)
0.1% by mass of monofluoroethylene carbonate (FEC (4-fluoro-1,3-dioxolan-2-one), see Chemical formula 6) and 0.01% by mass of DK are added to the total amount of the electrolyte. A battery was prepared in the same manner as in Example 1 except for the above.
（参考例７４）
電解質の総量に対してＦＥＣを０．５質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７５）
電解質の総量に対してＦＥＣを１質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７６）
電解質の総量に対してＦＥＣを２質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７７）
電解質の総量に対してＦＥＣを３質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例７８）
電解質の総量に対してＦＥＣを５質量％、ＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 74)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 75)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 76)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 77)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 0.01% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 78)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 0.01% by mass of DK were added to the total amount of the electrolyte.
（参考例７９）
電解質の総量に対してＦＥＣを０．１質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８０）
電解質の総量に対してＦＥＣを０．５質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８１）
電解質の総量に対してＦＥＣを１質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８２）
電解質の総量に対してＦＥＣを２質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８３）
電解質の総量に対してＦＥＣを３質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８４）
電解質の総量に対してＦＥＣを５質量％、ＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 79)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 80)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 81)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 82)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 83)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 0.1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 84)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 0.1% by mass of DK were added to the total amount of the electrolyte.
（参考例８５）
電解質の総量に対してＦＥＣを０．１質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８６）
電解質の総量に対してＦＥＣを０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８７）
電解質の総量に対してＦＥＣを１質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８８）
電解質の総量に対してＦＥＣを２質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例８９）
電解質の総量に対してＦＥＣを３質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９０）
電解質の総量に対してＦＥＣを５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 85)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 86)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 87)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 88)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 89)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 90)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 0.5% by mass of DK were added to the total amount of the electrolyte.
（参考例９１）
電解質の総量に対してＦＥＣを０．１質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９２）
電解質の総量に対してＦＥＣを０．５質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９３）
電解質の総量に対してＦＥＣを１質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９４）
電解質の総量に対してＦＥＣを２質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９５）
電解質の総量に対してＦＥＣを３質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９６）
電解質の総量に対してＦＥＣを５質量％、ＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 91)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 92)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 93)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 94)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 95)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 1% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 96)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 1% by mass of DK were added to the total amount of the electrolyte.
（参考例９７）
電解質の総量に対してＦＥＣを０．１質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９８）
電解質の総量に対してＦＥＣを０．５質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例９９）
電解質の総量に対してＦＥＣを１質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１００）
電解質の総量に対してＦＥＣを２質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０１）
電解質の総量に対してＦＥＣを３質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０２）
電解質の総量に対してＦＥＣを５質量％、ＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 97)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 98)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 99)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 100)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 101)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 2% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 102)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 2% by mass of DK were added to the total amount of the electrolyte.
（参考例１０３）
電解質の総量に対してＦＥＣを０．１質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０４）
電解質の総量に対してＦＥＣを０．５質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０５）
電解質の総量に対してＦＥＣを１質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０６）
電解質の総量に対してＦＥＣを２質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０７）
電解質の総量に対してＦＥＣを３質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１０８）
電解質の総量に対してＦＥＣを５質量％、ＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 103)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 104)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 105)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 106)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 107)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 3% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 108)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 3% by mass of DK were added to the total amount of the electrolyte.
（参考例１０９）
電解質の総量に対してＦＥＣを０．１質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１０）
電解質の総量に対してＦＥＣを０．５質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１１）
電解質の総量に対してＦＥＣを１質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１２）
電解質の総量に対してＦＥＣを２質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１３）
電解質の総量に対してＦＥＣを３質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１４）
電解質の総量に対してＦＥＣを５質量％、ＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 109)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 110)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 111)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 112)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 113)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 0.01% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 114)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 0.01% by mass of VA were added to the total amount of the electrolyte.
