JP2008218248A - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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JP2008218248A
JP2008218248A JP2007054997A JP2007054997A JP2008218248A JP 2008218248 A JP2008218248 A JP 2008218248A JP 2007054997 A JP2007054997 A JP 2007054997A JP 2007054997 A JP2007054997 A JP 2007054997A JP 2008218248 A JP2008218248 A JP 2008218248A
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negative electrode
secondary battery
lithium secondary
electrode mixture
density
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JP5097415B2 (en
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Naotaka Kimura
尚貴 木村
Masanori Yoshikawa
正則 吉川
Yoshimi Yanai
吉美 矢内
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Resonac Corp
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Hitachi Powdered Metals Co Ltd
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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
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    • Y02E60/10—Energy storage using batteries
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium secondary battery applicable to a hybrid vehicle and the like, and capable of remarkably improving a load characteristic and input/output density. <P>SOLUTION: In this lithium secondary battery, a positive electrode capable of storing/releasing lithium, and a negative electrode capable of storing/releasing lithium are formed through an electrolyte. The lithium secondary battery is characterized in that a mix coating amount to both surfaces of a negative electrode collector of a negative electrode mix prepared by mixing a conductive agent, a negative electrode active material and a binder is 6-8 mg/cm<SP>2</SP>, and density of the negative electrode mix is 1.4-1.7 g/cm<SP>3</SP>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、リチウム二次電池に関するものである。   The present invention relates to a lithium secondary battery.

近年、ハイブリッド自動車等への適用のため、リチウム二次電池あるいはキャパシタなどの電源装置の開発が盛んである。ハイブリッド自動車のような車載用途に適用するには、これら電源装置の高入出力密度化が重要な課題である。このような自動車分野への適用にはこれら電源装置のより一層の高出力化が重要である。さらには、回生によるエネルギーの有効利用を図るには、優れた入力特性も要求される。   2. Description of the Related Art In recent years, power source devices such as lithium secondary batteries or capacitors have been actively developed for application to hybrid vehicles and the like. In order to apply to in-vehicle applications such as hybrid vehicles, it is an important issue to increase the input / output density of these power supply devices. For the application to the automobile field, it is important to further increase the output of these power supply devices. Furthermore, excellent input characteristics are also required to effectively use energy by regeneration.

また、ハイブリッド自動車において、電気だけでの都市部の走行が可能な、いわゆるデュアルモードの要望も近年出てきている。このような要求に対応するには、入出力特性だけではなく、より大電流で良好な負荷特性が電池の特性として要求される。一般的にパソコン，携帯電話などの民生用機器に使用される電池は高容量が要求されるが、ハイレート特性は要求されず、負荷特性として要求されるのは高々１／３時間率（３Ｃ）程度である。一方、自動車の分野においては１／２０程度の時間率（２０Ｃ）、つまり、民生用機器に適用される電池の約７倍の大電流が要求され、優れた高負荷特性が要求される。上述のようなことから、負荷特性，入出力特性を大幅に向上させる電池技術は、極めて重要な課題である。   In recent years, there has also been a demand for a so-called dual mode in which a hybrid vehicle can run in an urban area using only electricity. In order to meet such demands, not only input / output characteristics but also good load characteristics with a larger current are required as battery characteristics. Generally, batteries used for consumer devices such as personal computers and mobile phones are required to have high capacity, but high rate characteristics are not required, and load characteristics are required at most 1/3 hour rate (3C). Degree. On the other hand, in the field of automobiles, a time rate (20C) of about 1/20, that is, a large current about 7 times that of a battery applied to a consumer device is required, and an excellent high load characteristic is required. From the above, battery technology that greatly improves load characteristics and input / output characteristics is a very important issue.

特許文献１及び特許文献２には、負極合剤の塗工量や密度に関しての検討が行われている。   In Patent Document 1 and Patent Document 2, studies on the coating amount and density of the negative electrode mixture are performed.

また、特許文献３には、負極活物質として、炭素材料を用いることが開示されている。   Patent Document 3 discloses using a carbon material as the negative electrode active material.

特開２００２−２６０６５７号公報JP 2002-260657 A 特開２００５−２８５５８１号公報Japanese Patent Laid-Open No. 2005-285581 特開２００３−２０８９２２号公報JP 2003-208922 A

本発明は、入出力特性及び負荷特性を向上させたリチウム二次電池を提供することを目的とするものである。   An object of the present invention is to provide a lithium secondary battery with improved input / output characteristics and load characteristics.

本発明は、リチウムを吸蔵・放出可能な正極と、リチウムを吸蔵・放出可能な負極と、が電解質を介して形成されるリチウム二次電池において、正極と負極とが捲回されて電極捲回体を形成しており、負極合剤の負極集電体への両面合剤塗工量が６mg／cm2 以上８mg／cm2以下であり、負極合剤の密度１.４ｇ／cm3以上１.７ｇ／cm3 以下であることを特徴とするものである。 The present invention relates to a lithium secondary battery in which a positive electrode capable of inserting and extracting lithium and a negative electrode capable of inserting and extracting lithium are formed via an electrolyte. The coating amount of the negative electrode mixture on the negative electrode current collector is 6 mg / cm 2 or more and 8 mg / cm 2 or less, and the density of the negative electrode mixture is 1.4 g / cm 3 or more and 1 0.7 g / cm 3 or less.

