JP5658821B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery Download PDFInfo
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- JP5658821B2 JP5658821B2 JP2013516809A JP2013516809A JP5658821B2 JP 5658821 B2 JP5658821 B2 JP 5658821B2 JP 2013516809 A JP2013516809 A JP 2013516809A JP 2013516809 A JP2013516809 A JP 2013516809A JP 5658821 B2 JP5658821 B2 JP 5658821B2
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- negative electrode
- secondary battery
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、高エネルギー密度で、優れた充放電サイクル特性を発揮し得る非水二次電池に関するものである。 The present invention relates to a non-aqueous secondary battery that can exhibit excellent charge / discharge cycle characteristics at a high energy density.
携帯電話、ノート型パーソナルコンピュータなどのポータブル電子機器の発達や、電気自動車の実用化などに伴い、小型・軽量でかつ高容量・高エネルギー密度の二次電池が必要とされるようになってきた。現在、この要求に応え得る二次電池として、正極活物質にＬｉＣｏＯ2などのＬｉ（リチウム）含有複合酸化物を用い、負極活物質に黒鉛などを用いたリチウムイオン二次電池に代表される非水二次電池が商品化されている。そして、非水二次電池の適用機器の更なる発達に伴って、非水二次電池の更なる高容量化・高エネルギー密度化が求められている。 With the development of portable electronic devices such as mobile phones and notebook personal computers, and the practical application of electric vehicles, secondary batteries with small size, light weight, high capacity, and high energy density have become necessary. . Currently, as a secondary battery capable of meeting this requirement, a non-representative lithium ion secondary battery using a Li (lithium) -containing composite oxide such as LiCoO 2 as a positive electrode active material and graphite or the like as a negative electrode active material. Water secondary batteries have been commercialized. And with the further development of the application equipment of a non-aqueous secondary battery, further higher capacity and higher energy density of the non-aqueous secondary battery are required.
非水二次電池の高容量化のための手法として、黒鉛などの炭素系負極材料に比べてより多くのＬｉを収容可能なＳｉやＳｎなどの負極材料の開発が進められている。中でも、Ｓｉの超微粒子がＳｉＯ2粒子中に分散した構造を持つＳｉＯxで表される材料が注目されている。この材料では、Ｌｉと反応するＳｉが超微粒子であるために充放電がスムーズに行われる。また、ＳｉＯx粒子自体は表面積が小さいため、負極合剤層を形成するための塗料（溶剤を含む負極合剤含有組成物）とした際の塗料性や負極合剤層の集電体に対する接着性も良好である。 As a technique for increasing the capacity of non-aqueous secondary batteries, development of negative electrode materials such as Si and Sn that can accommodate more Li than carbon-based negative electrode materials such as graphite is being promoted. In particular, a material expressed by SiO x having a structure in which ultrafine particles of Si are dispersed in SiO 2 particles has attracted attention. In this material, since Si that reacts with Li is an ultrafine particle, charging and discharging are performed smoothly. In addition, since the SiO x particles themselves have a small surface area, the paint properties and the adhesion of the negative electrode mixture layer to the current collector when used as a paint for forming the negative electrode mixture layer (a negative electrode mixture-containing composition containing a solvent) The property is also good.
しかしながら、ＳｉＯx粒子を用いた負極では、初期の充放電容量は大きいものの、充放電を繰り返すと容量が低下するという問題がある。これは、充放電による体積の膨張・収縮によってＳｉＯx粒子が徐々に粉砕され、表面に露出した活性な超微粒子のＳｉが非水電解質などと反応し、その反応により生成した反応生成物によりＳｉとＬｉとの反応が阻害されることにより、電池の内部抵抗が増大するためと推測される。 However, the negative electrode using SiO x particles has a large initial charge / discharge capacity, but there is a problem that the capacity decreases when charge / discharge is repeated. This is because SiO x particles are gradually pulverized by volume expansion and contraction due to charge and discharge, and active ultrafine Si exposed on the surface reacts with non-aqueous electrolyte and the like, and the reaction product generated by the reaction causes Si to It is presumed that the internal resistance of the battery is increased by inhibiting the reaction between Li and Li.
この問題を改善するために、非水電解質に添加剤としてハロゲン置換された環状カーボネートを含有させる方法が提案されている（特許文献１）。この方法では、ＳｉＯx粒子の粉砕によって生じる新生面に上記添加剤由来の皮膜が形成され、これが非水電解質とＳｉとの反応を抑制するために、前述の内部抵抗の増大が生ぜず、電池の充放電サイクルによる容量低下が改善される。 In order to improve this problem, a method has been proposed in which a non-aqueous electrolyte contains a halogen-substituted cyclic carbonate as an additive (Patent Document 1). In this method, a film derived from the additive is formed on the new surface generated by grinding the SiO x particles, and this suppresses the reaction between the non-aqueous electrolyte and Si, so that the increase in the internal resistance does not occur, and the battery Capacity reduction due to charge / discharge cycles is improved.
他方、非水二次電池の高エネルギー密度化を図る手法の一つとして、高電位で作動できる正極活物質を用いることが考えられる。例えば、一般式ＬｉＮｉ0.5Ｍｎ1.5Ｏ4で表されるスピネル結晶型のＬｉ含有複合酸化物は、リチウム基準で約４．７Ｖの高い電圧で作動し得ることが確認されている。 On the other hand, as one method for increasing the energy density of the nonaqueous secondary battery, it is conceivable to use a positive electrode active material that can operate at a high potential. For example, it has been confirmed that a spinel crystal type Li-containing composite oxide represented by the general formula LiNi 0.5 Mn 1.5 O 4 can operate at a high voltage of about 4.7 V based on lithium.
また、一般式ＬｉＭｅＯ2（Ｍｅは遷移元素）で表される層状構造のＬｉ含有複合酸化物でも、充電終止電圧を高めることによって平均放電電圧を上げることができる。 Even in a Li-containing composite oxide having a layered structure represented by the general formula LiMeO 2 (Me is a transition element), the average discharge voltage can be increased by increasing the charge end voltage.
高エネルギー密度の非水二次電池を実現するには、ＳｉＯxのような高容量の負極活物質を含有する負極と、前述のような高電位で作動できる正極活物質を含有する正極とを組み合わせることが有効と考えられるが、実際にこれらの負極と正極とを組み合わせ、更に非水電解質に添加剤としてハロゲン置換された環状カーボネートを含有させて、電池を高電位で作動させると、電池の充放電サイクル特性が著しく劣化することが本発明者らの検討により明らかとなった。これは、負極のＳｉＯx粒子を保護するために非水電解質に適用される上記添加剤が、従来よりも高電位になる正極側で酸化分解されて、負極側で果たすべき機能が損なわれるためと推測される。 In order to realize a high energy density non-aqueous secondary battery, a negative electrode containing a high-capacity negative electrode active material such as SiO x and a positive electrode containing a positive electrode active material operable at a high potential as described above are used. Although it is considered effective to combine them, when these batteries are actually combined with a negative electrode and a positive electrode, and further, a non-aqueous electrolyte containing a halogen-substituted cyclic carbonate as an additive and the battery is operated at a high potential, It has become clear from the study by the present inventors that the charge / discharge cycle characteristics deteriorate significantly. This is because the additive applied to the non-aqueous electrolyte for protecting the SiO x particles of the negative electrode is oxidatively decomposed on the positive electrode side, which has a higher potential than before, and the function to be performed on the negative electrode side is impaired. It is guessed.
本発明は、上記事情に鑑みてなされたものであり、高電位で作動できる正極活物質を含有する正極と、ケイ素（Ｓｉ）と酸素（Ｏ）とを含む材料からなる負極活物質を含有する負極とを備えつつ、充放電サイクル特性に優れた非水二次電池を提供することにある。 This invention is made | formed in view of the said situation, The positive electrode containing the positive electrode active material which can operate | move by a high potential, and the negative electrode active material which consists of a material containing silicon (Si) and oxygen (O) are contained. An object of the present invention is to provide a nonaqueous secondary battery having a negative electrode and excellent charge / discharge cycle characteristics.
本発明の非水二次電池は、正極、負極、セパレータおよび非水電解質を含む非水二次電池であって、前記負極は、ケイ素と酸素とを構成元素に含む負極材料であって、前記ケイ素に対する前記酸素の原子比ｘが０．５≦ｘ≦１．５である負極材料を含有する負極合剤層を含み、前記正極は、下記一般式（１）または下記一般式（２）で表される複合酸化物を含有する正極合剤層を含み、前記非水電解質は、４−フルオロ−１，３−ジオキソラン−２−オンと、ホウ酸トリエステルとを含むことを特徴とする。 The non-aqueous secondary battery of the present invention is a non-aqueous secondary battery including a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, and the negative electrode is a negative electrode material containing silicon and oxygen as constituent elements, The negative electrode mixture layer containing the negative electrode material whose atomic ratio x of the said oxygen with respect to silicon is 0.5 <= x <= 1.5, The said positive electrode is the following general formula (1) or the following general formula (2) And a non-aqueous electrolyte containing 4-fluoro-1,3-dioxolan-2-one and a boric acid triester.
ＬｉＮｉyＭｎ2-y-zＭ1 zＯ4 （１）
ただし、前記一般式（１）中、Ｍ1は、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ａｌ、Ｍｇ、ＺｎおよびＬｉよりなる群から選択される少なくとも１種の元素であり、ｙは０．４５≦ｙ≦０．５５、ｚは０≦ｚ≦０．１である。
LiNi y Mn 2-yz M 1 z O 4 (1)
In the general formula (1), M 1 is at least one element selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li, and y is 0.45 ≦ y ≦ 0.55, z is 0 ≦ z ≦ 0.1.
ＬｉＭ2Ｏ2 （２）
ただし、前記一般式（２）中、Ｍ2は、ＮｉおよびＣｏを含む２種以上の元素を少なくとも含み、Ｍ2の全元素数に対する、Ｎｉ、ＣｏおよびＭｎの元素数の割合を、それぞれａ（ｍｏｌ％）、ｂ（ｍｏｌ％）及びｃ（ｍｏｌ％）としたときに、２０≦ａ≦６５、１５≦ｂ≦５５、０≦ｃ≦４５、９０≦ａ＋ｂ＋ｃ≦１００である。
LiM 2 O 2 (2)
However, in the general formula (2), M 2 contains at least two or more elements including Ni and Co, and the ratio of the number of elements of Ni, Co and Mn to the total number of elements of M 2 is represented by a (Mol%), b (mol%) and c (mol%), 20 ≦ a ≦ 65, 15 ≦ b ≦ 55, 0 ≦ c ≦ 45, 90 ≦ a + b + c ≦ 100.