（参考例１１５）
電解質の総量に対してＦＥＣを０．１質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１６）
電解質の総量に対してＦＥＣを０．５質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１７）
電解質の総量に対してＦＥＣを１質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１８）
電解質の総量に対してＦＥＣを２質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１１９）
電解質の総量に対してＦＥＣを３質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２０）
電解質の総量に対してＦＥＣを５質量％、ＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 115)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 116)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 117)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 118)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 119)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 0.1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 120)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 0.1% by mass of VA were added to the total amount of the electrolyte.
（参考例１２１）
電解質の総量に対してＦＥＣを０．１質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２２）
電解質の総量に対してＦＥＣを０．５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２３）
電解質の総量に対してＦＥＣを１質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２４）
電解質の総量に対してＦＥＣを２質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２５）
電解質の総量に対してＦＥＣを３質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２６）
電解質の総量に対してＦＥＣを５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 121)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 122)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 123)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 124)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 125)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 126)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
（参考例１２７）
電解質の総量に対してＦＥＣを０．１質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２８）
電解質の総量に対してＦＥＣを０．５質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１２９）
電解質の総量に対してＦＥＣを１質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３０）
電解質の総量に対してＦＥＣを２質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３１）
電解質の総量に対してＦＥＣを３質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３２）
電解質の総量に対してＦＥＣを５質量％、ＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 127)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 128)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 129)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 130)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 131)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 1% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 132)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 1% by mass of VA were added to the total amount of the electrolyte.
（参考例１３３）
電解質の総量に対してＦＥＣを０．１質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３４）
電解質の総量に対してＦＥＣを０．５質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３５）
電解質の総量に対してＦＥＣを１質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３６）
電解質の総量に対してＦＥＣを２質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３７）
電解質の総量に対してＦＥＣを３質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１３８）
電解質の総量に対してＦＥＣを５質量％、ＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 133)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 134)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 135)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 136)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 137)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 2% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 138)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 2% by mass of VA were added to the total amount of the electrolyte.
（参考例１３９）
電解質の総量に対してＦＥＣを０．１質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１４０）
電解質の総量に対してＦＥＣを０．５質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１４１）
電解質の総量に対してＦＥＣを１質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１４２）
電解質の総量に対してＦＥＣを２質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１４３）
電解質の総量に対してＦＥＣを３質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１４４）
電解質の総量に対してＦＥＣを５質量％、ＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 139)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 140)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 141)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of FEC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 142)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 143)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC and 3% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 144)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC and 3% by mass of VA were added to the total amount of the electrolyte.
（参考例１４５）
電解質の総量に対してビニルエチレンカーボネート（ＶＥＣ（4-vinyl-1,3-dioxolan-2-one）、化７参照）を０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 145)
Add 0.5% by mass of vinyl ethylene carbonate (VEC (4-vinyl-1,3-dioxolan-2-one), see chemical formula 7), 0.5% by mass of DK to the total amount of electrolyte, and other than that Produced the same battery as in Example 1.
（参考例１４６）
電解質の総量に対してＶＥＣを０．５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 146)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
（参考例１４７）
電解質の総量に対してジビニルエチレンカーボネート（ＤＶＥＣ（4,5-divinyl-1,3-dioxolan-2-one）、化８参照）を０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 147)
0.5% by mass of divinylethylene carbonate (DVEC (4,5-divinyl-1,3-dioxolan-2-one), see Chemical Formula 8) and 0.5% by mass of DK are added to the total amount of the electrolyte, Otherwise, a battery similar to that of Example 1 was produced.
（参考例１４８）
電解質の総量に対してＤＶＥＣを０．５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 148)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of DVEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
（参考例１４９）
電解質の総量に対してモノクロロエチレンカーボネート（ＣｌＥＣ（4-chloro-1,3-dioxolan-2-one）、化９参照）を０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 149)
Add 0.5% by mass of monochloroethylene carbonate (ClEC (4-chloro-1,3-dioxolan-2-one), see chemical formula 9), 0.5% by mass of DK to the total amount of electrolyte, and other than that Produced the same battery as in Example 1.