また、本発明は、負極合剤の空隙率が２０％以上，３５％以下であることを特徴とする。   Further, the present invention is characterized in that the porosity of the negative electrode mixture is 20% or more and 35% or less.

本発明により、負荷特性及び入出力特性を向上させたリチウム二次電池を提供できる。   According to the present invention, a lithium secondary battery having improved load characteristics and input / output characteristics can be provided.

負極において、負極合剤の塗工量を低減させることにより、電極厚さが薄くなり、電池の内部抵抗が低下し、電池の負荷特性及び入出力特性の向上が期待できる。   In the negative electrode, by reducing the coating amount of the negative electrode mixture, the electrode thickness is reduced, the internal resistance of the battery is lowered, and the load characteristics and input / output characteristics of the battery can be expected to be improved.

しかし、粉砕分級作業等により微粒化し塗工することにより、塗工量を低減させる場合はコストが嵩む。さらに、微粒化による不可逆容量の増大も懸念され、電池容量が小さくなり、デュアルモードで要求されるエネルギーの確保，エネルギーの回生も難しくなる。   However, the cost increases when the amount of coating is reduced by pulverizing and coating by pulverization classification or the like. Furthermore, there is a concern about an increase in irreversible capacity due to atomization, the battery capacity is reduced, and it becomes difficult to secure energy and regenerate energy required in the dual mode.

一方、塗工量を多くすると、容量が上がる利点があるが、電極が厚くなり抵抗が上昇し、十分な入出力特性及び負荷特性が得られない。   On the other hand, increasing the coating amount has the advantage of increasing the capacity, but the electrode becomes thick and the resistance increases, and sufficient input / output characteristics and load characteristics cannot be obtained.

また、塗工量を低減させ電極を薄くすることによる容量の低下は負極合剤の高密度化により抑制する事が可能である。しかし、負極合剤の高密度化に際しては、負極合剤中の電解液との反応界面の確保を考慮しなければならない。負極合剤を高密度にすると、負極合剤における空隙率が低くなり、電極が保持できる電解液量が少なくなり、電解液と負極活物質表面とで形成される電極反応界面で起きる電極反応が阻害される。このような電極反応への悪影響が生じると、入出力が低下し、自動車分野で必要とされる入出力を確保できなくなる。一方、電極密度を低くし空隙率を高くすると、電極が保持できる電解液量が多くなり、電解液と負極活物質表面とで形成される電極反応界面で起きる電極反応は阻害されないが、空隙が多いため電極合剤内の電子伝導性が悪くなり、２０Ｃ程度のハイレート放電時の容量が低下する。   Moreover, the capacity | capacitance fall by reducing the coating amount and making an electrode thin can be suppressed by densification of the negative mix. However, when increasing the density of the negative electrode mixture, it is necessary to consider securing a reaction interface with the electrolyte in the negative electrode mixture. When the density of the negative electrode mixture is increased, the porosity in the negative electrode mixture is reduced, the amount of electrolyte solution that can be held by the electrode is reduced, and the electrode reaction that occurs at the electrode reaction interface formed between the electrolyte solution and the surface of the negative electrode active material is reduced. Be inhibited. When such an adverse effect on the electrode reaction occurs, the input / output is lowered, and the input / output required in the automobile field cannot be secured. On the other hand, when the electrode density is decreased and the porosity is increased, the amount of the electrolyte solution that can be held by the electrode increases, and the electrode reaction that occurs at the electrode reaction interface formed between the electrolyte solution and the negative electrode active material surface is not hindered. Since there are many, the electronic conductivity in an electrode mixture will worsen, and the capacity | capacitance at the time of the high-rate discharge of about 20C will fall.

以上述べたように、反応界面の確保が可能な高密度の電極構造が技術のポイントであり、塗工量，負極合剤の密度及び空隙率を好適な範囲とすることにより、容量減少を抑え、高入出力，高負荷特性なリチウムイオン二次電池を提供することができる。   As described above, a high-density electrode structure capable of securing a reaction interface is a technical point, and by reducing the coating amount, the density of the negative electrode mixture, and the porosity, the capacity reduction can be suppressed. A lithium ion secondary battery with high input / output and high load characteristics can be provided.

本発明では、種々検討した結果、負極合剤の塗工量を６mg／cm2以上８mg／cm2以下の範囲とし、負極合剤の密度１.４ｇ／cm3以上１.７ｇ／cm3以下の範囲とすることにより、負荷特性及び入出力特性の向上が達成できることが判った。また、塗工量を６mg／cm2 以上７.４mg／cm2以下の範囲にすることがより好ましいことが判った。 In the present invention, as a result of various studies, the coating amount of the negative electrode mixture is set in the range of 6 mg / cm 2 to 8 mg / cm 2 , and the density of the negative electrode mixture is 1.4 g / cm 3 to 1.7 g / cm 3. It was found that the load characteristics and the input / output characteristics can be improved by setting the above range. Further, it has been found preferable to a coating amount of 6 mg / cm 2 or more 7.4 mg / cm 2 or less.