本発明によれば、高電位で作動できる正極活物質を含有する正極と、ＳｉとＯとを含む材料からなる負極活物質を含有する負極とを備えつつ、充放電サイクル特性に優れた非水二次電池を提供することができる。 According to the present invention, a non-aqueous solution having a positive electrode containing a positive electrode active material capable of operating at a high potential and a negative electrode containing a negative electrode active material made of a material containing Si and O and having excellent charge / discharge cycle characteristics. A secondary battery can be provided.
本発明の非水二次電池は、下記の正極、負極、セパレータおよび非水電解質を含む非水二次電池である。以下、それぞれについて説明する。 The non-aqueous secondary battery of the present invention is a non-aqueous secondary battery including the following positive electrode, negative electrode, separator and non-aqueous electrolyte. Each will be described below.
〔負極〕
本発明の非水二次電池に係る負極は、例えば、負極活物質およびバインダなどを含有する負極合剤層を、集電体の片面または両面に有する構造のものである。
[Negative electrode]
The negative electrode according to the nonaqueous secondary battery of the present invention has a structure having, for example, a negative electrode mixture layer containing a negative electrode active material and a binder on one side or both sides of a current collector.
負極活物質には、ケイ素（Ｓｉ）と酸素（Ｏ）とを構成元素に含む負極材料であって、上記ケイ素に対する上記酸素の原子比ｘが０．５≦ｘ≦１．５である負極材料（以下、当該材料を「ＳｉＯx」という。）を使用する。 The negative electrode active material includes a negative electrode material containing silicon (Si) and oxygen (O) as constituent elements, wherein the atomic ratio x of oxygen to silicon is 0.5 ≦ x ≦ 1.5 (Hereinafter, this material is referred to as “SiO x ”).
ＳｉＯxは、Ｓｉの微結晶または非晶質相を含んでいてもよく、この場合、ＳｉとＯの原子比は、Ｓｉの微結晶または非晶質相のＳｉを含めた比率となる。すなわち、ＳｉＯxには、非晶質のＳｉＯ2マトリックス中にＳｉ（例えば、微結晶Ｓｉ）が分散した構造のものが含まれ、この非晶質のＳｉＯ2と、その中に分散しているＳｉを合わせて、上記原子比ｘが０．５≦ｘ≦１．５を満足していればよい。これは、ｘが小さすぎる場合には、ＳｉＯ2によるＳｉの保護効果が十分でなく、電池の充放電サイクルによって容量劣化が著しくなり、一方、ｘが大きすぎると、Ｌｉイオンを充放電するＳｉが減って初期の充放電容量が低下するからである。 The SiO x may contain Si microcrystal or amorphous phase. In this case, the atomic ratio of Si and O is a ratio including Si microcrystal or amorphous phase Si. That is, the SiO x, Si (e.g., microcrystalline Si) in the SiO 2 matrix of amorphous include the dispersed structure, the SiO 2 of the amorphous, dispersed therein In combination with Si, it is sufficient that the atomic ratio x satisfies 0.5 ≦ x ≦ 1.5. This is because, when x is too small, the protective effect of Si by SiO 2 is not sufficient, and the capacity deterioration becomes significant due to the charge / discharge cycle of the battery, while when x is too large, Si that charges and discharges Li ions. This is because the initial charge / discharge capacity decreases.
例えば、非晶質のＳｉＯ2マトリックス中にＳｉが分散した構造で、ＳｉＯ2とＳｉのモル比が１：１の材料の場合、材料全体でのＳｉに対するＯの原子比：ｘ＝１であるので、組成式としてはＳｉＯで表記される。このような構造の材料の場合、例えば、Ｘ線回折分析では、Ｓｉ（微結晶Ｓｉ）の存在に起因するピークが観察されない場合もあるが、透過型電子顕微鏡で観察すると、微細なＳｉの存在が確認できる。 For example, in the case of a material in which Si is dispersed in an amorphous SiO 2 matrix and the molar ratio of SiO 2 to Si is 1: 1, the atomic ratio of O to Si in the entire material is x = 1. Therefore, the composition formula is represented by SiO. In the case of a material having such a structure, for example, in X-ray diffraction analysis, a peak due to the presence of Si (microcrystalline Si) may not be observed, but when observed with a transmission electron microscope, the presence of fine Si Can be confirmed.
ＳｉＯxの表面は、炭素材料などの導電性材料で被覆されていることが好ましい。ＳｉＯxは電子伝導性が乏しいため、良好な電池特性を確保するには、その表面を炭素材料などの導電性材料で被覆して、電子伝導性を補うことが有効である。 The surface of SiO x is preferably covered with a conductive material such as a carbon material. Since SiO x has poor electron conductivity, it is effective to cover the surface with a conductive material such as a carbon material to supplement the electron conductivity in order to ensure good battery characteristics.
ＳｉＯxの表面を被覆するための炭素材料には、例えば、低結晶性炭素、カーボンナノチューブ、気相成長炭素繊維などを使用することができる。 As the carbon material for coating the surface of SiO x , for example, low crystalline carbon, carbon nanotube, vapor grown carbon fiber, or the like can be used.
炭化水素系ガスを気相中で加熱し、炭化水素系ガスの熱分解により生じた炭素を、ＳｉＯx粒子の表面上に堆積する方法［気相成長（ＣＶＤ）法］で、ＳｉＯxの表面を炭素材料で被覆すると、炭化水素系ガスがＳｉＯx粒子の隅々にまで行き渡り、粒子の表面や表面の空孔内に、電子伝導性を有する炭素材料を含む薄くて均一な皮膜（炭素被覆層）を形成できることから、少量の炭素材料によってＳｉＯx粒子に均一性よく電子伝導性を付与できる。 The hydrocarbon gas is heated in the gas phase, the carbon generated by thermal decomposition of hydrocarbon gas, a method of depositing on the surface of the SiO x particulate [vapor deposition (CVD) method, the surface of the SiO x When carbon is coated with a carbon material, the hydrocarbon gas spreads to every corner of the SiO x particle, and a thin and uniform film (carbon coating) containing a carbon material having electron conductivity is formed on the surface of the particle and in the pores of the surface. Layer), a small amount of carbon material can impart uniform electron conductivity to the SiO x particles.
上記ＣＶＤ法で使用する炭化水素系ガスの液体ソースとしては、トルエン、ベンゼン、キシレン、メシチレンなどを用いることができるが、取り扱いやすいトルエンが特に好ましい。これらを気化させる（例えば、窒素ガスでバブリングする）ことにより炭化水素系ガスを得ることができる。また、メタンガスやエチレンガス、アセチレンガスなどを用いることもできる。 As the liquid source of the hydrocarbon-based gas used in the CVD method, toluene, benzene, xylene, mesitylene and the like can be used, but toluene that is easy to handle is particularly preferable. A hydrocarbon-based gas can be obtained by vaporizing them (for example, bubbling with nitrogen gas). Moreover, methane gas, ethylene gas, acetylene gas, etc. can also be used.
上記ＣＶＤ法の処理温度としては、例えば、６００〜１２００℃であることが好ましい。また、ＣＶＤ法に供するＳｉＯxは、公知の手法で造粒した造粒体（複合粒子）であることが好ましい。 The processing temperature of the CVD method is preferably 600 to 1200 ° C., for example. Further, SiO x subjected to CVD method is preferably granulated material was granulated by a known method (composite particles).
上記ＳｉＯxの表面を炭素材料で被覆する場合、炭素材料の量は、ＳｉＯx：１００質量部に対して、５質量部以上であることが好ましく、１０質量部以上であることがより好ましく、また、９５質量部以下であることが好ましく、９０質量部以下であることがより好ましい。 When the surface of SiO x is coated with a carbon material, the amount of the carbon material is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to SiO x : 100 parts by mass, Moreover, it is preferable that it is 95 mass parts or less, and it is more preferable that it is 90 mass parts or less.
負極活物質には、例えば黒鉛質炭素材料を、ＳｉＯxと共に用いることができる。ＳｉＯxは高容量である一方で、電池の充放電に伴う体積変化量が大きいため、例えば負極の膨張・収縮を引き起こして電池特性を低下させる虞があるが、ＳｉＯxよりも充放電に伴う体積変化量の小さな黒鉛質炭素材料をＳｉＯxと併用することで、電池容量への影響を可及的に抑制しつつ、充放電に伴う負極の体積変化量を低減して、電池特性の低下などを抑えることができる。 As the negative electrode active material, for example, a graphitic carbon material can be used together with SiO x . While SiO x is a high capacity, because of the large volume change accompanying the charge and discharge of the battery, for example, there is a fear of lowering the battery characteristics causing expansion and contraction of the negative electrode, during charge and discharge than SiO x By using a graphite carbon material with a small volume change together with SiO x , the effect on the battery capacity is suppressed as much as possible, and the volume change of the negative electrode accompanying charge / discharge is reduced, resulting in a deterioration in battery characteristics. Etc. can be suppressed.
ＳｉＯxと併用し得る黒鉛質炭素材料としては、例えば、鱗片状黒鉛などの天然黒鉛；熱分解炭素類、メソフェーズカーボンマイクロビーズ（ＭＣＭＢ）、炭素繊維などの易黒鉛化炭素を２８００℃以上で黒鉛化処理した人造黒鉛；などが挙げられる。 Graphite carbon materials that can be used in combination with SiO x include, for example, natural graphite such as flaky graphite; graphitizable carbon such as pyrolytic carbons, mesophase carbon microbeads (MCMB), and carbon fibers at 2800 ° C. or more. Artificial graphite subjected to chemical treatment; and the like.