（参考例１５０）
電解質の総量に対してＣＩＥＣを０．５質量％、ＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１５１）
電解質の総量に対してＶＣを０．５質量％、ＦＥＣを０．５質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（参考例１５２）
電解質の総量に対してＶＣを１質量％、ＦＥＣを１質量％、ＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 150)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of CIEC and 0.5% by mass of VA were added to the total amount of the electrolyte.
(Reference Example 151)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC, 0.5% by mass of FEC, and 0.5% by mass of DK were added to the total amount of the electrolyte.
(Reference Example 152)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC, 1% by mass of FEC, and 0.5% by mass of DK were added to the total amount of the electrolyte.
（参考例１５３）
電解質の総量に対してＶＣを１質量％、プロピオン酸ビニル０．５質量％（化１０参照）添加し、それ以外は実施例１と同様の電池を作製した。
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl propionate (see Chemical formula 10) were added to the total amount of the electrolyte.
（参考例１５４）
電解質の総量に対してＶＣを１質量％、酪酸ビニル０．５質量％（化１１参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 154)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl butyrate (see Chemical Formula 11) were added to the total amount of the electrolyte.
（参考例１５５）
電解質の総量に対してＶＣを１質量％、カプロン酸ビニル０．５質量％（化１２参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 155)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl caproate (see Chemical formula 12) were added to the total amount of the electrolyte.
（参考例１５６）
電解質の総量に対してＶＣを１質量％、モノクロロ酢酸ビニル０．５質量％（化１３参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 156)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of monochlorovinyl acetate (see Chemical formula 13) were added to the total amount of the electrolyte.
（参考例１５７）
電解質の総量に対してＶＣを１質量％、モノフルオロ酢酸ビニル０．５質量％（化１４参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 157)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl monofluoroacetate (see Chemical formula 14) were added to the total amount of the electrolyte.
（参考例１５８）
電解質の総量に対してＶＣを１質量％、メタクリル酸ビニル０．５質量％（化１５参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 158)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl methacrylate (see Chemical formula 15) were added to the total amount of the electrolyte.
（参考例１５９）
電解質の総量に対してＶＣを１質量％、クロトン酸ビニル０．５質量％（化１６参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 159)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl crotonate (see Chemical formula 16) were added to the total amount of the electrolyte.
（参考例１６０）
電解質の総量に対してＶＣを１質量％、シクロヘキサンカルボン酸ビニル０．５質量％（化１７参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 160)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl cyclohexanecarboxylate (see Chemical formula 17) were added to the total amount of the electrolyte.
（参考例１６１）
電解質の総量に対してＶＣを１質量％、安息香酸ビニル０．５質量％（化１８参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 161)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl benzoate (see Chemical formula 18) were added to the total amount of the electrolyte.
（参考例１６２）
電解質の総量に対してＶＣを１質量％、桂皮酸ビニル０．５質量％（化１９参照）添加し、それ以外は実施例１と同様の電池を作製した。
(Reference Example 162)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 0.5% by mass of vinyl cinnamate (see Chemical formula 19) were added to the total amount of the electrolyte.
（比較例１）
電解質に添加剤を添加しておらず、それ以外は実施例１と同様の電池を作製した。
（比較例２）
電解質の総量に対してＤＫを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３）
電解質の総量に対してＤＫを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４）
電解質の総量に対してＤＫを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例５）
電解質の総量に対してＤＫを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例６）
電解質の総量に対してＤＫを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例７）
電解質の総量に対してＤＫを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 1)
A battery was prepared in the same manner as in Example 1 except that no additive was added to the electrolyte.
(Comparative Example 2)
A battery was manufactured in the same manner as in Example 1 except that 0.01% by mass of DK was added to the total amount of the electrolyte.
(Comparative Example 3)
A battery was prepared in the same manner as in Example 1 except that 0.1% by mass of DK was added to the total amount of the electrolyte.
(Comparative Example 4)
A battery was prepared in the same manner as in Example 1 except that 0.5% by mass of DK was added to the total amount of the electrolyte.
