JP4215263B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery Download PDFInfo
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- JP4215263B2 JP4215263B2 JP2006062547A JP2006062547A JP4215263B2 JP 4215263 B2 JP4215263 B2 JP 4215263B2 JP 2006062547 A JP2006062547 A JP 2006062547A JP 2006062547 A JP2006062547 A JP 2006062547A JP 4215263 B2 JP4215263 B2 JP 4215263B2
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- positive electrode
- secondary battery
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- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- LCBKDULHZJKFJQ-UHFFFAOYSA-N lithium chromium(3+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[Cr+3] LCBKDULHZJKFJQ-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
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- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、非水二次電池に関するものであり、さらに詳しくは、高容量で、かつサイクル特性が優れた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, and more particularly to a non-aqueous secondary battery having a high capacity and excellent cycle characteristics.
リチウムイオン電池に代表される非水二次電池は、容量が大きく、かつ高電圧、高エネルギー密度、高出力であることから、ますます需要が増える傾向にある。 Non-aqueous secondary batteries represented by lithium-ion batteries have a large capacity, high voltage, high energy density, and high output, and therefore demand is increasing.
しかしながら、本発明者らが上記非水二次電池のさらなる高容量化を目指して検討を進めているうちに、この非水二次電池では、電池の容量が増加するにつれてサイクル特性が低下する傾向があり、特に電極積層体単位面積当たりの放電容量が１３０ｍＡｈ／ｃｍ３以上の高容量になると、所望のサイクル特性が得られなくなることが判明した。 However, while the present inventors have been studying to further increase the capacity of the non-aqueous secondary battery, in this non-aqueous secondary battery, the cycle characteristics tend to decrease as the battery capacity increases. In particular, it has been found that when the discharge capacity per unit area of the electrode laminate becomes a high capacity of 130 mAh / cm 3 or more, desired cycle characteristics cannot be obtained.
本発明は、上記のような従来技術の問題点を解決し、電極積層体単位体積当たりの放電容量が１３０ｍＡｈ／ｃｍ３以上、とりわけ、１４０ｍＡｈ／ｃｍ３以上という高容量の非水二次電池においても、所望のサイクル特性が得られるようにし、高容量で、かつサイクル特性が優れた非水二次電池を提供することを目的とする。 The present invention solves the above-mentioned problems of the prior art, and in a high capacity non-aqueous secondary battery having a discharge capacity per unit volume of electrode laminate of 130 mAh / cm 3 or more, particularly 140 mAh / cm 3 or more. Another object of the present invention is to provide a non-aqueous secondary battery having desired cycle characteristics, high capacity, and excellent cycle characteristics.
本発明は、正極集電材として、厚みが１５μｍ以下で、アルミニウムを主成分とし、鉄を０．５〜２．０質量％含み、かつシリコンを０．０５〜１．０質量％含み、伸びが２％以上で、かつ引張り強度が１５０Ｎ／ｍｍ２以上である金属箔を用いることによって、電極積層体の単位面積当たりの放電容量が１４０ｍＡｈ／ｃｍ３以上という高容量の非水二次電池においても、良好なサイクル特性を得ることができ、上記課題を解決できることを見出したものである。 The present invention provides a positive electrode current collector having a thickness of 15 μm or less, containing aluminum as a main component, containing 0.5 to 2.0 mass% of iron, 0.05 to 1.0 mass% of silicon, and having an elongation. Even in a high capacity non-aqueous secondary battery having a discharge capacity per unit area of 140 mAh / cm 3 or more by using a metal foil of 2% or more and a tensile strength of 150 N / mm 2 or more. It has been found that good cycle characteristics can be obtained and the above-mentioned problems can be solved.
本発明によれば、電極積層体単位体積当たりの放電容量が１４０ｍＡｈ／ｃｍ３以上という高容量で、かつサイクル特性が良好な非水二次電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the discharge capacity per unit volume of electrode laminated bodies can provide the high capacity | capacitance of 140 mAh / cm < 3 > or more, and a non-aqueous secondary battery with favorable cycling characteristics can be provided.