負極活物質にＳｉＯxと黒鉛質炭素材料とを併用する場合、ＳｉＯxの使用による電池の高エネルギー密度化の効果を良好に確保する観点から、負極活物質１００質量％中のＳｉＯxの含有量を、３質量％以上とすることが好ましく、５質量％以上とすることがより好ましい。また、負極活物質にＳｉＯxと黒鉛質炭素材料とを併用する場合、黒鉛質炭素材料の使用による前述の効果を良好に確保する観点から、負極活物質１００質量％中のＳｉＯxの含有量を、９０質量％以下とすることが好ましく、８０質量％以下とすることがより好ましい。 When used in combination with SiO x and graphitic carbon material in the negative electrode active material, containing SiO x from the viewpoint of satisfactorily ensuring the effect of the high energy density of the battery by the use of SiO x, the negative electrode active material 100 wt% The amount is preferably 3% by mass or more, and more preferably 5% by mass or more. In addition, when SiO x and a graphitic carbon material are used in combination with the negative electrode active material, the content of SiO x in 100% by mass of the negative electrode active material is ensured from the viewpoint of ensuring the above-described effects by using the graphitic carbon material. Is preferably 90% by mass or less, and more preferably 80% by mass or less.
負極合剤層に係るバインダには、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレンブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロース（ＣＭＣ）などが好適に用いられる。更に、負極合剤層には、導電助剤として、アセチレンブラックなどの各種カーボンブラックやカーボンナノチューブ、炭素繊維などを添加してもよい。 For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), or the like is preferably used for the binder related to the negative electrode mixture layer. Furthermore, you may add various carbon blacks, such as acetylene black, a carbon nanotube, carbon fiber, etc. as a conductive support agent to a negative mix layer.
負極は、例えば、負極活物質およびバインダ、更には必要に応じて導電助剤を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）や水などの溶剤に分散させた負極合剤含有組成物を調製し（ただし、バインダは溶剤に溶解していてもよい。）、これを集電体の片面または両面に塗布し、乾燥した後に、必要に応じてカレンダー処理を施す工程を経て製造される。ただし、負極の製造方法は、上記の方法に制限される訳ではなく、他の製造方法で製造してもよい。 The negative electrode is prepared, for example, by preparing a negative electrode mixture-containing composition in which a negative electrode active material and a binder and, if necessary, a conductive additive are dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) or water. (However, the binder may be dissolved in a solvent.) After this is applied to one or both sides of the current collector and dried, it is manufactured through a step of applying a calender treatment if necessary. However, the manufacturing method of the negative electrode is not limited to the above method, and may be manufactured by other manufacturing methods.
負極合剤層の組成としては、例えば、負極活物質の量が８０〜９５質量％であることが好ましく、バインダの量が１〜２０質量％であることが好ましく、導電助剤を使用する場合には、その量が１〜１０質量％であることが好ましい。また、負極合剤層の厚みは、集電体の片面あたり、１０〜１００μｍであることが好ましい。 As a composition of the negative electrode mixture layer, for example, the amount of the negative electrode active material is preferably 80 to 95% by mass, the amount of the binder is preferably 1 to 20% by mass, and a conductive additive is used. The amount is preferably 1 to 10% by mass. Moreover, it is preferable that the thickness of a negative mix layer is 10-100 micrometers per single side | surface of a collector.
負極の集電体には、例えば、銅、ステンレス鋼、ニッケル、チタンまたはそれらの合金などからなる箔、パンチドメタル、エキスパンドメタル、網などを用い得るが、通常、厚みが５〜３０μｍの銅箔が好適に用いられる。 The negative electrode current collector may be, for example, a foil, punched metal, expanded metal, net, or the like made of copper, stainless steel, nickel, titanium, or an alloy thereof. Usually, copper having a thickness of 5 to 30 μm is used. A foil is preferably used.
〔正極〕
本発明の非水二次電池に係る正極は、例えば、正極活物質、導電助剤およびバインダを含有する正極合剤層を、集電体の片面または両面に有する構造のものである。
[Positive electrode]
The positive electrode according to the nonaqueous secondary battery of the present invention has, for example, a structure having a positive electrode mixture layer containing a positive electrode active material, a conductive additive and a binder on one side or both sides of a current collector.
正極活物質には、下記一般式（１）または下記一般式（２）で表されるＬｉ含有複合酸化物を使用する。 As the positive electrode active material, a Li-containing composite oxide represented by the following general formula (1) or the following general formula (2) is used.
ＬｉＮｉyＭｎ2-y-zＭ1 zＯ4 （１）
ただし、上記一般式（１）中、Ｍ1は、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ａｌ、Ｍｇ、ＺｎおよびＬｉよりなる群から選択される少なくとも１種の元素であり、ｙは０．４５≦ｙ≦０．５５、ｚは０≦ｚ≦０．１である。
LiNi y Mn 2-yz M 1 z O 4 (1)
However, in the general formula (1), M 1 is at least one element selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li, and y is 0.45 ≦ y ≦ 0.55, z is 0 ≦ z ≦ 0.1.
ＬｉＭ2Ｏ2 （２）
ただし、上記一般式（２）中、Ｍ2は、ＮｉおよびＣｏを含む２種以上の元素を少なくとも含み、Ｍ2の全元素数に対する、Ｎｉ、ＣｏおよびＭｎの元素数の割合を、それぞれａ（ｍｏｌ％）、ｂ（ｍｏｌ％）及びｃ（ｍｏｌ％）としたときに、２０≦ａ≦６５、１５≦ｂ≦５５、０≦ｃ≦４５、９０≦ａ＋ｂ＋ｃ≦１００である。
LiM 2 O 2 (2)
However, in the general formula (2), M 2 contains at least two or more elements including Ni and Co, and the ratio of the number of elements of Ni, Co and Mn to the total number of elements of M 2 is represented by a (Mol%), b (mol%) and c (mol%), 20 ≦ a ≦ 65, 15 ≦ b ≦ 55, 0 ≦ c ≦ 45, 90 ≦ a + b + c ≦ 100.
上記一般式（１）で表されるＬｉ含有複合酸化物は、スピネル型結晶の正極活物質ＬｉＭｎ2Ｏ4のＭｎの一部をＮｉに置換するなどしたもので、Ｌｉ基準で約４．７Ｖの高い放電電圧が得られる。 The Li-containing composite oxide represented by the general formula (1) is obtained by substituting a part of Mn of the spinel-type positive electrode active material LiMn 2 O 4 with Ni, and is about 4.7 V based on Li. A high discharge voltage can be obtained.
上記一般式（１）で表されるＬｉ含有複合酸化物において、Ｌｉイオンの脱離・挿入による電荷補償をしているのは、主にＮｉ2+／Ｎｉ4+の酸化・還元である。Ｎｉの置換量ｙは、０．５から大きくずれると放電電圧が低下するため、０．４５≦ｙ≦０．５５である必要がある。 In the Li-containing composite oxide represented by the above general formula (1), it is mainly oxidation / reduction of Ni 2+ / Ni 4+ that performs charge compensation by desorption / insertion of Li ions. Since the discharge voltage decreases when the Ni substitution amount y deviates significantly from 0.5, it is necessary that 0.45 ≦ y ≦ 0.55.
上記一般式（１）で表されるＬｉ含有複合酸化物は、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ａｌ、Ｍｇ、ＺｎおよびＬｉよりなる群から選択される少なくとも１種の添加元素Ｍ1を含有してもよい。ただし、これらの添加元素Ｍ1の量が多すぎると放電容量が低下するため、添加元素Ｍ1の量ｚは、０．１以下とする。 The Li-containing composite oxide represented by the general formula (1) contains at least one additive element M 1 selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li. May be. However, if the amount of these additive elements M 1 is too large, the discharge capacity decreases, so the amount z of the additive elements M 1 is set to 0.1 or less.
上記一般式（２）で表されるＬｉ含有複合酸化物は、ＬｉＣｏＯ2などと同じ層状結晶の正極活物質であるが、充電電圧をＬｉ基準で４．４Ｖ以上に高めることによって、高電圧かつ高容量の放電特性が得られる。この活物質では、Ｌｉイオンの脱離・挿入によって、Ｎｉ、Ｃｏ、Ｍｎの各々が価数変化して、充放電特性に寄与している。 The Li-containing composite oxide represented by the general formula (2) is a positive electrode active material having the same layered crystal as LiCoO 2 or the like. However, by increasing the charging voltage to 4.4 V or more on the basis of Li, high voltage and High capacity discharge characteristics can be obtained. In this active material, each of Ni, Co, and Mn changes in valence due to desorption / insertion of Li ions, contributing to charge / discharge characteristics.
上記一般式（２）で表されるＬｉ含有複合酸化物に係るＭ2は、ＮｉおよびＣｏを含む２種以上の元素を少なくとも含んでいる。 M 2 related to the Li-containing composite oxide represented by the general formula (2) contains at least two or more elements including Ni and Co.
上記一般式（２）で表されるＬｉ含有複合酸化物において、Ｎｉの量が少なすぎると、放電容量が低下する。よって、上記一般式（２）において、Ｍ2の全元素数を１００ｍｏｌ％としたとき、Ｎｉの割合ａは、２０ｍｏｌ％以上とする。また、上記一般式（２）で表されるＬｉ含有複合酸化物において、Ｎｉの量が多すぎると、例えば、ＣｏやＭｎの量が減って、これらによる効果が小さくなる虞がある。よって、上記一般組成式（２）おいて、Ｍ2の全元素数を１００ｍｏｌ％としたとき、Ｎｉの割合ａは、６５ｍｏｌ％以下とする。 In the Li-containing composite oxide represented by the general formula (2), if the amount of Ni is too small, the discharge capacity is reduced. Therefore, in the above general formula (2), when the total number of elements of M 2 is 100 mol%, the Ni ratio a is 20 mol% or more. Further, in the Li-containing composite oxide represented by the general formula (2), if the amount of Ni is too large, for example, the amount of Co or Mn is decreased, and the effect of these may be reduced. Therefore, in the general composition formula (2), when the total number of elements of M 2 is 100 mol%, the Ni ratio a is 65 mol% or less.