(Comparative Example 5)
A battery was prepared in the same manner as in Example 1 except that 1% by mass of DK was added to the total amount of the electrolyte.
(Comparative Example 6)
A battery was prepared in the same manner as in Example 1 except that 2% by mass of DK was added to the total amount of the electrolyte.
(Comparative Example 7)
A battery was prepared in the same manner as in Example 1 except that 3% by mass of DK was added to the total amount of the electrolyte.
（比較例８）
電解質の総量に対してＶＣを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例９）
電解質の総量に対してＶＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１０）
電解質の総量に対してＶＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１１）
電解質の総量に対してＶＣを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１２）
電解質の総量に対してＶＣを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１３）
電解質の総量に対してＶＣを５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 8)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VC was added to the total amount of the electrolyte.
(Comparative Example 9)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC was added to the total amount of the electrolyte.
(Comparative Example 10)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC was added to the total amount of the electrolyte.
(Comparative Example 11)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VC was added to the total amount of the electrolyte.
(Comparative Example 12)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VC was added to the total amount of the electrolyte.
(Comparative Example 13)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of VC was added to the total amount of the electrolyte.
（比較例１４）
電解質の総量に対してＶＡを０．０１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１５）
電解質の総量に対してＶＡを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１６）
電解質の総量に対してＶＡを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１７）
電解質の総量に対してＶＡを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１８）
電解質の総量に対してＶＡを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例１９）
電解質の総量に対してＶＡを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 14)
A battery was manufactured in the same manner as in Example 1 except that 0.01% by mass of VA was added to the total amount of the electrolyte.
(Comparative Example 15)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of VA was added to the total amount of the electrolyte.
(Comparative Example 16)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VA was added to the total amount of the electrolyte.
(Comparative Example 17)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VA was added to the total amount of the electrolyte.
(Comparative Example 18)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of VA was added to the total amount of the electrolyte.
(Comparative Example 19)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of VA was added to the total amount of the electrolyte.
（比較例２０）
電解質の総量に対してＦＥＣを０．１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２１）
電解質の総量に対してＦＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２２）
電解質の総量に対してＦＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２３）
電解質の総量に対してＦＥＣを２質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２４）
電解質の総量に対してＦＥＣを３質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２５）
電解質の総量に対してＦＥＣを５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 20)
A battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of FEC was added to the total amount of the electrolyte.
(Comparative Example 21)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of FEC was added to the total amount of the electrolyte.
(Comparative Example 22)
A battery was manufactured in the same manner as in Example 1 except that 1 mass% of FEC was added to the total amount of the electrolyte.
(Comparative Example 23)
A battery was manufactured in the same manner as in Example 1 except that 2% by mass of FEC was added to the total amount of the electrolyte.
(Comparative Example 24)
A battery was manufactured in the same manner as in Example 1 except that 3% by mass of FEC was added to the total amount of the electrolyte.
(Comparative Example 25)
A battery was manufactured in the same manner as in Example 1 except that 5% by mass of FEC was added to the total amount of the electrolyte.
（比較例２６）
電解質の総量に対してＶＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２７）
電解質の総量に対してＶＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２８）
電解質の総量に対してＤＶＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例２９）
電解質の総量に対してＤＶＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 26)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VEC was added to the total amount of the electrolyte.
(Comparative Example 27)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VEC was added to the total amount of the electrolyte.
(Comparative Example 28)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of DVEC was added to the total amount of the electrolyte.
(Comparative Example 29)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of DVEC was added to the total amount of the electrolyte.
（比較例３０）
電解質の総量に対してＡＬＯＭ−ＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３１）
電解質の総量に対してＡＬＯＭ−ＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３２）
電解質の総量に対してＰＧＯＭ−ＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３３）
電解質の総量に対してＰＧＯＭ−ＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 30)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of ALOM-EC was added to the total amount of the electrolyte.