本発明において用いる正極集電材は、アルミニウムを主成分とする金属箔であるが、その純度はアルミニウムが９８質量％以上９９．９質量％未満であることが好ましい。通常のリチウムイオン電池では一般に純度が９９．９質量％以上のアルミニウム箔が正極集電材として用いられているが、本発明においては、正極集電材として厚みが１５μｍ以下の薄い金属箔を使用するので、薄くても使用に耐え得る強度にする必要があり、そのため、純度は９９．９質量％（以下、特に断らない場合、％は質量％を示す）未満にして強度を高めるようにすることが好ましい。添加する金属元素は、鉄とシリコンである。鉄は０．５％以上が必要であり、好ましくは０．７％以上である。ただし、鉄が多くなりすぎると鉄イオンが溶出するようになるおそれがあるので、鉄は２％以下が必要であり、好ましくは１．３％以下である。シリコンは、０．０５％以上が必要であり、好ましくは０．２％以上である。ただし、シリコンが多くなりすぎると圧延むらやピンホールなどが生じやすくなるおそれがあるので、シリコンは、１．０％以下が必要であり、好ましくは０．３％以下である。なお、これらの鉄やシリコンはアルミニウムと合金化していることが必要であり、アルミニウム中に不純物として存在するものではない。 The positive electrode current collector used in the present invention is a metal foil containing aluminum as a main component, and the purity of aluminum is preferably 98% by mass or more and less than 99.9% by mass. In an ordinary lithium ion battery, an aluminum foil having a purity of 99.9% by mass or more is generally used as a positive electrode current collector. However, in the present invention, a thin metal foil having a thickness of 15 μm or less is used as the positive electrode current collector. The strength should be sufficient to withstand use even if it is thin. Therefore, the purity should be increased to less than 99.9% by mass (hereinafter, unless otherwise specified,% indicates mass%). preferable. Metal elements to be added are iron and silicon. Iron needs to be 0.5% or more, preferably 0.7% or more. However, since iron ions may be eluted when there is too much iron, iron needs to be 2% or less, preferably 1.3% or less. Silicon needs to be 0.05% or more, preferably 0.2% or more. However, if there is too much silicon, rolling unevenness, pinholes and the like are likely to occur, so silicon needs to be 1.0% or less, preferably 0.3% or less. These iron and silicon need to be alloyed with aluminum and do not exist as impurities in aluminum.
そして、正極集電材の引張り強度としては、１５０Ｎ／ｍｍ２以上が必要であり、好ましくは１８０Ｎ／ｍｍ２以上である。また、本発明において用いる正極集電材は、伸びが２％以上であることが必要であり、好ましくは３％以上である。これは、電極積層体単位体積当たりの放電容量が大きくなるにつれて電極合剤層の充電時の膨張が大きくなるため、その膨張によって正極集電材に応力が発生し、それによって、正極集電材に亀裂や切断などが発生しやすくなるが、正極集電材の伸びを大きくしておくと、その伸びによって応力を緩和し、正極集電材の亀裂や切断などを防止できるようになるからである。 And as tensile strength of a positive electrode current collector, 150 N / mm < 2 > or more is required, Preferably it is 180 N / mm < 2 > or more. Further, the positive electrode current collector used in the present invention needs to have an elongation of 2% or more, preferably 3% or more. This is because, as the discharge capacity per unit volume of the electrode laminate increases, the expansion of the electrode mixture layer during charging increases, and this expansion causes stress in the positive electrode current collector, thereby cracking the positive electrode current collector. This is because, if the elongation of the positive electrode current collector is increased, the stress is relieved by the elongation, and cracking or cutting of the positive electrode current collector can be prevented.
本発明においては、上記のように、正極集電材として厚みが１５μｍ以下のアルミニウムを主成分とする金属箔を用いるが、この正極集電材の厚みが１５μｍ以下であることを必要としているのは、厚みが１５μｍより厚くなると、そのぶん、正極活物質を減らさなければならず、その結果、電池の容量が低下するからであり、厚みが薄いほど電池の高容量化には好都合であるが、あまりにも薄くなりすぎると、製造時に正極集電材の強度不足による切断などが生じるおそれがあるため、正極集電材の厚みとしては、上記のように１５μｍ以下であって５μｍ以上、特に８μｍ以上が実用上適している。 In the present invention, as described above, a metal foil mainly composed of aluminum having a thickness of 15 μm or less is used as the positive electrode current collector, but the positive electrode current collector needs to have a thickness of 15 μm or less. If the thickness is greater than 15 μm, the positive electrode active material must be reduced, and as a result, the capacity of the battery is reduced. The thinner the thickness, the better the capacity of the battery, but too much. If the thickness of the positive electrode current collector is too thin, cutting due to insufficient strength of the positive electrode current collector may occur at the time of manufacture. Therefore, the thickness of the positive electrode current collector is 15 μm or less as described above, and 5 μm or more, particularly 8 μm or more is practical. Is suitable.
本発明において、電極積層体体積とは、正極、負極およびセパレータを積層したものまたは正極、負極およびセパレータを巻回したものの電池内における嵩体積であって、後者のように巻回したものにあっては、巻回に際して使用した巻き軸に基づく巻回体中心部の透孔などは体積として含まない。要は正極、負極、セパレータが占める嵩体積を合計したものである。これら正極、負極、セパレータの３つの体積は電池の容量を決定する重要な因子であり、電池の大きさに拘わらず、電極積層体の単位体積当たりの放電容量（放電容量／電極積層体体積）を計算することによって、電池の容量密度を比較することができる。また、ここでいう放電容量とは、その電池の標準使用条件で充放電させた場合の放電容量である。本発明においては、電極積層体単位体積当たりの放電容量が１４０ｍＡｈ／ｃｍ３以上の非水二次電池を対象としており、高容量化という観点からは、電極積層体単位体積当たりの放電容量が１５０ｍＡｈ／ｃｍ３以上であることが好ましい。 In the present invention, the volume of the electrode laminate is the volume of the positive electrode, the negative electrode and the separator laminated or the positive electrode, the negative electrode and the separator wound in the battery, and the volume wound like the latter. Thus, the through hole in the center of the wound body based on the winding shaft used for winding is not included as a volume. In short, the total volume occupied by the positive electrode, the negative electrode, and the separator. These three volumes of the positive electrode, the negative electrode, and the separator are important factors that determine the capacity of the battery, and the discharge capacity per unit volume of the electrode stack (discharge capacity / electrode stack volume) regardless of the size of the battery. Can be compared to compare the capacity densities of the batteries. The discharge capacity here is the discharge capacity when charging and discharging under the standard use conditions of the battery. In the present invention, a non-aqueous secondary battery having a discharge capacity per unit volume of electrode stack of 140 mAh / cm 3 or more is targeted. From the viewpoint of increasing the capacity, the discharge capacity per unit volume of electrode stack is 150 mAh. / Cm 3 or more is preferable.