本発明のリチウム二次電池の正極活物質にはリチウム遷移金属複合酸化物を用いることができる。ニッケル酸リチウム，コバルト酸リチウムなどの正極活物質のＮｉ，Ｃｏなどの一部を１種あるいはそれ以上の遷移金属で置換して用いることができる。   A lithium transition metal composite oxide can be used for the positive electrode active material of the lithium secondary battery of the present invention. A part of a positive electrode active material such as lithium nickelate or lithium cobaltate, such as Ni or Co, can be substituted with one or more transition metals.

負極活物質としては、炭素材料を用いる。その中でも天然黒鉛，人造黒鉛などの黒鉛を用いることが好ましい。また黒鉛は、結晶格子の面間隔を表すｄ002が３.３５６Å以下であり、結晶子サイズを表すＬｃ(002)が１０００Å以上、Ｌａ(110)が１０００Å以上のものが好ましい。Ｘ線回折により測定した本発明の黒鉛材料の(００２)面の面間隔ｄ002 は、特に制限されないが、通常３.３５６Å 以下の範囲である。この範囲を上回る場合、即ち、結晶性が劣る場合には、電極を製造したときに活物質の単位重量当たりの放電容量が小さくなる。一方、この面間隔ｄ002 の下限は、理論的限界として通常３.３５４Å である。また、Ｘ線回折により測定した本発明の黒鉛材料のｃ軸方向の結晶子の大きさＬｃ及びａ軸方向の結晶子の大きさＬａは、それぞれ特に制限されないが、通常、１０００Å以上の範囲である。この範囲を下回ると、これを用いて電極を製造した場合に、活物質重量当たりの放電容量が小さくなるためである。また、Ｘ線回折により測定した面間隔ｄ002 、結晶子の大きさＬｃ及びＬａとしては、炭素材料学会の学振法に従って測定される値を用いることができる。なお、学振法においては１００ｎｍ（１０００Å）以上の値は区別されず、全て「＞１０００（Å）」と記述される。 A carbon material is used as the negative electrode active material. Of these, graphite such as natural graphite and artificial graphite is preferably used. The graphite preferably has a d 002 representing a crystal lattice spacing of 3.356 mm or less, a Lc (002) representing a crystallite size of 1000 mm or more, and a La (110) of 1000 mm or more. Plane spacing d 002 of (002) plane of the graphite material of the present invention measured by X-ray diffraction is not particularly limited, in the range of usually less than 3.356A. When exceeding this range, that is, when the crystallinity is inferior, the discharge capacity per unit weight of the active material becomes small when the electrode is manufactured. On the other hand, the lower limit of the surface spacing d 002 is usually 3.354Å as a theoretical limit. Further, the crystallite size Lc in the c-axis direction and the crystallite size La in the a-axis direction of the graphite material of the present invention measured by X-ray diffraction are not particularly limited, but are usually in the range of 1000 mm or more. is there. This is because if the thickness is less than this range, the discharge capacity per weight of the active material becomes small when an electrode is produced using this. In addition, as the interplanar spacing d 002 and crystallite sizes Lc and La measured by X-ray diffraction, values measured in accordance with the Japan Society for Carbon Materials Science and Technology can be used. In the Gakushin method, values of 100 nm (1000 Å) or more are not distinguished and are all described as “> 1000 (Å)”.

また、負極合剤の（００４）／（１００）の積分強度比が２１〜３２のものを用いることが好ましい。   Moreover, it is preferable to use a negative electrode mixture having an integrated intensity ratio of (004) / (100) of 21 to 32.

なお、この（００４）／（１００）の積分強度比とは、負極合剤のＸ線回折測定により得られる（１１０）面及び（００４）面に帰属されるピーク強度を比較することにより得られる。即ち、（１１０）面に帰属されるピーク強度に対する（００４）面に帰属されるピーク強度比を示す。   The integrated intensity ratio of (004) / (100) is obtained by comparing the peak intensity attributed to the (110) plane and (004) plane obtained by X-ray diffraction measurement of the negative electrode mixture. . That is, the ratio of the peak intensity attributed to the (004) plane to the peak intensity attributed to the (110) plane is shown.

正極合剤，負極合剤には、一般的に活物質のほかに結着剤，導電剤等が含まれているが、これらの種類や量によって、発明の効果はなんら損なわれない。   The positive electrode mixture and the negative electrode mixture generally contain a binder, a conductive agent, and the like in addition to the active material, but the effects of the invention are not impaired by these types and amounts.