(Comparative Example 31)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of ALOM-EC was added to the total amount of the electrolyte.
(Comparative Example 32)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of PGOM-EC was added to the total amount of the electrolyte.
(Comparative Example 33)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of PGOM-EC was added to the total amount of the electrolyte.
（比較例３４）
電解質の総量に対してＣＩＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３５）
電解質の総量に対してＣＩＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３６）
電解質の総量に対してＶＣを０．５質量％、ＦＥＣを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３７）
電解質の総量に対してＶＣを１質量％、ＦＥＣを１質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 34)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of CIEC was added to the total amount of the electrolyte.
(Comparative Example 35)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of CIEC was added to the total amount of the electrolyte.
(Comparative Example 36)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of VC and 0.5% by mass of FEC were added to the total amount of the electrolyte.
(Comparative Example 37)
A battery was manufactured in the same manner as in Example 1 except that 1% by mass of VC and 1% by mass of FEC were added to the total amount of the electrolyte.
（比較例３８）
電解質の総量に対してプロピオン酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例３９）
電解質の総量に対して酪酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４０）
電解質の総量に対してモノクロロ酢酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４１）
電解質の総量に対してモノフルオロ酢酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４２）
電解質の総量に対してメタクリル酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 38)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinyl propionate was added to the total amount of the electrolyte.
(Comparative Example 39)
A battery was prepared in the same manner as in Example 1 except that 0.5% by mass of vinyl butyrate was added to the total amount of the electrolyte.
(Comparative Example 40)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinyl monochloroacetate was added to the total amount of the electrolyte.
(Comparative Example 41)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinyl monofluoroacetate was added to the total amount of the electrolyte.
(Comparative Example 42)
A battery was prepared in the same manner as in Example 1 except that 0.5% by mass of vinyl methacrylate was added to the total amount of the electrolyte.
（比較例４３）
電解質の総量に対してクロトン酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４４）
電解質の総量に対してシクロヘキサンカルボン酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４５）
電解質の総量に対して安息香酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
（比較例４６）
電解質の総量に対して桂皮酸ビニルを０．５質量％添加し、それ以外は実施例１と同様の電池を作製した。
(Comparative Example 43)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinyl crotonate was added to the total amount of the electrolyte.
(Comparative Example 44)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinylcyclohexanecarboxylate was added to the total amount of the electrolyte.
(Comparative Example 45)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinyl benzoate was added to the total amount of the electrolyte.
(Comparative Example 46)
A battery was manufactured in the same manner as in Example 1 except that 0.5% by mass of vinyl cinnamate was added to the total amount of the electrolyte.
上述した各実施例、各参考例、及び各比較例の電池に対し、後述する初期容量、電池厚み、容量保持率（充放電サイクル寿命特性）を確認した。初期容量については、作製した電池を、電流８００ｍＡで４．２Ｖまで３時間定電流定電圧充電し、その後電流８００ｍＡで３Ｖまで放電を行い、放電容量［ｍＡｈ］（初期容量）を確認した。 The initial capacity, battery thickness, and capacity retention rate (charge / discharge cycle life characteristics) described later were confirmed for the batteries of the above-described Examples, Reference Examples, and Comparative Examples. Regarding the initial capacity, the produced battery was charged at a constant current and a constant voltage to 4.2 V at a current of 800 mA for 3 hours, and then discharged to 3 V at a current of 800 mA to confirm the discharge capacity [mAh] (initial capacity).
電池厚みについては、作製した電池を、電流８００ｍＡで４．２Ｖまで３時間定電流定電圧充電した後、８５℃の恒温槽中で５０時間放置した後、電池の厚さ［ｍｍ］（電池厚み）を確認した。 Regarding the battery thickness, the prepared battery was charged at a current of 800 mA to 4.2 V at a constant current and a constant voltage for 3 hours, then left in a constant temperature bath at 85 ° C. for 50 hours, and then the battery thickness [mm] (battery thickness) )It was confirmed.