また、正極集電材の表面は片面が粗面化していることが好ましい。そして、粗な面が巻回体、すなわち、正極、負極およびセパレータを巻回した巻回構造の電極積層体の外側にあることが好ましい。これは、上記巻回体の場合、外側の面が巻回中心部ほど対向する負極が多く存在しているので正極が劣化しやすいため、外側に粗な面を用いて接着性を高めることにより電極の劣化を低減できるからである。粗な面の好ましい平均粗度はＲａで０．１〜０．５μｍであり、より好ましくは０．２〜０．３μｍである。そして、光沢面の好ましい平均粗度はＲａで０．２μｍ以下で、より好ましくは０．１μｍ以下である。 Moreover, it is preferable that the surface of the positive electrode current collector is roughened on one side. And it is preferable that a rough surface exists in the outer side of a wound body, ie, the electrode laminated body of the winding structure which wound the positive electrode, the negative electrode, and the separator. This is because, in the case of the above wound body, since the negative electrode is more likely to be deteriorated because the outer surface is opposed to the winding center portion, the positive electrode is likely to be deteriorated. This is because electrode deterioration can be reduced. The preferable average roughness of the rough surface is 0.1 to 0.5 μm in Ra, and more preferably 0.2 to 0.3 μm. And the preferable average roughness of a glossy surface is Ra of 0.2 micrometer or less, More preferably, it is 0.1 micrometer or less.
また、正極集電材の濡れ性が悪い場合、電池をサイクルさせた場合にサイクルの劣化が生じやすい傾向にある。そのような場合は濡れ性が３７ｄｙｎｅ／ｃｍ以上であることが好ましい。 Moreover, when the wettability of the positive electrode current collector is poor, the cycle tends to deteriorate when the battery is cycled. In such a case, the wettability is preferably 37 dyne / cm or more.
本発明において、正極活物質としては、例えば、ＬｉＣｏＯ2などのリチウムコバルト酸化物、ＬｉＭｎ2Ｏ4などのリチウムマンガン酸化物、ＬｉＮｉＯ2などのリチウムニッケル酸化物、二酸化マンガン、五酸化バナジウム、クロム酸化物などの金属酸化物または二硫化チタン、二硫化モリブデンなどの金属硫化物が用いられ、特にＬｉＮｉＯ2、ＬｉＣｏＯ2、ＬｉＭｎ2Ｏ4などの充電時の開路電圧がＬｉ基準で４Ｖ以上を示すリチウム複合酸化物を正極活物質として用いる場合には、高エネルギー密度で高容量が得られるので好ましい。とりわけ、ＬｉＮｉＯ2は最も高容量が得られるので特に好ましい。 In the present invention, as the positive electrode active material, for example, lithium cobalt oxide such as LiCoO 2 , lithium manganese oxide such as LiMn 2 O 4 , lithium nickel oxide such as LiNiO 2 , manganese dioxide, vanadium pentoxide, chromium oxide Lithium oxide, or metal sulfides such as titanium disulfide and molybdenum disulfide are used, and in particular, LiNiO 2 , LiCoO 2 , LiMn 2 O 4, etc. have an open circuit voltage of 4 V or more on the basis of Li. When a composite oxide is used as the positive electrode active material, it is preferable because a high capacity can be obtained at a high energy density. In particular, LiNiO 2 is particularly preferable because the highest capacity can be obtained.
正極は、例えば、上記正極活物質に、必要に応じて、鱗片状黒鉛などの導電助剤やポリフッ化ビニリデンなどのバインダを加え、混合して正極合剤を調製し、それを溶剤で分散させてペーストにし（バインダはあらかじめ溶剤に溶解させてから正極活物質などと混合してもよい）、その正極合剤ペーストを厚みが１５μｍ以下のアルミニウムを主成分とする金属箔からなる正極集電材に塗布し、乾燥して、正極集電材の少なくとも一方の面に正極合剤層を形成することによって作製される。ただし、正極の作製方法は、上記例示の方法に限られることなく、他の方法によってもよい。 For the positive electrode, for example, a conductive additive such as flaky graphite or a binder such as polyvinylidene fluoride is added to the positive electrode active material, if necessary, and mixed to prepare a positive electrode mixture, which is dispersed with a solvent. (The binder may be dissolved in a solvent in advance and then mixed with the positive electrode active material, etc.), and the positive electrode mixture paste is formed into a positive electrode current collector made of a metal foil whose main component is aluminum having a thickness of 15 μm or less. It is produced by applying and drying to form a positive electrode mixture layer on at least one surface of the positive electrode current collector. However, the method for manufacturing the positive electrode is not limited to the above-described method, and other methods may be used.