また、上記一般式（２）で表されるＬｉ含有複合酸化物において、Ｃｏの量が少なすぎると、４．４Ｖ以上で高電圧充電したときの、放電電圧および放電容量の増加が少なくなる。よって、上記一般式（２）において、Ｍ2の全元素数を１００ｍｏｌ％としたときに、Ｃｏの割合ｂは、１５ｍｏｌ％以上とする。また、上記一般式（２）で表されるＬｉ含有複合酸化物において、Ｃｏの量が多すぎると、充電時にＬｉが脱離したときの結晶の安定性が低下する。よって、上記一般式（２）において、Ｍ2の全元素数を１００ｍｏｌ％としたときに、Ｃｏの割合ｂは、５５ｍｏｌ％以下とする。 In addition, in the Li-containing composite oxide represented by the general formula (2), if the amount of Co is too small, an increase in discharge voltage and discharge capacity when charged at a high voltage of 4.4 V or higher is reduced. Therefore, in the general formula (2), when the total number of elements of M 2 is 100 mol%, the Co ratio b is 15 mol% or more. Further, in the Li-containing composite oxide represented by the general formula (2), if the amount of Co is too large, the stability of the crystal when Li is desorbed during charging is lowered. Therefore, in the general formula (2), when the total number of elements of M 2 is 100 mol%, the Co ratio b is 55 mol% or less.
上記一般式（２）で表されるＬｉ含有複合酸化物は、Ｍｎを含有していてもよい。ただし、上記一般式（２）で表されるＬｉ含有複合酸化物中のＭｎの量が多すぎると放電容量が低下する。よって、上記一般式（２）において、Ｍ2の全元素数を１００ｍｏｌ％としたときに、Ｍｎの割合ｃは、０ｍｏｌ％以上４５ｍｏｌ％以下とする。 The Li-containing composite oxide represented by the general formula (2) may contain Mn. However, if the amount of Mn in the Li-containing composite oxide represented by the general formula (2) is too large, the discharge capacity decreases. Therefore, in the general formula (2), when the total number of elements of M 2 is 100 mol%, the ratio c of Mn is 0 mol% or more and 45 mol% or less.
上記一般式（２）で表されるＬｉ含有複合酸化物に係るＭ2は、Ｎｉ、ＣｏおよびＭｎ以外の添加元素を含有していてもよい。このような添加元素としては、例えば、Ａｌ、Ｍｇ、Ｚｎ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｌｉなどが挙げられる。ただし、上記一般式（２）で表されるＬｉ含有複合酸化物において、これらの添加元素の量が多すぎると、放電容量が低下する虞がある。よって、上記一般式（２）において、Ｍ2の全元素数を１００ｍｏｌ％としたときに、Ｎｉ、ＣｏおよびＭｎ以外の添加元素の割合は、１０ｍｏｌ％以下であることが好ましい。すなわち、上記一般式（２）で表されるＬｉ含有複合酸化物において、元素群Ｍ2の全元素数を１００ｍｏｌ％としたときに、Ｎｉの割合ａと、Ｃｏの割合ｂと、Ｍｎの割合ｃとの合計（ａ＋ｂ＋ｃ）は、９０ｍｏｌ％以上１００ｍｏｌ％以下とする。 M 2 related to the Li-containing composite oxide represented by the general formula (2) may contain an additive element other than Ni, Co, and Mn. Examples of such additive elements include Al, Mg, Zn, Ca, Ti, Cr, Zr, and Li. However, in the Li-containing composite oxide represented by the general formula (2), if the amount of these additive elements is too large, the discharge capacity may be reduced. Therefore, in the general formula (2), when the total number of elements of M 2 is 100 mol%, the ratio of additive elements other than Ni, Co, and Mn is preferably 10 mol% or less. That is, in the Li-containing composite oxide represented by the general formula (2), when the total number of elements in the element group M 2 is 100 mol%, the Ni ratio a, the Co ratio b, and the Mn ratio The total (a + b + c) with c is 90 mol% or more and 100 mol% or less.
本発明の非水二次電池に係る正極活物質には、上記一般式（１）で表されるＬｉ含有複合酸化物および上記一般式（２）で表されるＬｉ含有複合酸化物のいずれか一方のみを使用してもよく、両方を併用してもよく、上記一般式（１）で表されるＬｉ含有複合酸化物および上記一般式（２）で表されるＬｉ含有複合酸化物のいずれか一方または両方と、他の正極活物質とを併用してもよい。 The positive electrode active material according to the non-aqueous secondary battery of the present invention includes any one of the Li-containing composite oxide represented by the general formula (1) and the Li-containing composite oxide represented by the general formula (2). Only one of them may be used, or both of them may be used together. Either of the Li-containing composite oxide represented by the general formula (1) and the Li-containing composite oxide represented by the general formula (2) Either one or both may be used in combination with another positive electrode active material.
上記一般式（１）で表されるＬｉ含有複合酸化物や上記一般式（２）で表されるＬｉ含有複合酸化物と併用し得る他の正極活物質としては、例えば、ＬｉＣｏＯ2；ＬｉＣｏＯ2のＣｏの一部を、Ｔｉ、Ｚｒ、Ｍｇ、Ａｌなどの他の金属元素で置換したＬｉ含有複合酸化物［ただし、上記一般式（２）を満たさないもの］；などが挙げられる。 Examples of other positive electrode active materials that can be used in combination with the Li-containing composite oxide represented by the general formula (1) and the Li-containing composite oxide represented by the general formula (2) include LiCoO 2 ; LiCoO 2. Li-containing composite oxides in which a part of Co is substituted with other metal elements such as Ti, Zr, Mg, and Al [however, those that do not satisfy the general formula (2)]; and the like.
正極活物質に、上記一般式（１）で表されるＬｉ含有複合酸化物や上記一般式（２）で表されるＬｉ含有複合酸化物と、他の正極活物質とを併用する場合には、上記一般式（１）で表されるＬｉ複合酸化物および上記一般式（２）で表されるＬｉ含有複合酸化物の全正極活物質中における量［上記一般式（１）で表されるＬｉ複合酸化物および上記一般式（２）で表されるＬｉ含有複合酸化物のうち、いずれか一方のみを使用する場合は、その量であり、両方を使用する場合はそれらの合計量。］を、例えば、５０質量％以上とすることが好ましく、８０質量％以上とすることがより好ましい。 When the Li-containing composite oxide represented by the general formula (1) or the Li-containing composite oxide represented by the general formula (2) and another positive electrode active material are used in combination with the positive electrode active material The amount of the Li composite oxide represented by the above general formula (1) and the Li-containing composite oxide represented by the above general formula (2) in all the positive electrode active materials [represented by the above general formula (1) When only one of Li composite oxide and Li-containing composite oxide represented by the above general formula (2) is used, it is the amount thereof, and when both are used, the total amount thereof. ] Is preferably 50% by mass or more, and more preferably 80% by mass or more.
正極の導電助剤には、通常の非水二次電池と同様に、黒鉛；カーボンブラック（アセチレンブラック、ケッチェンブラックなど）や、表面に非晶質炭素を生成させた炭素材料などの非晶質炭素材料；繊維状炭素（気相成長炭素繊維、ピッチを紡糸した後に炭化処理して得られる炭素繊維など）；カーボンナノチューブ（各種の多層または単層のカーボンナノチューブ）などを用いることができる。正極の導電助剤には、上記例示のものを１種単独で用いてもよく、２種以上を併用してもよい。 As a normal non-aqueous secondary battery, the conductive additive for the positive electrode is non-crystalline such as graphite; carbon black (acetylene black, ketjen black, etc.) or a carbon material with amorphous carbon formed on the surface. Carbonaceous materials (fibre-grown carbon fibers, carbon fibers obtained by carbonizing after spinning a pitch), carbon nanotubes (various multi-layer or single-wall carbon nanotubes), and the like can be used. As the conductive additive for the positive electrode, those exemplified above may be used alone or in combination of two or more.
正極のバインダには、ＰＶＤＦ、ポリテトラフルオロエチレンなどのフッ素樹脂；ポリアクリル酸；ＳＢＲ；などを用いることができる。 For the binder of the positive electrode, fluororesins such as PVDF and polytetrafluoroethylene; polyacrylic acid; SBR; and the like can be used.
正極は、例えば、正極活物質、バインダおよび導電助剤を、ＮＭＰなどの溶剤に分散させたペースト状やスラリー状の正極合剤含有組成物を調製し（ただし、バインダは溶剤に溶解していてもよい。）、これを集電体の片面または両面に塗布し、乾燥した後に、必要に応じてカレンダー処理を施す工程を経て製造される。ただし、正極の製造方法は、上記の方法に制限される訳ではなく、他の製造方法で製造してもよい。 For the positive electrode, for example, a paste-like or slurry-like positive electrode mixture-containing composition in which a positive electrode active material, a binder, and a conductive additive are dispersed in a solvent such as NMP is prepared (however, the binder is dissolved in the solvent). It may be manufactured through a step of applying a calender treatment if necessary after applying it to one or both sides of the current collector and drying it. However, the manufacturing method of a positive electrode is not necessarily restricted to said method, You may manufacture with another manufacturing method.
正極合剤層の組成としては、例えば、正極活物質が７０〜９９質量％であることが好ましく、導電助剤が１〜２０質量％であることが好ましく、バインダが１〜３０質量％であることが好ましい。また、正極合剤層の厚みは、集電体の片面あたり、１〜１００μｍであることが好ましい。 As a composition of a positive mix layer, it is preferable that a positive electrode active material is 70-99 mass%, for example, it is preferable that a conductive support agent is 1-20 mass%, and a binder is 1-30 mass%. It is preferable. Moreover, it is preferable that the thickness of a positive mix layer is 1-100 micrometers per single side | surface of a collector.
正極の集電体には、例えば、アルミニウム、ステンレス鋼、ニッケル、チタンまたはそれらの合金からなる箔、パンチドメタル、エキスパンドメタル、網などを用い得るが、通常、厚みが１０〜３０μｍのアルミニウム箔が好適に用いられる。 For the positive electrode current collector, for example, a foil made of aluminum, stainless steel, nickel, titanium, or an alloy thereof, a punched metal, an expanded metal, a net, or the like can be used. Usually, an aluminum foil having a thickness of 10 to 30 μm is used. Are preferably used.