電解質としては、例えば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，ジメチルカーボネート，エチルメチルカーボネート，ジエチルカーボネート、γ−ブチロラクトン，γ−バレロラクトン，メチルアセテート，エチルアセテート，メチルプロピオネート，テトラヒドロフラン，２−メチルテトラヒドロフラン，１，２−ジメトキシエタン，１−エトキシ−２−メトキシエタン，３−メチルテトラヒドロフラン，１，２−ジオキサン，１，３−ジオキサン，１，４−ジオキサン，１，３−ジオキソラン，２−メチル−１，３−ジオキソラン，４−メチル−１，３−ジオキソラン等より少なくとも１種以上選ばれた非水溶媒に、例えば、ＬｉＰＦ6，ＬｉＢＦ4，ＬｉＣｌＯ4，
ＬｉＮ(Ｃ2Ｆ5ＳＯ2)2等より少なくとも１種以上選ばれたリチウム塩を溶解させた有機電解液あるいはリチウムイオンの伝導性を有する固体電解質あるいはゲル状電解質あるいは溶融塩など一般に炭素系材料などを負極活物質として用いた電池で使用される既知の電解質を用いることができる。また、電池の構成上の必要性に応じて微孔性セパレータを用いても本発明の効果はなんら損なわれない。 Examples of the electrolyte include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, γ-valerolactone, methyl acetate, ethyl acetate, methyl propionate, tetrahydrofuran, and 2-methyltetrahydrofuran. , 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 3-methyltetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, 2-methyl- Non-aqueous solvents selected from at least one selected from 1,3-dioxolane, 4-methyl-1,3-dioxolane, etc. include, for example, LiPF 6 , LiBF 4 , LiClO 4 ,
Generally, a carbon-based material such as an organic electrolytic solution in which at least one lithium salt selected from LiN (C 2 F 5 SO 2 ) 2 or the like is dissolved, a solid electrolyte having lithium ion conductivity, a gel electrolyte, or a molten salt A known electrolyte used in a battery using the above as a negative electrode active material can be used. Moreover, even if a microporous separator is used according to the structural requirements of the battery, the effect of the present invention is not impaired at all.

以下に実施例を挙げ、本発明を説明する。なお、本発明は以下に述べる実施例に限定されるものではない。   The following examples illustrate the invention. In addition, this invention is not limited to the Example described below.

（実施例１）
まず、正極を作製した。正極活物質としてＬｉ(ＮｉＭｎＣｏ)1/3Ｏ2、導電剤として黒鉛、結着剤としてポリフッ化ビニリデンを８５：１０：５の重量比で混練機を用い、３０分間混練し正極合剤を得た。正極合剤を厚さ２０μｍのアルミニウム箔に両面塗工した。 (Example 1)
First, a positive electrode was produced. A positive electrode mixture is obtained by kneading Li (NiMnCo) 1/3 O 2 as a positive electrode active material, graphite as a conductive agent, and polyvinylidene fluoride as a binder in a weight ratio of 85: 10: 5 for 30 minutes using a kneader. It was. The positive electrode mixture was coated on both sides of an aluminum foil having a thickness of 20 μm.

次に、負極を作製した。負極活物質として天然黒鉛、導電剤として黒鉛、結着剤としてポリフッ化ビニリデンを用いて、負極活物質：導電剤：結着剤＝９０：５：５の重量比で正極と同様の作製方法で混練した。得られた負極合剤を厚さ１０μｍの銅箔に両面塗工した。   Next, a negative electrode was produced. Using natural graphite as the negative electrode active material, graphite as the conductive agent, and polyvinylidene fluoride as the binder, the negative electrode active material: conductive agent: binder = 90: 5: 5 weight ratio is the same as that of the positive electrode Kneaded. The obtained negative electrode mixture was coated on both sides of a copper foil having a thickness of 10 μm.

なお、天然黒鉛は、粒径が１０μｍ以上３０μｍ以下の範囲にある粒子を９５％以上含有しているものを用いた。なお、粒子の最大粒径は１００μｍであり、最小粒径は数μｍ程度である。   Note that natural graphite containing 95% or more of particles having a particle size in the range of 10 μm to 30 μm was used. The maximum particle size of the particles is 100 μm, and the minimum particle size is about several μm.

作製した正極及び負極は、プレス機を用いて１３〜１４ｔで圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤密度は１.４ｇ／cm3、負極集電体の両面合剤塗工量は６.０mg／cm2、空隙率は３３％、（００４）／(１００)の積分強度比は２１であった。 The produced positive electrode and negative electrode were roll-formed at 13 to 14 t using a press machine and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.4 g / cm 3 , the coating amount of the negative electrode current collector on both sides is 6.0 mg / cm 2 , the porosity is 33%, and the integrated strength ratio of (004) / (100) is 21 Met.

なお、負極合剤の密度及び空隙率の測定は以下の通り行った。   The density and porosity of the negative electrode mixture were measured as follows.

負極合剤の密度は、電極の重量から集電体である箔の重量を差し引いた重量と単位面積との商から求め、負極合剤の空隙率は、真密度を用いて算出した。   The density of the negative electrode mixture was determined from the quotient of the weight obtained by subtracting the weight of the foil as a current collector from the weight of the electrode and the unit area, and the porosity of the negative electrode mixture was calculated using the true density.

なお、真密度とは、活物質内の空孔を差し引いた場合、即ち空隙がないものとして算出した密度のことをいい、ピクノメーターを用いて算出した。   The true density means the density calculated when the voids in the active material are subtracted, that is, without voids, and was calculated using a pycnometer.