容量保持率については、２５℃の環境下で、電流８００ｍＡで４．２Ｖまで３時間定電流定電圧充電し、その後電流８００ｍＡで３Ｖまで放電を行い、その後も上述した充電及び放電を繰返し５００サイクル行い、初期放電容量に対する５００サイクル後の放電容量の比［％］（容量保持率）を求めた。 Regarding the capacity retention rate, the battery was charged at a constant current and a constant voltage for 3 hours at a current of 800 mA to 4.2 V in an environment of 25 ° C., and then discharged to 3 V at a current of 800 mA. The ratio [%] (capacity retention) of the discharge capacity after 500 cycles to the initial discharge capacity was determined.
各実施例、各参考例、及び各比較例の電池の初期容量、電池厚み、容量保持率を表１〜９に示す。 Tables 1 to 9 show the initial capacity, battery thickness, and capacity retention rate of each example, each reference example, and each comparative example.
また、参考例１〜１４４、比較例１〜２５に関しては、初期容量、電池厚み、容量保持率を添加剤の添加量に応じて並べ替えたものを表１０〜表２５に示す。 Moreover, regarding Reference Examples 1 to 144 and Comparative Examples 1 to 25, Tables 10 to 25 show the initial capacities, battery thicknesses, and capacity retention rates rearranged according to the amount of additive added.
表１４，１７，２０，２３等に示すように、０．０１質量％以上２質量％以下のＤＫ又はＶＡを添加することにより初期容量が向上する。また、０．１質量％以上３質量％以下のＶＣ又はＦＥＣを添加することにより初期容量が向上する。 As shown in Tables 14, 17, 20, 23, etc., the initial capacity is improved by adding 0.01% by mass or more and 2% by mass or less of DK or VA. Moreover, initial capacity improves by adding 0.1 mass% or more and 3 mass% or less of VC or FEC.
表１５，１８，２１，２４等に示すように、０．０１質量％以上のＤＫ又はＶＡを添加することにより電池厚みの増加が抑制される。 As shown in Tables 15, 18, 21, 24, etc., an increase in battery thickness is suppressed by adding 0.01% by mass or more of DK or VA.
比較例のように、環状炭酸エステル誘導体としてのＶＣ、ＦＥＣ、ＶＥＣ、ＤＶＥＣ、ＡＬＯＭ−ＥＣ、ＰＧＯＭ−ＥＣ、及びＣＩＥＣの何れかを単独で添加したり、ビニルエステル誘導体としてのＤＫ、ＶＡ、プロピオン酸ビニル、酪酸ビニル、モノクロロ酢酸ビニル、モノフルオロ酢酸ビニル、メタクリル酸ビニル、クロトン酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニル及び桂皮酸ビニルの何れかを単独で添加するよりも、実施例のように、環状炭酸エステル誘導体としてのＡＬＯＭ−ＥＣ、ＰＧＯＭ−ＥＣと、ビニルエステル誘導体としてのＤＫ、ＶＡとを混合して添加する方が、初期容量、容量保持率（サイクル特性）が向上すると共に高温放置時の電池厚みの増加を抑制することが分かる。 As in the comparative example, any one of VC, FEC, VEC, DVEC, ALOM-EC, PGOM-EC, and CIEC as a cyclic carbonate derivative is added alone, or DK, VA, and propion as vinyl ester derivatives Example 1 rather than adding any one of vinyl acid vinyl, vinyl butyrate, vinyl monochloroacetate, vinyl monofluoroacetate, vinyl methacrylate, vinyl crotonate, vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl cinnamate alone In addition, when ALOM-EC or PGOM-EC as a cyclic carbonate derivative and DK or VA as a vinyl ester derivative are mixed and added, the initial capacity and capacity retention (cycle characteristics) are improved and the temperature is increased. It can be seen that the increase in battery thickness when left untreated is suppressed.