本発明において、負極活物質としては、リチウムイオンをドープ、脱ドープできるものであればよく、そのような負極活物質の具体例としては、例えば、黒鉛、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物焼成体、メソカーボンマイクロビーズ、炭素繊維、活性炭などの炭素材料が挙げられるが、特に２０００℃以上で焼成した炭素材料は、充放電に伴う体積変化が大きく本発明の効果を発現しやすい。また、Ｓｉ、Ｓｎ、Ｉｎなどの合金あるいはＬｉに近い低電圧で充放電できる酸化物などの化合物なども負極活物質として用いることができる。 In the present invention, the negative electrode active material may be any material that can be doped and dedoped with lithium ions. Specific examples of such a negative electrode active material include, for example, graphite, pyrolytic carbons, cokes, and glass. Carbon materials such as carbons, organic polymer compound fired bodies, mesocarbon microbeads, carbon fibers, activated carbon and the like can be mentioned. Particularly, carbon materials fired at 2000 ° C. or more have a large volume change due to charge / discharge. It is easy to produce an effect. Further, an alloy such as Si, Sn, or In or a compound such as an oxide that can be charged and discharged at a low voltage close to Li can be used as the negative electrode active material.
負極活物質として炭素材料を用いる場合、該炭素材料は下記の特性を持つものが好ましい。すなわち、そのＸ線回折での（００２）面の層間距離ｄ002に関しては、３．５Å以下が好ましく、より好ましくは３．４５Å以下、さらに好ましくは３．４Å以下である。また、ｃ軸方向の結晶子の大きさＬｃは３０Å以上が好ましく、より好ましくは８０Å以上、さらに好ましくは２５０Å以上である。そして、上記炭素材料の平均粒径は８〜１５μｍ、特に１０〜１３μｍが好ましく、純度は９９．９％以上が好ましい。 When a carbon material is used as the negative electrode active material, the carbon material preferably has the following characteristics. That is, for the interlayer distance d 002 of (002) plane in the X-ray diffraction, is preferably from 3.5 Å, more preferably 3.45Å or less, more preferably not more than 3.4 Å. Further, the crystallite size Lc in the c-axis direction is preferably 30 mm or more, more preferably 80 mm or more, and further preferably 250 mm or more. And the average particle diameter of the said carbon material is 8-15 micrometers, especially 10-13 micrometers is preferable, and purity is 99.9% or more.
負極は、例えば、上記負極活物質に、必要に応じ、正極の場合と同様の導電助剤やバインダなどを加え、混合して負極合剤を調製し、それを溶剤に分散させてペーストにし（バインダはあらかじめ溶剤に溶解させておいてから負極活物質などと混合してもよい）、その負極合剤ペーストを銅箔などからなる集電材に塗布し、乾燥して、集電材の少なくとも一方の面に負極合剤層を形成することによって作製される。ただし、負極の作製方法は上記例示の方法に限られることなく、他の方法によってもよい。 For example, the negative electrode active material may be added to the negative electrode active material, if necessary, as in the case of the positive electrode, and mixed to prepare a negative electrode mixture, which is then dispersed in a solvent to form a paste ( The binder may be dissolved in a solvent in advance and then mixed with the negative electrode active material, etc.), and the negative electrode mixture paste is applied to a current collector made of copper foil and dried, and then dried, at least one of the current collectors It is produced by forming a negative electrode mixture layer on the surface. However, the manufacturing method of the negative electrode is not limited to the above-described method, and other methods may be used.
上記負極集電材としては、例えば、銅箔、アルミニウム箔、ニッケル箔、ステンレス鋼箔などの金属箔や、それらの金属を網状にしたものなどが用いられるが、特に銅箔が適している。 Examples of the negative electrode current collector include metal foils such as copper foil, aluminum foil, nickel foil, and stainless steel foil, and those made of these metals in a net shape. Copper foil is particularly suitable.
本発明において、電解質としては、通常、有機溶媒などの非水溶媒にリチウム塩などの溶質を溶解させることによって調製した非水溶媒系の液状電解質が用いられる。その液状電解質の溶媒成分としては鎖状エステルが粘度が低くリチウムイオンが移動しやすいことから、よく用いられる。特によく用いられる鎖状エステルは、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、プロピオン酸メチルなどの鎖状のＣＯＯ−結合を有する有機溶媒である。 In the present invention, as the electrolyte, a nonaqueous solvent-based liquid electrolyte prepared by dissolving a solute such as a lithium salt in a nonaqueous solvent such as an organic solvent is usually used. As a solvent component of the liquid electrolyte, a chain ester is often used because of its low viscosity and easy movement of lithium ions. Particularly used chain esters are organic solvents having a chain-like COO-bond such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and methyl propionate.