Figure 2008218248
Figure 2008218248

乾燥後、正極と負極とをセパレータを介して捲回し、電池缶に挿入した。負極集電リード片６はニッケルの負極集電リード部８に集めて超音波溶接し、集電リード部を缶底溶接した。一方、正極集電リード片５はアルミニウムの集電リード部７に超音波溶接した後、アルミニウムのリード部を蓋９に抵抗溶接した。電解液（１ＭＬｉＰＦ6 ／ＥＣ：ＥＭＣ＝１：３）を注入後、缶４のカシメにより蓋を封口し、電池を得た。なお、缶の上端と蓋の間にはガスケット１２を挿入した。このようにして７Ａｈ級の電池を製造した。作製したリチウム二次電池の概略図を図１に示す。 After drying, the positive electrode and the negative electrode were wound through a separator and inserted into a battery can. The negative electrode current collecting lead piece 6 was collected on the nickel negative electrode current collecting lead portion 8 and ultrasonically welded, and the current collecting lead portion was welded to the bottom of the can. On the other hand, the positive electrode current collector lead piece 5 was ultrasonically welded to the aluminum current collector lead portion 7 and then the aluminum lead portion was resistance welded to the lid 9. After injecting the electrolytic solution (1M LiPF 6 / EC: EMC = 1: 3), the lid was sealed with caulking of the can 4 to obtain a battery. A gasket 12 was inserted between the upper end of the can and the lid. In this way, a 7 Ah class battery was manufactured. A schematic view of the produced lithium secondary battery is shown in FIG.

＜電池性能試験＞
電池性能試験として、充電終止電圧４.１Ｖ，放電終止電圧２.７Ｖ，充放電レート１Ｃ（定格電気容量の１時間率）で充放電し、電池容量を求めた。また、ＳＯＣ（state of
charge）５０％の状態で、１Ｃ，３Ｃ，５Ｃ，１０Ｃ，２０Ｃの電流を１０秒間印加し、それぞれの電流値における１０秒目の電圧を測定し、入出力特性を調べた。電池の放電終止電圧（ＶD）と電流電圧特性の直線を放電終止電圧まで外挿したときの電流値（ＩD）を用いて、式ＰO＝ＩD×ＶD より出力密度を求めた。一方、入力密度は電池の充電終止電圧（ＶC）と電流電圧特性の直線を充電終止電圧まで外挿したときの電流値（ＩC）を用いて、式ＰI＝ＩC×ＶC より求めた。入出力密度測定結果を表２に示す。また、負荷特性試験として、１／３Ｃ充電し、１／３Ｃで放電したときの放電容量を容量維持率１００％とし、１／３Ｃで充電し、２０Ｃで放電したときの放電容量と１／３Ｃで放電したときの放電容量から維持率を求め、表２に示す。図２には、塗工量(密度１.４ｇ／cm3一定)と２０Ｃ放電維持率との関係、図３には、密度（塗工量８.０mg／cm2一定）と２０Ｃ放電維持率との関係を示し、図４には、密度（塗工量８.０mg／cm2一定）と入出力との関係を示した。図５には塗工量８.０mg／cm2における空隙率と２０Ｃ放電維持率との関係、図６には塗工量８.０mg／cm2における空隙率と入出力との関係を示した。 <Battery performance test>
As a battery performance test, the battery capacity was determined by charging and discharging at a charge end voltage of 4.1 V, a discharge end voltage of 2.7 V, and a charge / discharge rate of 1 C (1 hour rate of the rated electric capacity). Also, SOC (state of
charge) In the state of 50%, the currents of 1C, 3C, 5C, 10C, and 20C were applied for 10 seconds, the voltage at the 10th second at each current value was measured, and the input / output characteristics were examined. Using the current value (I D ) when extrapolating the discharge end voltage (V D ) of the battery and the current-voltage characteristics line to the end of discharge voltage, the output density was calculated from the formula P O = I D × V D . On the other hand, the input density is obtained from the formula P I = I C × V C using the current value (I C ) when the line of the charge end voltage (V C ) and the current-voltage characteristic is extrapolated to the charge end voltage. Asked. Table 2 shows the input / output density measurement results. In addition, as a load characteristic test, the discharge capacity when charging at 1 / 3C and discharging at 1 / 3C is assumed to be a capacity maintenance rate of 100%, and the discharge capacity when charging at 1 / 3C and discharging at 20C is 1 / 3C. Table 2 shows the retention rate obtained from the discharge capacity when discharged at. FIG. 2 shows the relationship between the coating amount (density 1.4 g / cm 3 constant) and the 20 C discharge maintenance rate, and FIG. 3 shows the density (coating amount 8.0 mg / cm 2 constant) and the 20 C discharge maintenance rate. FIG. 4 shows the relationship between density (coating amount 8.0 mg / cm 2 constant) and input / output. FIG. 5 shows the relationship between the porosity at a coating amount of 8.0 mg / cm 2 and the 20C discharge maintenance rate, and FIG. 6 shows the relationship between the porosity at a coating amount of 8.0 mg / cm 2 and input / output. .