ビニルエステル誘導体を比較した場合、参考例５１、参考例１５３〜１５５、比較例１６、比較例３８、３９より、アルキル鎖長が長くなるに従い、高温放置時の電池厚みの増加が抑制されることが分かる。これは、耐酸化性が向上し、また、沸点が高くなるためと考えられる。
アルキル鎖長が長くなるに従い、容量保持率（サイクル特性）は若干低下している。これは、負極上に形成される負極保護被膜の性状の違いによるものであると考えられる。
When vinyl ester derivatives are compared, the increase in battery thickness when left at high temperatures is suppressed as the alkyl chain length becomes longer than in Reference Example 51, Reference Examples 153-155, Comparative Example 16, and Comparative Examples 38 and 39. I understand. This is presumably because the oxidation resistance is improved and the boiling point is increased.
As the alkyl chain length increases, the capacity retention (cycle characteristics) slightly decreases. This is considered to be due to the difference in properties of the negative electrode protective film formed on the negative electrode.
参考例１５６、比較例４０より、クロロ化されている場合、高温放置時の電池厚みの増加が抑制されることが分かる。これは、耐酸化性が向上したためと考えられる。
クロロ化されている場合、容量保持率は若干低下している。これは、塩素を含むことにより、負極保護被膜の性状が変わるためであると考えられる。
From Reference Example 156 and Comparative Example 40, it can be seen that when chlorinated, the increase in battery thickness when left at high temperature is suppressed. This is thought to be due to improved oxidation resistance.
When chlorinated, the capacity retention is slightly reduced. This is considered to be because the properties of the negative electrode protective film change due to the inclusion of chlorine.
参考例１５７、比較例４１より、フルオロ化されている場合、高温放置時の電池厚みの増加はさらに抑制されることが分かる。これは、耐酸化性が向上したためであると考えられる。容量保持率もクロロ化されている場合より良好である。これは、フッ素を含むので、ＬｉＦ等の安定な負極保護被膜を形成するためであると考えられる。 From Reference Example 157 and Comparative Example 41, it can be seen that when fluorinated, the increase in battery thickness when left at high temperature is further suppressed. This is considered to be due to the improved oxidation resistance. Capacity retention is also better than when chlorinated. This is considered to be for forming a stable negative electrode protective film such as LiF because it contains fluorine.
参考例１５８、１５９、比較例４２、４３の高温放置時の電池の膨れは、他より大きい。これは、ビニル基が複数あるので、耐酸化性が低下し、正極上で酸化分解したためであると考えられる。容量保持率は良好である。ビニル基が複数あるので、強固な負極保護被膜を形成したためと考えられる。 The swelling of the batteries when the reference examples 158 and 159 and the comparative examples 42 and 43 are left at a high temperature is larger than the others. This is considered to be due to the fact that since there are a plurality of vinyl groups, the oxidation resistance is lowered and oxidative decomposition occurs on the positive electrode. The capacity retention is good. This is probably because a strong negative electrode protective film was formed because there are a plurality of vinyl groups.
参考例１６０、比較例４４のようにシクロヘキシル基を有する場合、アルキル基を有する場合より高温放置時の電池の膨れが小さくなることが分かる。容量保持率は、アルキル基を有する場合と比較して良くなかった。負極保護被膜の性状の違いによるものと考えられる。 As shown in Reference Example 160 and Comparative Example 44, it can be seen that the swelling of the battery when left at high temperature is smaller when it has a cyclohexyl group than when it has an alkyl group. The capacity retention was not good as compared with the case having an alkyl group. This is thought to be due to the difference in properties of the negative electrode protective film.
参考例１６１、１６２、比較例４５、４６より、シクロヘキシル基を有するよりフェニル基を有する方が、高温放置時の電池の膨れが大きくなることが分かる。これは、フェニル基を有する方が酸化分解を受けやすいためであると考えられる。容量保持率はシクロヘキシル基を有する場合より良好であった。負極保護被膜の性状によるものと考えられる。 From Reference Examples 161 and 162 and Comparative Examples 45 and 46, it can be seen that the battery having a phenyl group is more swollen when left at high temperature than the cyclohexyl group. This is considered to be because the one having a phenyl group is more susceptible to oxidative decomposition. The capacity retention was better than that having a cyclohexyl group. This is considered to be due to the properties of the negative electrode protective film.