また、上記鎖状エステルに下記の誘電率が高いエステル（誘電率３０以上）を混合して用いると、高伝導度や優れた電池特性が得られるので、特に好ましい。そのような誘電率が高いエステルとしては、例えば、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ブチレンカーボネート（ＢＣ）、ガンマーブチロラクトン（γ−ＢＬ）、エチレングリコールサルファイト（ＥＧＳ）などが挙げられる。特に環状構造のものが好ましく、エチレンカーボネート（ＥＣ）が最も好ましい。 In addition, it is particularly preferable to use an ester having the following high dielectric constant (dielectric constant of 30 or more) in combination with the chain ester because high conductivity and excellent battery characteristics can be obtained. Examples of such an ester having a high dielectric constant include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), gamma-butyrolactone (γ-BL), ethylene glycol sulfite (EGS), and the like. . A ring structure is particularly preferable, and ethylene carbonate (EC) is most preferable.
上記誘電率の高いエステルの電解質の全溶媒中で占める量としては、上記エステルが多くなりすぎると粘度が高くなり、リチウムイオンの移動が妨げられるおそれがあるので、４０体積％未満が好ましく、より好ましくは３０体積％以下、さらに好ましくは２５体積％以下である。そして、これら誘電率の高いエステルによる電池特性などの向上は、上記エステルが電解質の全溶媒中で１０体積％以上になると顕著になり、２０体積％に達するとさらに向上が見られるようになる。 The amount of the electrolyte having a high dielectric constant in the total solvent is preferably less than 40% by volume, because if the amount of the ester is excessive, the viscosity increases and the migration of lithium ions may be hindered. Preferably it is 30 volume% or less, More preferably, it is 25 volume% or less. The improvement in battery characteristics and the like due to the ester having a high dielectric constant becomes remarkable when the ester becomes 10% by volume or more in the total solvent of the electrolyte, and further improvement is seen when the ester reaches 20% by volume.
上記エステル以外に併用可能な溶媒としては、例えば、１，２−ジメトキシエタン（ＤＭＥ）、１，３−ジオキソラン（ＤＯ）、テトラヒドロフラン（ＴＨＦ）、２−メチル−テトラヒドロフラン（２Ｍｅ−ＴＨＦ）、ジエチルエーテル（ＤＥＥ）などが挙げられる。そのほか、アミン系またはイミド系有機溶媒や、含イオウ系または含フッ素系有機溶媒なども用いることができる。 Examples of solvents that can be used in addition to the ester include 1,2-dimethoxyethane (DME), 1,3-dioxolane (DO), tetrahydrofuran (THF), 2-methyl-tetrahydrofuran (2Me-THF), and diethyl ether. (DEE). In addition, amine-based or imide-based organic solvents, sulfur-containing or fluorine-containing organic solvents, and the like can also be used.
電解質の溶質としては、例えば、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＣ4Ｆ9ＳＯ3、ＬｉＣＦ3ＣＯ2、Ｌｉ2Ｃ2Ｆ4（ＳＯ3）2、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＣnＦ2n+1ＳＯ3（ｎ≧２）、ＬｉＮ（ＲｆＯＳＯ2）2〔ここでＲｆはフルオロアルキル基〕などが単独でまたは２種以上混合して用いられる。特にＬｉＰＦ6や炭素数が２以上のフルオロアルキル基を有するリチウム塩などが好ましい。液状電解質中における溶質の濃度は、特に限定されるものではないが、濃度を１ｍｏｌ／ｌ以上の多めにすると安全性が良くなるので好ましく、１．２ｍｏｌ／ｌ以上がより好ましい。また、１．７ｍｏｌ／ｌより少ないと電気特性が良くなるので好ましく、１．５ｍｏｌ／ｌより少ないとより好ましい。
The solute of the electrolyte, for example, LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6,
セパレータとしては、特に限定されることはないが、例えば、厚みが２０μｍ以下の微孔性ポリエチレンフィルム、微孔性ポリプロピレンフィルム、微孔性エチレン−プロピレンコポリマーフィルムなどのポリオレフィン系セパレータは、薄くても充分な強度を有しているので、正極活物質や負極活物質などの充填量を高めることができるとともに、熱伝導性が改善され、電池内部の発熱に対しても放熱を促進するので、本発明において好適に使用される。特に電極積層体と電池ケースとの間にセパレータが介在する場合は電池内部の熱を放熱する効果が大きい。 The separator is not particularly limited. For example, a polyolefin-based separator such as a microporous polyethylene film having a thickness of 20 μm or less, a microporous polypropylene film, or a microporous ethylene-propylene copolymer film may be thin. Since it has sufficient strength, the filling amount of the positive electrode active material and the negative electrode active material can be increased, the thermal conductivity is improved, and heat dissipation is promoted against the heat generation inside the battery. It is preferably used in the invention. In particular, when a separator is interposed between the electrode laminate and the battery case, the effect of radiating the heat inside the battery is great.