〔セパレータ〕
本発明の非水二次電池において、上記負極と上記正極とは、例えば、セパレータを介在させつつ積層した積層電極体や、更にこれを渦巻状に巻回した巻回電極体の形で用いられる。
[Separator]
In the nonaqueous secondary battery of the present invention, the negative electrode and the positive electrode are used, for example, in the form of a laminated electrode body laminated with a separator interposed therebetween, or a wound electrode body obtained by winding the separator in a spiral shape. .
セパレータとしては、強度が十分で、かつ非水電解質を多く保持できるものがよく、そのような観点から、厚さが１０〜５０μｍで開口率が３０〜７０％の、ポリエチレン、ポリプロピレン、またはエチレン−プロピレン共重合体を含む微多孔フィルムや不織布などが好ましい。 As the separator, a separator having sufficient strength and capable of holding a large amount of nonaqueous electrolyte is preferable. From such a viewpoint, polyethylene, polypropylene, or ethylene having a thickness of 10 to 50 μm and an aperture ratio of 30 to 70% is used. A microporous film or a nonwoven fabric containing a propylene copolymer is preferred.
〔非水電解質〕
本発明の非水二次電池に係る非水電解質には、通常、有機溶媒にリチウム塩などの電解質塩が溶解した非水系の液状電解質（非水電解液）が用いられる。そして、本発明に係る非水電解質には、ハロゲン置換された環状カーボネートと、ホウ酸トリエステルとを含有させる。かかる非水電解質の使用によって、高電圧での充放電を繰り返したときの充放電容量の低下を抑制できることから、非水二次電池の高エネルギー密度化を図りつつ、優れた充放電サイクル特性を確保することができる。
[Non-aqueous electrolyte]
For the nonaqueous electrolyte according to the nonaqueous secondary battery of the present invention, a nonaqueous liquid electrolyte (nonaqueous electrolyte) in which an electrolyte salt such as a lithium salt is dissolved in an organic solvent is usually used. The nonaqueous electrolyte according to the present invention contains a halogen-substituted cyclic carbonate and a boric acid triester. By using such a non-aqueous electrolyte, it is possible to suppress a decrease in charge / discharge capacity when repeated charge / discharge at a high voltage, so that excellent charge / discharge cycle characteristics are achieved while increasing the energy density of the non-aqueous secondary battery. Can be secured.
本発明による充放電サイクル劣化の抑制機構については、以下のように考えられる。ＳｉＯxを負極活物質に用いた負極での充放電サイクル劣化は、充放電による体積の膨張・収縮によってＳｉＯx粒子が徐々に粉砕され、表面に露出した活性な超微粒子のＳｉが非水電解質の溶媒などと反応し、その反応により生成した反応生成物によりＳｉとＬｉとの反応が阻害されることにより、電池の内部抵抗を増大させることにより生じると考えられる。非水電解質に含有させるハロゲン置換された環状カーボネートは、非水二次電池の非水電解質溶媒として一般に用いられているカーボネートに比べて還元されやすい性質を有しているため、負極側で優先的に還元分解し、ＳｉＯxの膨張・収縮による粉砕によって生じた新生面に皮膜を形成し、この皮膜が非水電解質とＳｉとの反応を抑制すると考えられる。 The charging / discharging cycle deterioration suppressing mechanism according to the present invention is considered as follows. Charge / discharge cycle deterioration in the negative electrode using SiO x as the negative electrode active material is due to the fact that the SiO x particles are gradually pulverized by the expansion and contraction of the volume due to charge and discharge, and the active ultrafine Si exposed on the surface is non-aqueous electrolyte. This is considered to be caused by increasing the internal resistance of the battery by inhibiting the reaction between Si and Li by the reaction product produced by the reaction with the above solvent. The halogen-substituted cyclic carbonate contained in the non-aqueous electrolyte has a property that it is more easily reduced than the carbonate generally used as a non-aqueous electrolyte solvent for non-aqueous secondary batteries. It is considered that the film is reduced and decomposed to form a film on the new surface produced by grinding by expansion and contraction of SiO x , and this film suppresses the reaction between the nonaqueous electrolyte and Si.
一方、非水電解質中のハロゲン置換された環状カーボネートは耐酸化性が高いため、正極側では分解され難い。しかし、上記一般式（１）で表されるＬｉ含有複合酸化物や上記一般式（２）で表されるＬｉ含有複合酸化物を正極活物質とする正極を有し、高電位で充電される非水二次電池においては、ハロゲン置換された環状カーボネートが正極側で従来よりも高い電位に晒されるため、酸化分解してしまうと考えられる。ハロゲン置換された環状カーボネートが正極側で酸化分解すると、負極側で果たすべき機能が失われるため、ＳｉＯx粒子の新生面における非水電解質とＳｉとの反応を十分に制御することができず、電池の充放電サイクル特性が低下してしまう。 On the other hand, the halogen-substituted cyclic carbonate in the non-aqueous electrolyte is highly resistant to oxidation, and is therefore difficult to decompose on the positive electrode side. However, it has a positive electrode using the Li-containing composite oxide represented by the general formula (1) or the Li-containing composite oxide represented by the general formula (2) as a positive electrode active material, and is charged at a high potential. In a non-aqueous secondary battery, it is considered that the halogen-substituted cyclic carbonate is exposed to a higher potential than the conventional one on the positive electrode side and is therefore oxidatively decomposed. When the halogen-substituted cyclic carbonate is oxidatively decomposed on the positive electrode side, the function to be performed on the negative electrode side is lost, so the reaction between the nonaqueous electrolyte and Si on the new surface of the SiO x particles cannot be sufficiently controlled, and the battery The charge / discharge cycle characteristics of the battery deteriorate.
これに対して、本発明に係る非水電解質に含有させるホウ酸トリエステルは、例えば非水電解質溶媒に汎用されるカーボネートよりも酸化されやすいため、正極側で優先的に酸化分解して、正極表面に皮膜を形成することが期待される。このホウ酸トリエステル由来の皮膜が、ハロゲン置換された環状カーボネートの正極側での分解を抑制する保護作用を発揮し、ハロゲン置換された環状カーボネートが負極表面で良好に皮膜形成できることから、本発明の非水二次電池では、充放電サイクル特性の劣化が改善される。ホウ酸トリエステルは耐還元性が高いために負極側で還元分解し難く、正極側での上記保護作用が良好に発揮されると推測される。 On the other hand, the boric acid triester contained in the nonaqueous electrolyte according to the present invention is more easily oxidized than, for example, carbonates commonly used in nonaqueous electrolyte solvents. It is expected to form a film on the surface. This boric acid triester-derived film exhibits a protective action to suppress decomposition of the halogen-substituted cyclic carbonate on the positive electrode side, and the halogen-substituted cyclic carbonate can form a film on the negative electrode surface. In the non-aqueous secondary battery, deterioration of charge / discharge cycle characteristics is improved. Since boric acid triester has high reduction resistance, it is difficult to reduce and decompose on the negative electrode side, and it is presumed that the protective action on the positive electrode side is exhibited well.
非水電解質に含有させるハロゲン置換された環状カーボネートとしては、下記一般式（３）で表される化合物を用いることができる。 As the halogen-substituted cyclic carbonate contained in the nonaqueous electrolyte, a compound represented by the following general formula (3) can be used.
上記一般式（３）中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、水素、ハロゲン元素または炭素数１〜１０のアルキル基を表しており、アルキル基の水素の一部または全部がハロゲン元素で置換されていてもよく、Ｒ1、Ｒ2、Ｒ3およびＲ4のうちの少なくとも１つはハロゲン元素であり、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれが異なっていてもよく、２つ以上が同一であってもよい。Ｒ1、Ｒ2、Ｒ3およびＲ4がアルキル基である場合、その炭素数は少ないほど好ましい。上記ハロゲン元素としては、フッ素が特に好ましい。 In the general formula (3), R 1 , R 2 , R 3 and R 4 represent hydrogen, a halogen element or an alkyl group having 1 to 10 carbon atoms, and a part or all of the hydrogen of the alkyl group is halogen. may be substituted with an element, at least one of R 1, R 2, R 3 and R 4 are halogen, R 1, R 2, R 3 and R 4 have different respective Two or more may be the same. When R 1 , R 2 , R 3 and R 4 are alkyl groups, the smaller the number of carbon atoms, the better. As the halogen element, fluorine is particularly preferable.
このようなハロゲン元素で置換された環状カーボネートの中でも、４−フルオロ−１，３−ジオキソラン−２−オン（ＦＥＣ）が特に好ましい。 Among the cyclic carbonates substituted with such a halogen element, 4-fluoro-1,3-dioxolan-2-one (FEC) is particularly preferable.
非水二次電池に使用する非水電解質中におけるハロゲン置換された環状カーボネートの含有量は、負極におけるＳｉＯx粒子の新生面での反応抑制効果をより良好に確保する観点から、０．５質量％以上であることが好ましく、１質量％以上であることがより好ましい。ただし、非水電解質中のハロゲン置換された環状カーボネートの量が多すぎると、負極活物質であるＳｉＯxの活性が低下したり、皮膜形成の際に過剰なガスが発生して電池外装体の膨れの原因となったりする虞がある。よって、非水二次電池に使用する非水電解質中におけるハロゲン置換された環状カーボネートの含有量は、２０質量％以下であることが好ましく、１０質量％以下であることがより好ましい。 The content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used in the non-aqueous secondary battery is 0.5% by mass from the viewpoint of better ensuring the reaction suppressing effect on the new surface of the SiO x particles in the negative electrode. The above is preferable, and the content is more preferably 1% by mass or more. However, if the amount of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte is too large, the activity of SiO x , which is the negative electrode active material, decreases or excessive gas is generated during film formation, and There is a risk of causing swelling. Therefore, the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used in the non-aqueous secondary battery is preferably 20% by mass or less, and more preferably 10% by mass or less.