以上より、０．１質量％以上３質量％以下の環状炭酸エステル誘導体としてのＡＬＯＭ−ＥＣ、ＰＧＯＭ−ＥＣと、０．０１質量％以上２質量％以下のビニルエステル誘導体としてのＤＫ、ＶＡを添加することにより、電池の初期容量、容量保持率（サイクル特性）が向上すると共に高温放置時の電池厚さの増加を抑制することが出来ることが分かる。 Based on the above, ALOM-EC and PGOM-EC as cyclic carbonate derivatives of 0.1% by mass to 3% by mass and DK and VA as vinyl ester derivatives of 0.01% by mass to 2% by mass are added. By doing this, it is understood that the initial capacity and capacity retention rate (cycle characteristics) of the battery can be improved and an increase in battery thickness when left at high temperature can be suppressed.
１ 非水電解質二次電池
２ 電極群
３ 負極
４ 正極
５ セパレータ
６ 電池ケース
７ 電池蓋
８ 安全弁
９ 負極端子
１０ 負極リード
DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte
Claims (3)
前記電解質は、
下記化１で表されるＡＬＯＭ−ＥＣ（4-(2- プロペニルオキシメチル)-1,3-ジオキソラン-2- オン）、及び下記化２で表されるＰＧＯＭ−ＥＣ（4-(2- プロピニルオキシメチル)-1,3-ジオキソラン-2- オン）のうちの少なくとも１種からなる環状炭酸エステル誘導体と、
下記化３で表されるＤＫ（ジケテン）、及び下記化４で表されるＶＡ（酢酸ビニル）のうちの少なくとも１種からなるビニルエステル誘導体と
を含んでなることを特徴とする非水電解質二次電池。
The electrolyte is
ALOM-EC ( 4- (2-propenyloxymethyl) -1,3-dioxolan-2-one ) represented by the following chemical formula 1 and PGOM-EC ( 4- (2-propynyl ) represented by the following chemical formula 2 A cyclic carbonate derivative comprising at least one of oxymethyl) -1,3-dioxolan-2-one ),
A non-aqueous electrolyte comprising: a DK (diketene) represented by the following chemical formula 3; and a vinyl ester derivative comprising at least one of VA (vinyl acetate) represented by the following chemical formula 4. Next battery.
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| KR102103898B1 (en) * | 2017-01-23 | 2020-04-24 | 주식회사 엘지화학 | Additive for nonaqueous electrolyte, nonaqueous electrolyte for lithium secondary battery comprising the same, and lithium secondary battery |
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| US11945776B2 (en) * | 2018-01-30 | 2024-04-02 | Daikin Industries, Ltd. | Electrolyte, electrochemical device, lithium ion secondary battery, and module |
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| JP4051953B2 (en) * | 2001-02-23 | 2008-02-27 | 三菱化学株式会社 | Non-aqueous electrolyte secondary battery |
| JP4315705B2 (en) * | 2003-02-27 | 2009-08-19 | 三洋電機株式会社 | Non-aqueous lithium secondary battery |
| CN100452520C (en) * | 2003-08-26 | 2009-01-14 | 独立行政法人宇宙航空研究开发机构 | Non-inflammable non aqueous electrolyte and lithium-ion battery containing the same |
| JP4968615B2 (en) * | 2004-12-16 | 2012-07-04 | 日本電気株式会社 | Secondary battery electrolyte and secondary battery |
| US7851093B2 (en) * | 2004-12-24 | 2010-12-14 | Panasonic Corporation | Nonaqueous electrolyte for secondary battery and secondary battery including the same |
| JP4606334B2 (en) * | 2005-03-08 | 2011-01-05 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
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2006
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