（実施例２）
実施例１と同様の方法で、正極及び負極を作製した。作製した正極及び負極は、いずれもプレス機で圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤の密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤の密度は１.４ｇ／cm3 、負極集電体の両面合剤塗工量は７.４mg／
cm2、空隙率は３３％、（００４）／（１００）の積分強度比は２１であった。 (Example 2)
In the same manner as in Example 1, a positive electrode and a negative electrode were produced. The produced positive electrode and negative electrode were both roll-formed with a press and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.4 g / cm 3 , and the coating amount of the negative electrode current collector on both sides is 7.4 mg / cm 2.
cm 2 , the porosity was 33%, and the integrated intensity ratio of (004) / (100) was 21.

また、実施例１と同様の電池性能試験を行い、その結果を表２，図２に示す。   Moreover, the battery performance test similar to Example 1 was done, and the result is shown in Table 2 and FIG.

（実施例３）
実施例１と同様の方法で、正極及び負極を作製した。作製した正極及び負極は、いずれもプレス機で圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤の密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤の密度は１.４ｇ／cm3 、負極集電体の両面合剤塗工量は８.０mg／
cm2、空隙率は３３％、（００４）／（１００）の積分強度比は２１であった。 (Example 3)
In the same manner as in Example 1, a positive electrode and a negative electrode were produced. The produced positive electrode and negative electrode were both roll-formed with a press and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.4 g / cm 3 , and the coating amount of the negative electrode current collector on both sides is 8.0 mg / cm 2 .
cm 2 , the porosity was 33%, and the integrated intensity ratio of (004) / (100) was 21.

また、実施例１と同様の電池性能試験を行い、その結果を表２，図２〜図６に示す。   Moreover, the battery performance test similar to Example 1 was done, and the result is shown in Table 2 and FIGS.

（実施例４）
実施例１と同様の方法で、正極及び負極を作製した。作製した正極及び負極は、いずれもプレス機で圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤の密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤の密度は１.７ｇ／cm3 、負極集電体の両面合剤塗工量は８.０mg／
cm2、空隙率は２０％、（００４）／（１００）の積分強度比は３２であった。 Example 4
In the same manner as in Example 1, a positive electrode and a negative electrode were produced. The produced positive electrode and negative electrode were both roll-formed with a press and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.7 g / cm 3 and the coating amount of the negative electrode current collector on both sides is 8.0 mg / cm 2 .
cm 2 , the porosity was 20%, and the integrated intensity ratio of (004) / (100) was 32.

また、実施例１と同様の電池性能試験を行い、その結果を表２，図２〜図６に示す。   Moreover, the battery performance test similar to Example 1 was done, and the result is shown in Table 2 and FIGS.

（比較例１）
実施例１と同様の方法で、正極及び負極を作製した。作製した正極及び負極は、いずれもプレス機で圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤の密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤の密度は１.４ｇ／cm3、負極集電体の両面合剤塗工量は１０.５mg／cm2、空隙率は３３％、（００４）／（１００）の積分強度比は２０であった。 (Comparative Example 1)
In the same manner as in Example 1, a positive electrode and a negative electrode were produced. The produced positive electrode and negative electrode were both roll-formed with a press and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.4 g / cm 3 , the double-sided mixture coating amount of the negative electrode current collector is 10.5 mg / cm 2 , the porosity is 33%, and the integrated strength ratio of (004) / (100) is It was 20.

また、実施例１と同様の電池性能試験を行い、その結果を表２，図２に示す。   Moreover, the battery performance test similar to Example 1 was done, and the result is shown in Table 2 and FIG.

（比較例２）
実施例１と同様の方法で、正極及び負極を作製した。作製した正極及び負極は、いずれもプレス機で圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤の密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤の密度は１.０ｇ／cm3 、負極集電体の両面合剤塗工量は８.０mg／
cm2、空隙率は５２％、（００４）／（１００）の積分強度比は２０であった。 (Comparative Example 2)
In the same manner as in Example 1, a positive electrode and a negative electrode were produced. The produced positive electrode and negative electrode were both roll-formed with a press and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.0 g / cm 3 , and the coating amount of the negative electrode current collector on both sides is 8.0 mg / cm 2 .
cm 2 , the porosity was 52%, and the integrated intensity ratio of (004) / (100) was 20.

また、実施例１と同様の電池性能試験を行い、その結果を表２，図２〜図６に示す。   Moreover, the battery performance test similar to Example 1 was done, and the result is shown in Table 2 and FIGS.