非水電解質に含有させるホウ酸トリエステルとしては、ホウ酸のトリアルキルエステルが好ましい。ホウ酸のトリアルキルエステルにおけるアルキル部分は、炭素数が１〜４であることが好ましく、また、アルキル部分の水素の一部または全部がフッ素で置換されていてもよい。ホウ酸のトリアルキルエステルにおける３つのアルキル部分は、全てが同じ構造であってもよく、２つが同じ構造で他の１つが異なる構造であってもよく、全てが互いに異なる構造であってもよい。 As the boric acid triester contained in the non-aqueous electrolyte, a trialkyl ester of boric acid is preferable. The alkyl moiety in the trialkyl ester of boric acid preferably has 1 to 4 carbon atoms, and part or all of the hydrogen in the alkyl moiety may be substituted with fluorine. The three alkyl moieties in the trialkyl ester of boric acid may all be the same structure, two may be the same structure and the other one may be different, or all may be different from each other. .
ホウ酸トリエステルの好適な具体例としては、例えば、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル、ジメチルエチルホウ酸などが挙げられる。ホウ酸トリエステルは、例えば、上記例示のものを１種単独で用いてもよく、２種以上を併用してもよい。上記例示のホウ酸トリエステルの中でも、ホウ酸トリエチル（ＴＥＢ）が特に好ましい。 Specific examples of preferred boric acid triesters include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, dimethylethyl boric acid, and the like. As the boric acid triester, for example, those exemplified above may be used alone or in combination of two or more. Of the boric acid triesters exemplified above, triethyl borate (TEB) is particularly preferred.
非水二次電池に使用する非水電解質中におけるホウ酸トリエステルの含有量は、正極表面により良好な皮膜を形成できるようにして、前述の保護作用を良好に発揮させる観点から、０．１質量％以上であることが好ましく、０．２質量％以上であることがより好ましい。ただし、非水電解質中のホウ酸トリエステルの量が多すぎると、Ｌｉイオンの移動を阻害する虞がある。よって、非水二次電池に使用する非水電解質中におけるホウ酸トリエステルの含有量は、１質量％以下であることが好ましく、０．８質量％以下であることがより好ましい。 The content of boric acid triester in the non-aqueous electrolyte used for the non-aqueous secondary battery is 0.1% from the viewpoint of allowing the positive electrode surface to form a good film and exhibiting the above-described protective action well. The content is preferably at least mass%, more preferably at least 0.2 mass%. However, if the amount of boric acid triester in the non-aqueous electrolyte is too large, the movement of Li ions may be inhibited. Therefore, the content of boric acid triester in the non-aqueous electrolyte used in the non-aqueous secondary battery is preferably 1% by mass or less, and more preferably 0.8% by mass or less.
非水電解質に係る有機溶媒としては、特に限定されることはないが、例えば、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネートなどの鎖状エステル；エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネートなどの誘電率の高い環状エステル；鎖状エステルと環状エステルとの混合溶媒；などが挙げられ、特に鎖状エステルを主溶媒とした環状エステルとの混合溶媒が適している。 The organic solvent related to the non-aqueous electrolyte is not particularly limited. For example, chain esters such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methyl propyl carbonate; ethylene carbonate, propylene carbonate, butylene carbonate, vinylene A cyclic ester having a high dielectric constant such as carbonate; a mixed solvent of a chain ester and a cyclic ester; and the like. In particular, a mixed solvent with a cyclic ester having a chain ester as a main solvent is suitable.
また、非水電解質の調製にあたって有機溶媒に溶解させる電解質塩としては、例えば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＣ4Ｆ9ＳＯ3、ＬｉＣＦ3ＣＯ2、Ｌｉ2Ｃ2Ｆ4（ＳＯ3）2、ＬｉＣnＦ2n+1ＳＯ3（２≦ｎ≦７）、ＬｉＮ（ＲｆＳＯ2）（Ｒｆ’ＳＯ2）、ＬｉＣ（ＲｆＳＯ2）3、ＬｉＮ（ＲｆＯＳＯ2）2〔ここで、Ｒｆ、Ｒｆ’はフルオロアルキル基を表す。〕などが単独でまたは２種以上混合して用いられる。非水電解質中における電解質塩の濃度は、特に限定されることはないが、０．３ｍｏｌ／Ｌ以上であることが好ましく、０．４ｍｏｌ／Ｌ以上であることがより好ましく、また、１．７ｍｏｌ／Ｌ以下であることが好ましく、１．５ｍｏｌ／Ｌ以下であることがより好ましい。
As the non-aqueous electrolyte electrolyte salt to be dissolved in the organic solvent In the preparation of, for example, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6,
本発明の非水二次電池において、非水電解質には、上記液状電解質（非水電解液）以外にも、上記非水電解液をポリマーなどからなるゲル化剤でゲル化したゲル状電解質も使用することができる。 In the non-aqueous secondary battery of the present invention, as the non-aqueous electrolyte, in addition to the liquid electrolyte (non-aqueous electrolyte), a gel electrolyte obtained by gelling the non-aqueous electrolyte with a gelling agent composed of a polymer or the like is also included. Can be used.
〔電池の形態〕
本発明の非水二次電池の形態としては、例えば、スチール缶やアルミニウム缶などを外装缶として使用した筒形（角筒形や円筒形など）が挙げられる。また、金属を蒸着したラミネートフィルムを外装体としたソフトパッケージ電池とすることもできる。
[Battery form]
As a form of the non-aqueous secondary battery of the present invention, for example, a tubular shape (such as a square tubular shape or a cylindrical shape) using a steel can, an aluminum can, or the like as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
図１Ａは、本発明の非水二次電池の一例を示す平面図であり、図１Ｂは、図１Ａの断面図である。また、図２は、図１Ａ、Ｂに示す本発明の非水二次電池の斜視図である。 FIG. 1A is a plan view showing an example of the non-aqueous secondary battery of the present invention, and FIG. 1B is a cross-sectional view of FIG. 1A. 2 is a perspective view of the nonaqueous secondary battery of the present invention shown in FIGS. 1A and 1B.
図１Ｂに示すように、正極１と負極２はセパレータ３を介して渦巻状に巻回した後、扁平状になるように加圧して扁平状の巻回電極体６として、角筒形の外装缶４に非水電解液と共に収容されている。但し、図１Ｂでは、煩雑化を避けるため、正極１や負極２の作製にあたって使用した集電体としての金属箔や非水電解液などは図示しておらず、また、巻回電極体６の内周側の部分は断面にしていない。
As shown in FIG. 1B, the positive electrode 1 and the
外装缶４はアルミニウム合金製で電池の外装体を構成するものであり、この外装缶４は正極端子を兼ねている。そして、外装缶４の底部にはポリエチレンシートからなる絶縁体５が配置され、正極１、負極２およびセパレータ３からなる巻回電極体６からは、正極１および負極２のそれぞれ一端に接続された正極リード体７と負極リード体８が引き出されている。また、外装缶４の開口部を封口するアルミニウム合金製の封口用の蓋板９にはポリプロピレン製の絶縁パッキング１０を介してステンレス鋼製の端子１１が取り付けられ、この端子１１には絶縁体１２を介してステンレス鋼製のリード板１３が取り付けられている。
The
そして、この蓋板９は外装缶４の開口部に挿入され、両者の接合部を溶接することによって、外装缶４の開口部が封口され、電池内部が密閉されている。また、図１Ａ、Ｂの電池では、蓋板９に非水電解液注入口１４が設けられており、この非水電解液注入口１４には、封止部材が挿入された状態で、例えばレーザー溶接などにより溶接封止されて、電池の密閉性が確保されている。従って、図１Ａ、Ｂおよび図２の電池では、実際には、非水電解液注入口１４は、非水電解液注入口と封止部材であるが、説明を容易にするために、非水電解液注入口１４として示している。更に、蓋板９には、電池の温度が上昇した際に内部のガスを外部に排出する機構として、開裂ベント１５が設けられている。
And this
上記電池では、正極リード体７を蓋板９に直接溶接することによって外装缶４と蓋板９とが正極端子として機能し、負極リード体８をリード板１３に溶接し、そのリード板１３を介して負極リード体８と端子１１とを導通させることによって端子１１が負極端子として機能するようになっているが、外装缶４の材質などによっては、その正負が逆になる場合もある。
In the battery, by directly welding the positive
図３は、本発明の非水二次電池の他の例を示す平面図である。図３において、本発明の非水二次電池２０は、正極、負極、および非水電解質が、平面視で矩形のアルミニウムラミネートフィルムからなる外装体２１内に収容されている。そして、正極外部端子２２および負極外部端子２３が、外装体２１の同じ辺から引き出されている。
FIG. 3 is a plan view showing another example of the nonaqueous secondary battery of the present invention. In FIG. 3, in the nonaqueous
本発明の非水二次電池は、高電圧充電を行っても優れた充放電サイクル特性を発揮し得る。本発明の電池は、このような特性を生かして、電子機器（特に携帯電話やノート型パーソナルコンピュータなどのポータブル電子機器）、電源システム、乗り物（電気自動車、電動自転車など）などの各種機器の電源用途などに、好ましく用いることができる。 The nonaqueous secondary battery of the present invention can exhibit excellent charge / discharge cycle characteristics even when high voltage charging is performed. The battery of the present invention makes use of such characteristics, and power sources for various devices such as electronic devices (especially portable electronic devices such as mobile phones and notebook personal computers), power supply systems, vehicles (electric cars, electric bicycles, etc.). It can be preferably used for applications.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.
（実施例１）
＜正極の作製＞
正極活物質であるＬｉＮｉ0.5Ｍｎ1.5Ｏ4［前述の一般式（１）で表されるＬｉ含有複合酸化物に該当、平均粒径：１５μｍ］：８５質量部と、導電助剤であるアセチレンブラック（平均粒径：５０ｎｍ）：１０質量部と、バインダであるＰＶＤＦ：５質量部とを混合して正極合剤とし、これをＮＭＰに分散させて正極合剤含有ペーストを調製した。この正極合剤含有ペーストを、厚みが１５μｍのアルミニウム箔からなる集電体の片面に塗布し、乾燥して正極合剤層を形成し、プレスした後に１２０℃で乾燥して正極シート材を得た。この正極シート材を、直径１３ｍｍの円形に打ち抜いて正極とした。得られた正極は、正極合剤層の厚みが６０μｍであり、正極合剤層における導電助剤およびバインダを除いた正極活物質の量は１５ｍｇ／ｃｍ2であった。
Example 1
<Preparation of positive electrode>
LiNi 0.5 Mn 1.5 O 4 as a positive electrode active material [corresponding to the Li-containing composite oxide represented by the above general formula (1), average particle size: 15 μm]: 85 parts by mass, and acetylene black as a conductive auxiliary agent (Average particle diameter: 50 nm): 10 parts by mass and PVDF as a binder: 5 parts by mass were mixed to form a positive electrode mixture, which was dispersed in NMP to prepare a positive electrode mixture-containing paste. This positive electrode mixture-containing paste is applied to one side of a current collector made of an aluminum foil having a thickness of 15 μm, dried to form a positive electrode mixture layer, pressed, and then dried at 120 ° C. to obtain a positive electrode sheet material. It was. This positive electrode sheet material was punched into a circle having a diameter of 13 mm to obtain a positive electrode. In the positive electrode obtained, the positive electrode mixture layer had a thickness of 60 μm, and the amount of the positive electrode active material excluding the conductive additive and binder in the positive electrode mixture layer was 15 mg / cm 2 .