つぎに、実施例をあげて本発明をより具体的に説明する。ただし、本発明はそれらの実施例のみに限定されるものではない。 Next, the present invention will be described more specifically with reference to examples. However, this invention is not limited only to those Examples.
実施例１
メチルエチルカーボネートとエチレンカーボネートとを体積比７５：２５で混合し、この混合溶媒にＬｉＰＦ6を１．４モル／リットル溶解させて、組成が１．４ｍｏｌ／ｌＬｉＰＦ6／ＥＣ：ＭＥＣ（２５：７５体積比）で示される液状電解質を調製した。
Example 1
Methyl ethyl carbonate and ethylene carbonate are mixed at a volume ratio of 75:25, LiPF 6 is dissolved in 1.4 mol / liter in this mixed solvent, and the composition is 1.4 mol / l LiPF 6 / EC: MEC (25:75 A liquid electrolyte represented by a volume ratio) was prepared.
上記液状電解質におけるＥＣはエチレンカーボネートの略称であり、ＭＥＣはメチルエチルカーボネートの略称である。従って、上記液状電解質を示す１．４ｍｏｌ／ｌＬｉＰＦ6／ＥＣ：ＭＥＣ（２５：７５体積比）は、メチルエチルカーボネート７５体積％とエチレンカーボネート２５体積％との混合溶媒にＬｉＰＦ6を１．４ｍｏｌ／ｌを溶解させたものであることを示している。 EC in the liquid electrolyte is an abbreviation for ethylene carbonate, and MEC is an abbreviation for methyl ethyl carbonate. Accordingly, 1.4 mol / l LiPF 6 / EC: MEC (25:75 volume ratio) indicating the above liquid electrolyte is obtained by adding 1.4 mol / liter of LiPF 6 to a mixed solvent of 75% by volume of methyl ethyl carbonate and 25% by volume of ethylene carbonate. 1 is dissolved.
上記とは別に、ＬｉＣｏＯ2に導電助剤として鱗片状黒鉛を重量比１００：４．９で加えて混合し、この混合物と、ポリフッ化ビニリデンをＮ−メチルピロリドンに溶解させた溶液とを混合してペースト状にした。このポリフッ化ビニリデンの量はＬｉＣｏＯ2に対して重量比で１００：３．８（ＬｉＣｏＯ2１００重量部に対してポリフッ化ビニリデン３．８重量部）であった。この正極合剤ペーストを７０メッシュの網を通過させて大きなものを取り除いた後、厚さ１５μｍのアルミニウムを主成分とする金属箔からなる正極集電材の両面に塗布量が２４．８ｍｇ／ｃｍ２（ただし、乾燥後の正極合剤重量）となるように均一に塗布して乾燥し、その後、ローラプレス機により圧縮成形した後、切断し、リード体を溶接して、帯状の正極を作製した。 Apart from the above, flaky graphite as a conductive additive is added to LiCoO 2 at a weight ratio of 100: 4.9 and mixed, and this mixture is mixed with a solution in which polyvinylidene fluoride is dissolved in N-methylpyrrolidone. To make a paste. The amount of polyvinylidene fluoride in a weight ratio to LiCoO 2 100: was 3.8 (polyvinylidene fluoride 3.8 parts by weight based on LiCoO 2 100 parts by weight). The positive electrode mixture paste was passed through a 70-mesh net to remove a large one, and then the coating amount was 24.8 mg / cm 2 on both surfaces of a positive electrode current collector made of a metal foil whose main component was aluminum having a thickness of 15 μm. (However, the weight of the positive electrode mixture after drying) was uniformly applied and dried, then compression-molded with a roller press, cut, and welded with the lead body to produce a strip-shaped positive electrode. .
上記正極集電材として用いたアルミニウムを主成分とする金属箔は、鉄を１％、シリコンを０．１５％含んでおり、純度は９８．８％であった。また、正極集電材として用いたアルミニウムを主成分とする金属箔の引っ張り強度は１８５Ｎ／ｍｍ２であり、粗面の平均粗度Ｒａは０．２μｍで、光沢面の平均粗度Ｒａは０．０４μｍであった。そして、上記正極集電材として用いたアルミニウムを主成分とする金属箔の濡れ性は３８ｄｙｎｅ／ｃｍで、伸びは３％であった。 The metal foil mainly composed of aluminum used as the positive electrode current collector contained 1% iron and 0.15% silicon, and the purity was 98.8%. Further, the tensile strength of the metal foil mainly composed of aluminum used as the positive electrode current collector is 185 N / mm 2 , the average roughness Ra of the rough surface is 0.2 μm, and the average roughness Ra of the glossy surface is 0. 0. It was 04 μm. The wettability of the metal foil mainly composed of aluminum used as the positive electrode current collector was 38 dyne / cm, and the elongation was 3%.