（比較例３）
実施例１と同様の方法で、正極及び負極を作製した。作製した正極及び負極は、いずれもプレス機で圧延成型した後、１２０℃で１２時間真空乾燥した。このときの負極合剤の密度，負極集電体の両面合剤塗工量，空隙率及び（００４）／（１００）の積分強度比を表１に示す。負極合剤の密度は１.９ｇ／cm3 、負極集電体の両面合剤塗工量は８.０mg／
cm2、空隙率は１０％、（００４）／（１００）の積分強度比は３４であった。 (Comparative Example 3)
In the same manner as in Example 1, a positive electrode and a negative electrode were produced. The produced positive electrode and negative electrode were both roll-formed with a press and then vacuum-dried at 120 ° C. for 12 hours. Table 1 shows the density of the negative electrode mixture, the coating amount of the double-sided mixture of the negative electrode current collector, the porosity, and the integrated strength ratio of (004) / (100). The density of the negative electrode mixture is 1.9 g / cm 3 and the coating amount of the negative electrode current collector on both sides is 8.0 mg / cm 2 .
cm 2 , the porosity was 10%, and the integrated intensity ratio of (004) / (100) was 34.

また、実施例１と同様の電池性能試験を行い、その結果を表２，図２〜図６に示す。   Moreover, the battery performance test similar to Example 1 was done, and the result is shown in Table 2 and FIGS.

Figure 2008218248
Figure 2008218248

表２より、最も塗工量の少ない電池においても電極密度を高くすることにより、エネルギー密度７０Ｗｈ／kgと高く、回生エネルギーの利用可能な電池を提供できることがわかる。   Table 2 shows that by increasing the electrode density even in the battery with the smallest coating amount, it is possible to provide a battery that has a high energy density of 70 Wh / kg and can use regenerative energy.

図２より、負極合剤両面塗工量が６mg／cm2以上８mg／cm2以下の範囲では、２０Ｃ放電容量維持率が６５％以上と良好な値を示し、塗工量７.４mg／cm2以下では２０Ｃ放電容量維持率が９０％前後と高い値を示した。 As shown in FIG. 2, when the coating amount on both sides of the negative electrode mixture is 6 mg / cm 2 or more and 8 mg / cm 2 or less, the 20C discharge capacity retention rate is 65% or more, which is a good value, and the coating amount is 7.4 mg / cm. Below 2 , the 20C discharge capacity retention rate was as high as around 90%.

図３及び図４より、２０Ｃ放電容量維持率が６５％以上である良好な密度の範囲は、
１.４ｇ／cm3以上１.９ｇ／cm3以下であり、入出力特性を考慮すると１.４ｇ／cm3以上
１.７ｇ／cm3以下がより好ましい範囲であることが判る。 From FIG.3 and FIG.4, the range of the favorable density whose 20C discharge capacity maintenance factor is 65% or more is
It is 1.4 g / cm 3 or more and 1.9 g / cm 3 or less, and considering input / output characteristics, it is understood that 1.4 g / cm 3 or more and 1.7 g / cm 3 or less is a more preferable range.

また、図５及び図６より、負極合剤の空隙率が２０％以上，３５％以下の範囲が、電極捲回体を形成するリチウム二次電池において、負荷特性及び入出力特性の観点から最も好適である。   5 and 6, the negative electrode mixture has a porosity of 20% or more and 35% or less in the lithium secondary battery forming the electrode winding body from the viewpoint of load characteristics and input / output characteristics. Is preferred.

本発明の電極捲回体を示す側面断面図。Side surface sectional drawing which shows the electrode winding body of this invention. 密度１.４ｇ／cm3における塗工量と２０Ｃ放電維持率との関係図。The relationship figure of the coating amount in a density of 1.4 g / cm < 3 >, and a 20C discharge maintenance factor. 塗工量８.０mg／cm2における密度と２０Ｃ放電維持率との関係図。The relationship figure of the density in the coating amount of 8.0 mg / cm < 2 >, and a 20C discharge maintenance factor. 塗工量８.０mg／cm2における密度と入出力との関係図。The relationship diagram of density and input / output at a coating amount of 8.0 mg / cm 2 . 塗工量８.０mg／cm2における空隙率と２０Ｃ放電維持率との関係図。The relationship figure of the porosity and 20C discharge maintenance factor in coating amount 8.0mg / cm < 2 >. 塗工量８.０mg／cm2における空隙率と入出力との関係図。The relationship figure of the porosity and input / output in the coating amount of 8.0 mg / cm < 2 >.

符号の説明Explanation of symbols

１ 正極
２ 負極
３ セパレータ
４ 電池缶
５ 正極集電リード片
６ 負極集電リード片
７ 正極集電リード部
８ 負極集電リード部
９ 電池蓋
１０ 破裂弁
１１ 正極端子部
１２ ガスケット DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Battery can 5 Positive electrode current collection lead piece 6 Negative electrode current collection lead piece 7 Positive electrode current collection lead part 8 Negative electrode current collection lead part 9 Battery cover 10 Rupture valve 11 Positive electrode terminal part 12 Gasket

Claims (13)