＜負極の作製＞
非晶質のＳｉＯ2マトリックス中にＳｉが分散した構造で、ＳｉＯ2とＳｉのモル比が１：１の材料であるＳｉＯ粒子を、ＣＶＤ法によって炭素材料で被覆して負極活物質とした。その炭素被覆ＳｉＯ（平均粒径：５μｍ）：８２質量部と、導電助剤であるケッチェンブラック（平均粒径４０ｎｍ）：１０質量部と、バインダであるＰＶＤＦ：８質量部とを混合して負極合剤とし、これをＮＭＰに分散させて負極合剤含有ペーストを調製した。上記炭素被覆ＳｉＯにおいて、ＣＶＤ法による被覆前後の質量変化から求めたＳｉＯと炭素材料との比率（質量比）は、８０：２０であった。
<Production of negative electrode>
SiO particles having a structure in which Si was dispersed in an amorphous SiO 2 matrix and having a molar ratio of SiO 2 and Si of 1: 1 were coated with a carbon material by a CVD method to obtain a negative electrode active material. Carbon coated SiO (average particle size: 5 μm): 82 parts by mass, Ketjen black (average particle size 40 nm) as a conductive auxiliary agent: 10 parts by mass, PVDF as a binder: 8 parts by mass A negative electrode mixture-containing paste was prepared by dispersing it in NMP as a negative electrode mixture. In the carbon-coated SiO, the ratio (mass ratio) between SiO and the carbon material determined from the mass change before and after the CVD method was 80:20.
上記負極合剤含有ペーストを、厚みが１５μｍの銅箔からなる集電体の片面に塗布し、乾燥して負極合剤層を形成し、プレスした後に１２０℃で乾燥して負極シート材を得た。この負極シート材を、直径１４ｍｍの円形に打ち抜いて負極とした。得られた負極は、負極合剤層の厚みが２５μｍであり、負極合剤層における導電助剤およびバインダを除いた負極活物質の量は３ｍｇ／ｃｍ2であった。 The negative electrode mixture-containing paste is applied to one side of a current collector made of a copper foil having a thickness of 15 μm, dried to form a negative electrode mixture layer, pressed, and dried at 120 ° C. to obtain a negative electrode sheet material. It was. This negative electrode sheet material was punched into a circle having a diameter of 14 mm to form a negative electrode. In the obtained negative electrode, the thickness of the negative electrode mixture layer was 25 μm, and the amount of the negative electrode active material excluding the conductive additive and the binder in the negative electrode mixture layer was 3 mg / cm 2 .
＜非水電解質の調製＞
エチレンカーボネートとジエチルカーボネートとの体積比３：７の混合溶媒に、ＬｉＰＦ6を１．２ｍｏｌ／Ｌの濃度で溶解させた溶液を調製し、この溶液に、８質量％の量となるＦＥＣと、０．３質量％の量となるＴＥＢとを添加し、攪拌・混合して非水電解質を得た。
<Preparation of non-aqueous electrolyte>
A solution in which LiPF 6 was dissolved at a concentration of 1.2 mol / L in a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 3: 7 was prepared, and in this solution, FEC in an amount of 8% by mass; TEB in an amount of 0.3% by mass was added and stirred and mixed to obtain a nonaqueous electrolyte.
＜電池の組み立て＞
電池の組み立てはアルゴングローブボックス内で行った。セパレータには、多孔性のポリエチレンフィルム（厚さ：１６μｍ）を用いた。電池の外装体には宝泉株式会社製の「ＨＳフラットセル」を用い、正極、セパレータ、負極の順に積み重ねた積層体を外装体内に収容した後に、ＦＥＣとＴＥＢとを添加した上記非水電解質を１００μＬ注入した。その後、外装体を封止して、非水二次電池を作製した。
<Battery assembly>
The battery was assembled in an argon glove box. As the separator, a porous polyethylene film (thickness: 16 μm) was used. The above-mentioned non-aqueous electrolyte in which a “HS flat cell” manufactured by Hosen Co., Ltd. is used as the battery outer package, and a laminate in which the positive electrode, the separator, and the negative electrode are stacked in this order is accommodated in the outer package, and then FEC and TEB are added. Was injected at 100 μL. Then, the exterior body was sealed and the non-aqueous secondary battery was produced.
上記非水二次電池について、下記の方法で充放電特性として初期特性および充放電サイクル特性を評価した。 With respect to the non-aqueous secondary battery, initial characteristics and charge / discharge cycle characteristics were evaluated as charge / discharge characteristics by the following method.
＜初期特性＞
上記非水二次電池を、２５℃の環境下で、電池電圧が５Ｖになるまで０．２ｍＡ／ｃｍ2の定電流で充電し、その後、０．２ｍＡ／ｃｍ2の定電流で電池電圧が３．０Ｖになるまで放電した。この一連の操作を１サイクルとして５サイクル繰り返して、５サイクル目の放電容量を初期放電容量とした。
<Initial characteristics>
The non-aqueous secondary battery is charged at a constant current of 0.2 mA / cm 2 in a 25 ° C. environment until the battery voltage reaches 5 V, and then the battery voltage is constant at a constant current of 0.2 mA / cm 2. It discharged until it became 3.0V. This series of operations was repeated 5 cycles, and the discharge capacity at the 5th cycle was defined as the initial discharge capacity.
＜充放電サイクル特性＞
初期特性を測り終えた非水二次電池を、２５℃の環境下で、電池電圧が４．８５Ｖ（充電終了電圧）になるまで１ｍＡ／ｃｍ2の定電流で充電し、その後、１ｍＡ／ｃｍ2の定電流で電池電圧が３．０Ｖ（放電終了電圧）になるまで放電した。この一連の操作を１サイクルとして１００サイクル繰り返した。次に、この１００サイクル充放電した電池を、電池電圧が５Ｖになるまで０．２ｍＡ／ｃｍ2の定電流で充電し、その後、０．２ｍＡ／ｃｍ2の定電流で電池電圧が３．０Ｖになるまで放電し、この放電容量を充放電サイクル後の放電容量とした。そして、上記初期特性として測定した初期放電容量を充放電サイクル前の放電容量として、この充放電サイクル前の放電容量に対する上記充放電サイクル後の放電容量の割合を百分率で表して、容量維持率を求めた。
<Charge / discharge cycle characteristics>
The non-aqueous secondary battery whose initial characteristics have been measured is charged at a constant current of 1 mA / cm 2 until the battery voltage reaches 4.85 V (charge end voltage) in an environment of 25 ° C., and then 1 mA / cm. The battery was discharged at a constant current of 2 until the battery voltage reached 3.0 V (discharge end voltage). This series of operations was repeated as 100 cycles for 100 cycles. Next, the battery charged and discharged for 100 cycles was charged with a constant current of 0.2 mA / cm 2 until the battery voltage reached 5 V, and then the battery voltage was 3.0 V with a constant current of 0.2 mA / cm 2. The discharge capacity was taken as the discharge capacity after the charge / discharge cycle. Then, the initial discharge capacity measured as the initial characteristic is defined as the discharge capacity before the charge / discharge cycle, and the ratio of the discharge capacity after the charge / discharge cycle to the discharge capacity before the charge / discharge cycle is expressed as a percentage. Asked.
（実施例２）
正極活物質を、ＬｉＮｉ0.5Ｃｏ0.2Ｍｎ0.3Ｏ2［前述の一般式（２）で表されるＬｉ含有複合酸化物に該当、平均粒径：１０μｍ］に変更した以外は、実施例１と同様にして正極を作製した。この正極の正極合剤層における導電助剤およびバインダを除いた正極活物質の量は、１０ｍｇ／ｃｍ2であった。そして、この正極を用いた以外は、実施例１と同様にして非水二次電池を作製した。
(Example 2)
The same as in Example 1 except that the positive electrode active material was changed to LiNi 0.5 Co 0.2 Mn 0.3 O 2 [corresponding to the Li-containing composite oxide represented by the above general formula (2), average particle size: 10 μm]. Thus, a positive electrode was produced. The amount of the positive electrode active material excluding the conductive additive and the binder in the positive electrode mixture layer of this positive electrode was 10 mg / cm 2 . And the non-aqueous secondary battery was produced like Example 1 except having used this positive electrode.
上記非水二次電池について、充電終了電圧を４．６Ｖとし、放電終了電圧を２．５Ｖとした以外は、実施例１の非水二次電池と同様の方法で充放電サイクル特性（容量維持率）を評価した。 For the non-aqueous secondary battery, charge / discharge cycle characteristics (capacity maintenance) were performed in the same manner as the non-aqueous secondary battery of Example 1 except that the charge end voltage was 4.6 V and the discharge end voltage was 2.5 V. Rate).
（比較例１）
ＴＥＢを添加しない以外は、実施例１と同様にして非水電解質を調製し、この非水電解質を用いた以外は、実施例１と同様にして非水二次電池を作製した。そして、この非水二次電池について、実施例１の非水二次電池と同じ方法で充放電サイクル特性（容量維持率）を評価した。
(Comparative Example 1)
A nonaqueous electrolyte was prepared in the same manner as in Example 1 except that TEB was not added, and a nonaqueous secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used. And about this non-aqueous secondary battery, the charge / discharge cycle characteristic (capacity maintenance factor) was evaluated by the same method as the non-aqueous secondary battery of Example 1.