つぎに、黒鉛系炭素材料〔ただし、（００２）面の層間距離ｄ002＝３．３７Å、ｃ軸方向の結晶子の大きさＬｃ＝９５０Å、平均粒径１５μｍ、純度９９．９％以上という特性を持つ黒鉛化炭素材料〕を、ポリフッ化ビニリデンをＮ−メチルピロリドンに溶解させた溶液と混合してペースト状にした。このポリフッ化ビニリデンの量は黒鉛系炭素材料に対して重量比で９０：１０（黒鉛系炭素材料１００重量部に対してポリフッ化ビニリデン１１．１重量部）であった。この負極合剤ペーストを７０メッシュの網を通過させて大きなものを取り除いた後、厚さ１０μｍの帯状の銅箔からなる負極集電体の両面に１２．１ｍｇ／ｃｍ２（ただし、乾燥後の負極合剤重量）となるように均一に塗布して乾燥し、その後、ローラプレス機により圧縮成形し、切断した後、リード体を溶接して、帯状の負極を作製した。
Next, a graphitic carbon material [however, the (002) plane interlayer distance d 002 = 3.37 mm, c-axis direction crystallite size Lc = 950 mm,
前記帯状の正極を厚さ２０μｍの微孔性ポリエチレンフィルムを介して上記帯状の負極に重ね、渦巻状に巻回して渦巻状巻回構造の電極積層体とした。この電極積層体の体積は１０．８６ｃｍ３であった。その後、この電極積層体を外径１８ｍｍの有底円筒状の電池ケース内に充填し、正極および負極のリード体の溶接を行った。 The belt-like positive electrode was overlapped on the belt-like negative electrode through a microporous polyethylene film having a thickness of 20 μm and wound in a spiral shape to obtain an electrode laminate having a spiral winding structure. The volume of this electrode laminate was 10.86 cm 3 . Thereafter, the electrode laminate was filled in a bottomed cylindrical battery case having an outer diameter of 18 mm, and the positive and negative lead bodies were welded.
つぎに、上記液状電解質を電池ケース内に注入し、液状電解質がセパレータなどに充分に浸透した後、封口し、予備充電、エイジングを行い、図１の模式図に示すような構造の筒形の非水二次電池を作製した。 Next, the liquid electrolyte is poured into the battery case, and after the liquid electrolyte has sufficiently permeated the separator and the like, the liquid electrolyte is sealed, precharged, and subjected to aging, and has a cylindrical shape as shown in the schematic diagram of FIG. A non-aqueous secondary battery was produced.
図１に示す電池について説明すると、１は前記の正極で、２は前記の負極である。ただし、図１では、繁雑化を避けるため、正極１や負極２の作製にあたって使用された集電材などは図示していない。そして、これらの正極１と負極２はセパレータ３を介して渦巻状に巻回され、渦巻状巻回構造の電極積層体として上記の液状電解質４と共に電池ケース５内に収容されている。
Referring to the battery shown in FIG. 1, 1 is the positive electrode and 2 is the negative electrode. However, in FIG. 1, in order to avoid complication, the current collecting material used in manufacturing the
電池ケース５は前記のようにステンレス鋼製で、その底部には上記渦巻状巻回構造の電極積層体の挿入に先立って、ポリプロピレンからなる絶縁体６が配置されている。封口板７はアルミニウム製で、円板状をしていて、中央部に薄肉部７ａを厚み方向の両端面より内部側に設け、かつ上記薄肉部７ａの周囲に電池内圧を防爆弁９に作用させるための圧力導入口７ｂとしての孔が設けられている。そして、この薄肉部７ａの上面に防爆弁９の突出部９ａが溶接され、溶接部分１１を構成している。なお、上記の封口板７に設けた薄肉部７ａや防爆弁９の突出部９ａなどは、図面上での理解がしやすいように、切断面のみを図示しており、切断面後方の輪郭線は図示を省略している。また、封口板７の薄肉部７ａと防爆弁９の突出部９ａとの溶接部分１１も、図面上での理解が容易なように、実際よりは誇張した状態に図示している。
The
端子板８は、圧延鋼製で表面にニッケルメッキが施され、周縁部が鍔状になった帽子状をしており、この端子板８にはガス排出孔８ａが設けられている。防爆弁９は、アルミニウム製で、円板状をしており、その中央部には発電要素側（図１では、下側）に先端部を有する突出部９ａが設けられ、かつ薄肉部９ｂが設けられ、上記突出部９ａの下面が、前記したように、封口板７の薄肉部７ａの上面に溶接され、溶接部分１１を構成している。絶縁パッキング１０は、ポリプロピレン製で、環状をしており、封口板７の周縁部の上部に配置され、その上部に防爆弁９が配置していて、封口板７と防爆弁９とを絶縁するとともに、両者の間から液状電解質が漏れないように両者の間隙を封止している。環状ガスケット１２はポリプロピレン製で、リード体１３はアルミニウム製で、前記封口板７と正極１とを接続し、渦巻状巻回構造の電極積層体の上部には絶縁体１４が配置され、負極２と電池ケース５の底部とはニッケル製のリード体１５で接続されている。
The terminal board 8 is made of rolled steel, has a nickel plating on the surface, and has a hat shape with a peripheral edge portion, and the terminal board 8 is provided with a
実施例２
正極合剤の塗布量を２３．９ｍｇ／ｃｍ２（ただし、乾燥後の正極合剤層量）とし、負極合剤の塗布量を１１．６ｍｇ／ｃｍ２（ただし、乾燥後の負極合剤層量）とし、セパレータとして従来と同様の厚さ２５μｍの微孔性ポリエチレンフィルムを用いた以外は、実施例１と同様に非水二次電池を作製した。
Example 2
The coating amount of the positive electrode mixture is 23.9 mg / cm 2 (however, the positive electrode mixture layer amount after drying), and the coating amount of the negative electrode mixture is 11.6 mg / cm 2 (however, the negative electrode mixture layer after drying) A non-aqueous secondary battery was produced in the same manner as in Example 1 except that a microporous polyethylene film having a thickness of 25 μm as in the past was used as a separator.