リチウムを吸蔵放出可能な正極と、リチウムを吸蔵放出可能な負極と、が電解質及びセパレータを介して形成されるリチウム二次電池において、
前記正極と、前記負極と、が捲回されて電極捲回体を形成しており、
前記負極は、負極集電体と負極合剤とを有し、
前記負極合剤は炭素材料を有し、
前記負極合剤の密度が１.４ｇ／cm3以上，１.７ｇ／cm3以下であり、
前記負極合剤の前記負極集電体への塗工量が６mg／cm2以上，８mg／cm2以下であることを特徴とするリチウム二次電池。 In a lithium secondary battery in which a positive electrode capable of inserting and extracting lithium and a negative electrode capable of inserting and extracting lithium are formed via an electrolyte and a separator,
The positive electrode and the negative electrode are wound to form an electrode winding body,
The negative electrode has a negative electrode current collector and a negative electrode mixture,
The negative electrode mixture has a carbon material,
The density of the negative electrode mixture is 1.4 g / cm 3 or more and 1.7 g / cm 3 or less,
The lithium secondary battery, wherein the amount of the negative electrode mixture applied to the negative electrode current collector is 6 mg / cm 2 or more and 8 mg / cm 2 or less. 前記炭素材料が、黒鉛であることを特徴とする請求項１に記載のリチウム二次電池。   The lithium secondary battery according to claim 1, wherein the carbon material is graphite. 前記負極合剤が、負極活物質と導電剤と結着剤とを含み、前記負極活物質が黒鉛であることを特徴とする請求項１に記載のリチウム二次電池。   The lithium secondary battery according to claim 1, wherein the negative electrode mixture includes a negative electrode active material, a conductive agent, and a binder, and the negative electrode active material is graphite. 前記負極合剤の空隙率が２０％以上，３５％以下であることを特徴とする請求項１に記載のリチウム二次電池。   The lithium secondary battery according to claim 1, wherein a porosity of the negative electrode mixture is 20% or more and 35% or less. 前記負極合剤の前記負極集電体への塗工量が６mg／cm2以上，７.４mg／cm2 以下であることを特徴とする請求項１に記載のリチウム二次電池。 2. The lithium secondary battery according to claim 1, wherein an amount of the negative electrode mixture applied to the negative electrode current collector is 6 mg / cm 2 or more and 7.4 mg / cm 2 or less. 前記炭素材料の、ｄ002が３.３５６Å以下、Ｌｃ(002)が１０００Å以上、Ｌａ(110)が１０００Å以上であることを特徴とする請求項１に記載のリチウム二次電池。 2. The lithium secondary battery according to claim 1, wherein the carbon material has d 002 of 3.356 ３ or less, Lc (002) of 1000 Å or more, and La (110) of 1000 Å or more. 前記炭素材料の（００４）／（１００）の積分強度比が、２１〜３２であることを特徴とする請求項１に記載のリチウム二次電池。   2. The lithium secondary battery according to claim 1, wherein an integrated intensity ratio of (004) / (100) of the carbon material is 21 to 32. 3. リチウムを吸蔵放出可能な正極と、リチウムを吸蔵放出可能な負極と、が電解質及びセパレータを介して形成されるリチウム二次電池において、
前記正極と、前記負極と、が捲回されて電極捲回体を形成しており、
前記負極は、負極集電体と負極合剤とを有し、
前記負極合剤は炭素材料を有し、
前記負極合剤の空隙率が２０％以上，３５％以下であり、
前記負極合剤の前記負極集電体への塗工量が６mg／cm2以上，８mg／cm2以下であることを特徴とするリチウム二次電池。 In a lithium secondary battery in which a positive electrode capable of inserting and extracting lithium and a negative electrode capable of inserting and extracting lithium are formed via an electrolyte and a separator,
The positive electrode and the negative electrode are wound to form an electrode winding body,
The negative electrode has a negative electrode current collector and a negative electrode mixture,
The negative electrode mixture has a carbon material,
The porosity of the negative electrode mixture is 20% or more and 35% or less,
The lithium secondary battery, wherein the amount of the negative electrode mixture applied to the negative electrode current collector is 6 mg / cm 2 or more and 8 mg / cm 2 or less. 前記負極合剤が、負極活物質と導電剤と結着剤とを含み、前記負極活物質が炭素材料であることを特徴とする請求項８に記載のリチウム二次電池。   The lithium secondary battery according to claim 8, wherein the negative electrode mixture includes a negative electrode active material, a conductive agent, and a binder, and the negative electrode active material is a carbon material. 前記炭素材料が、黒鉛であることを特徴とする請求項９に記載のリチウム二次電池。   The lithium secondary battery according to claim 9, wherein the carbon material is graphite. 前記炭素材料の、ｄ002が３.３５６Å以下であることを特徴とする請求項８に記載のリチウム二次電池。 The lithium secondary battery according to claim 8, wherein d 002 of the carbon material is not more than 3.356 Å. 前記負極合剤の（００４）／（１００）の積分強度比が、２１〜３２であることを特徴とする請求項８に記載のリチウム二次電池。   9. The lithium secondary battery according to claim 8, wherein an integrated intensity ratio of (004) / (100) of the negative electrode mixture is 21 to 32. 10. 前記黒鉛は、粒径が１０μｍ以上３０μｍ以下の範囲にある粒子を９５％以上含有していることを特徴とする請求項１０に記載のリチウム二次電池。   11. The lithium secondary battery according to claim 10, wherein the graphite contains 95% or more of particles having a particle size in a range of 10 μm to 30 μm.
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