（比較例２）
ＦＥＣを添加しない以外は、実施例１と同様にして非水電解質を調製し、この非水電解質を用いた以外は、実施例１と同様にして非水二次電池を作製した。そして、この非水二次電池について、実施例１の非水二次電池と同じ方法で充放電サイクル特性（容量維持率）を評価した。
(Comparative Example 2)
A nonaqueous electrolyte was prepared in the same manner as in Example 1 except that FEC was not added, and a nonaqueous secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used. And about this non-aqueous secondary battery, the charge / discharge cycle characteristic (capacity maintenance factor) was evaluated by the same method as the non-aqueous secondary battery of Example 1.
実施例１〜２および比較例１〜２の非水二次電池における充放電サイクル前後での容量維持率の測定結果を表１に示す。 Table 1 shows the measurement results of the capacity retention ratios before and after the charge / discharge cycle in the nonaqueous secondary batteries of Examples 1-2 and Comparative Examples 1-2.
表１に示す通り、ハロゲン置換された環状カーボネートとホウ酸トリエステルとを含有する非水電解質を用いた実施例１、２の非水二次電池は、ＳｉＯxを負極活物質とする負極と、前述の一般式（１）で表されるＬｉ含有複合酸化物または前述の一般式（２）で表されるＬｉ含有複合酸化物を正極活物質とする正極とを有していて、高電位での充放電を行っても、充放電サイクル前後での容量維持率が高く、良好な充放電サイクル特性を確保できていることが分かる。 As shown in Table 1, the non-aqueous secondary batteries of Examples 1 and 2 using a non-aqueous electrolyte containing a halogen-substituted cyclic carbonate and a boric acid triester include a negative electrode using SiO x as a negative electrode active material, A positive electrode having a Li-containing composite oxide represented by the general formula (1) or a Li-containing composite oxide represented by the general formula (2) as a positive electrode active material, and having a high potential. It can be seen that the capacity retention rate before and after the charging / discharging cycle is high even when charging / discharging is performed, and good charging / discharging cycle characteristics can be secured.
これに対し、ホウ酸トリエステルを含有しない非水電解質を用いた比較例１の電池、およびハロゲン置換された環状カーボネートを含有しない非水電解質を用いた比較例２の電池では、充放電サイクル前後での容量維持率が低く、充放電に伴うＳｉＯxの膨張・収縮に起因すると考えられる充放電サイクル特性の低下が十分に抑制できていないことが分かる。 On the other hand, in the battery of Comparative Example 1 using a non-aqueous electrolyte not containing boric acid triester and the battery of Comparative Example 2 using a non-aqueous electrolyte containing no halogen-substituted cyclic carbonate, before and after the charge / discharge cycle It can be seen that the capacity retention rate at the time is low, and the deterioration of the charge / discharge cycle characteristics, which is considered to be caused by the expansion / contraction of SiO x accompanying charge / discharge, is not sufficiently suppressed.
本発明は、その趣旨を逸脱しない範囲で、上記以外の形態としても実施が可能である。本出願に開示された実施形態は一例であって、これらに限定はされない。本発明の範囲は、上述の明細書の記載よりも、添付されている請求の範囲の記載を優先して解釈され、請求の範囲と均等の範囲内での全ての変更は、請求の範囲に含まれるものである。 The present invention can be implemented in other forms than the above without departing from the spirit of the present invention. The embodiments disclosed in the present application are merely examples, and the present invention is not limited thereto. The scope of the present invention is construed in preference to the description of the appended claims rather than the description of the above specification, and all modifications within the scope equivalent to the claims are construed in the scope of the claims. It is included.
１ 正極
２ 負極
３ セパレータ
４ 外装缶
５ 絶縁体
６ 巻回電極体
７ 正極リード体
８ 負極リード体
９ 蓋板
１０ 絶縁パッキング
１１ 端子
１２ 絶縁体
１３ リード板
１４ 非水電解液注入口
１５ 開裂ベント
２０ 非水二次電池
２１ 外装体
２２ 正極外部端子
２３ 負極外部端子
DESCRIPTION OF SYMBOLS 1
Claims (10)
前記負極は、ケイ素と酸素とを構成元素に含む負極材料であって、前記ケイ素に対する前記酸素の原子比ｘが０．５≦ｘ≦１．５である負極材料を含有する負極合剤層を含み、
前記正極は、下記一般式（１）で表される複合酸化物を含有する正極合剤層を含み、
ＬｉＮｉyＭｎ2-y-zＭ1 zＯ4 （１）
前記一般式（１）中、Ｍ1は、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ａｌ、Ｍｇ、ＺｎおよびＬｉよりなる群から選択される少なくとも１種の元素であり、ｙは０．４５≦ｙ≦０．５５、ｚは０≦ｚ≦０．１であり、
前記非水電解質は、４−フルオロ−１，３−ジオキソラン−２−オンと、ホウ酸トリエステルとを含むことを特徴とする非水二次電池。 A non-aqueous secondary battery including a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte,
The negative electrode is a negative electrode material containing silicon and oxygen as constituent elements, and a negative electrode mixture layer containing a negative electrode material in which an atomic ratio x of the oxygen to silicon is 0.5 ≦ x ≦ 1.5 Including
The positive electrode includes a positive electrode mixture layer containing a composite oxide represented by the following general formula (1),
LiNi y Mn 2-yz M 1 z O 4 (1)
In the general formula (1), M 1 is at least one element selected from the group consisting of Co, Cr, Fe, Ti, Al, Mg, Zn, and Li, and y is 0.45 ≦ y ≦. 0.55, z is 0 ≦ z ≦ 0.1,
The non-aqueous electrolyte includes 4-fluoro-1,3-dioxolan-2-one and a boric acid triester.
前記負極は、ケイ素と酸素とを構成元素に含む負極材料であって、前記ケイ素に対する前記酸素の原子比ｘが０．５≦ｘ≦１．５である負極材料を含有する負極合剤層を含み、
前記正極は、下記一般式（２）で表される複合酸化物を含有する正極合剤層を含み、
ＬｉＭ2Ｏ2 （２）
前記一般式（２）中、Ｍ2は、ＮｉおよびＣｏを含む２種以上の元素を少なくとも含み、Ｍ2の全元素数に対する、Ｎｉ、ＣｏおよびＭｎの元素数の割合を、それぞれａ（ｍｏｌ％）、ｂ（ｍｏｌ％）及びｃ（ｍｏｌ％）としたときに、２０≦ａ≦６５、１５≦ｂ≦５５、０≦ｃ≦４５、９０≦ａ＋ｂ＋ｃ≦１００であり、
前記非水電解質は、４−フルオロ−１，３−ジオキソラン−２−オンと、ホウ酸トリエステルとを含むことを特徴とする非水二次電池。 A non-aqueous secondary battery including a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte,
The negative electrode is a negative electrode material containing silicon and oxygen as constituent elements, and a negative electrode mixture layer containing a negative electrode material in which an atomic ratio x of the oxygen to silicon is 0.5 ≦ x ≦ 1.5 Including
The positive electrode includes a positive electrode mixture layer containing a composite oxide represented by the following general formula (2),
LiM 2 O 2 (2)
In the general formula (2), M 2 includes at least two elements including Ni and Co, and the ratio of the number of elements of Ni, Co, and Mn to the total number of elements of M 2 is represented by a (mol %), B (mol%) and c (mol%), 20 ≦ a ≦ 65, 15 ≦ b ≦ 55, 0 ≦ c ≦ 45, 90 ≦ a + b + c ≦ 100,
The non-aqueous electrolyte includes 4-fluoro-1,3-dioxolan-2-one and a boric acid triester.
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| CN103943883A (en) * | 2014-04-23 | 2014-07-23 | 华南师范大学 | Application of borate compound serving as additive for high-voltage lithium-ion battery electrolyte |
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| JP6396136B2 (en) * | 2014-09-18 | 2018-09-26 | マクセルホールディングス株式会社 | Lithium secondary battery |
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| CN105390747A (en) * | 2015-11-13 | 2016-03-09 | 华南师范大学 | Trimethyl borate additive-containing electrolyte solution, preparation method therefor and application thereof |
| CN105244540A (en) * | 2015-11-13 | 2016-01-13 | 华南师范大学 | Electrolyte containing triethyl borate additive as well as preparation method and application thereof |
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| CN106207122A (en) * | 2016-08-12 | 2016-12-07 | 联想(北京)有限公司 | Polymer Li-ion battery negative material and polymer Li-ion battery and electronic equipment |
| CN109964354B (en) * | 2017-01-30 | 2022-04-29 | 松下电器产业株式会社 | Nonaqueous electrolyte secondary battery |
| JP6918638B2 (en) * | 2017-08-23 | 2021-08-11 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003132946A (en) * | 2001-10-24 | 2003-05-09 | Mitsui Chemicals Inc | Nonaqueous electrolytic solution and secondary battery using the same |
| JP2011054406A (en) * | 2009-09-01 | 2011-03-17 | Mitsui Chemicals Inc | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| JP2011077029A (en) * | 2009-09-07 | 2011-04-14 | Adeka Corp | Nonaqueous electrolytic solution, and nonaqueous electrolytic solution secondary battery using the nonaqueous electrolytic solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003132946A (en) * | 2001-10-24 | 2003-05-09 | Mitsui Chemicals Inc | Nonaqueous electrolytic solution and secondary battery using the same |
| JP2011054406A (en) * | 2009-09-01 | 2011-03-17 | Mitsui Chemicals Inc | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| JP2011077029A (en) * | 2009-09-07 | 2011-04-14 | Adeka Corp | Nonaqueous electrolytic solution, and nonaqueous electrolytic solution secondary battery using the nonaqueous electrolytic solution |
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| Publication number | Publication date |
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| CN103415951B (en) | 2016-01-20 |
| CN103415951A (en) | 2013-11-27 |
| WO2013042419A1 (en) | 2013-03-28 |
| KR101489335B1 (en) | 2015-02-03 |
| JPWO2013042419A1 (en) | 2015-03-26 |
| KR20130119956A (en) | 2013-11-01 |
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