比較例１
正極集電材として厚みが２０μｍ（従来の正極集電材と同じ厚み）のアルミニウムを主成分とする金属箔を用いた。このアルミニウムを主成分とする金属箔は、鉄を０．０３％、シリコンを０．０２％含んでおり、純度は９９．９４％であった。また、上記正極集電材としてのアルミニウムを主成分とする金属箔の引っ張り強度は１４０Ｎ／ｍｍ２（１５μｍ換算値）であり、両面光沢面であって、その平均粗度Ｒａは０．０４μｍであった。そして、濡れ性は３６ｄｙｎｅ／ｃｍで、伸びは３％であった。
Comparative Example 1
As the positive electrode current collector, a metal foil mainly composed of aluminum having a thickness of 20 μm (the same thickness as a conventional positive electrode current collector) was used. This aluminum-based metal foil contained 0.03% iron and 0.02% silicon, and the purity was 99.94%. Further, the tensile strength of the metal foil mainly composed of aluminum as the positive electrode current collector is 140 N / mm 2 (15 μm equivalent value), is a double-sided glossy surface, and the average roughness Ra is 0.04 μm. It was. The wettability was 36 dyne / cm and the elongation was 3%.
上記正極集電材に実施例１と同様の正極合剤ペーストを２３．９ｍｇ／ｃｍ２（ただし、乾燥後の正極合剤重量）となるように均一に塗布して乾燥し、その後、ローラプレス機により圧縮成形し、切断し、リード体を溶接して、帯状の正極を作製した。また、負極は、負極合剤の塗布量を１１．１８ｍｇ／ｃｍ２（ただし、乾燥後の負極合剤重量）とした以外は、実施例２と同様に作製し、それらの正極と負極を用いた以外は、実施例２と同様に筒形の非水二次電池を作製した。 A positive electrode mixture paste similar to that of Example 1 was uniformly applied to the positive electrode current collector so as to be 23.9 mg / cm 2 (however, the positive electrode mixture weight after drying) and dried, and then a roller press machine Compression-molding, cutting, and welding the lead body to produce a strip-like positive electrode. The negative electrode was prepared in the same manner as in Example 2 except that the coating amount of the negative electrode mixture was 11.18 mg / cm 2 (however, the negative electrode mixture weight after drying), and the positive electrode and the negative electrode were used. A cylindrical nonaqueous secondary battery was produced in the same manner as in Example 2 except that.
上記実施例１〜２および比較例１の電池を、１６００ｍＡ（１Ｃ）で２．７５Ｖまで放電した後１６００ｍＡで充電し、４．２Ｖに達した後は４．２Ｖの定電圧に保つ条件で２時間半の充電を行った。その後、電池を１６００ｍＡで２．７５Ｖまで放電し、その充放電を繰り返し、その５０サイクルでの１サイクル目に対する容量保持率を求めた。その結果を表１に示す。 The batteries of Examples 1 and 2 and Comparative Example 1 were discharged at 1600 mA (1 C) to 2.75 V, then charged at 1600 mA, and after reaching 4.2 V, 2 was maintained under a constant voltage of 4.2 V. Charged for half an hour. Thereafter, the battery was discharged at 1600 mA to 2.75 V, the charge and discharge were repeated, and the capacity retention rate for the first cycle in 50 cycles was obtained. The results are shown in Table 1.
表１に示すように、比較例１の電池では、５０サイクル後の容量保持率が８０％近くまで低下したのに対して、実施例１〜２の電池は、９５％以上の容量保持率を有していて、サイクル特性が良好であった。また、実施例１〜２の電池は、電極積層体単位体積当たりの放電容量が１４７ｍＡｈ／ｃｍ３以上と高容量であり、特にセパレータを薄くして正極合剤や負極合剤の量を多くした実施例１の電池は放電容量が大きかった。 As shown in Table 1, in the battery of Comparative Example 1, the capacity retention after 50 cycles decreased to nearly 80%, whereas the batteries of Examples 1 and 2 had a capacity retention of 95% or more. And had good cycle characteristics. In addition, the batteries of Examples 1 and 2 have a high discharge capacity of 147 mAh / cm 3 or more per unit volume of the electrode laminate, and in particular, the separator was thinned to increase the amount of the positive electrode mixture and the negative electrode mixture. The battery of Example 1 had a large discharge capacity.
１ 正極
２ 負極
３ セパレータ
４ 電解質
1
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