JP2008108740A - Electrode material for battery and secondary battery - Google Patents
Electrode material for battery and secondary battery Download PDFInfo
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Abstract
Description
この発明は、二次電池、特にリチウム二次電池、鉛二次電池などに好適な炭素繊維、特に気相成長炭素繊維（ＶＧＣＦ）を使用した電池用電極材（以下、電極材と略記することがある。）に関する。 The present invention relates to a battery electrode material (hereinafter abbreviated as an electrode material) using carbon fibers suitable for secondary batteries, particularly lithium secondary batteries, lead secondary batteries, etc., particularly vapor-grown carbon fibers (VGCF). There is.)
従来、この種の気相成長炭素繊維を用いた電極材として、特開平４−１５５７７６号公報に開示されたものがある。この先行発明の電極材は、コークスを高温熱処理して得られた黒鉛粉末と気相成長炭素繊維を混合したものであり、これをリチウムイオン二次電池の負極として使用するものである。 Conventionally, as an electrode material using this type of vapor-grown carbon fiber, there is one disclosed in JP-A-4-155576. This electrode material of the prior invention is a mixture of graphite powder obtained by high-temperature heat treatment of coke and vapor-grown carbon fiber, and is used as a negative electrode of a lithium ion secondary battery.
また、特開平４−２３７９７１号公報に記載の電極材は、メソカーボンマイクロビースと気相成長炭素繊維を混合したもので、これをやはりリチウムイオン二次電池の負極として使用するものである。
これらの先行発明にあっては、二次電池の充放電を繰り返すことによって生じる電極活物質である黒鉛粉末等の膨張を防止でき、電極材の変形、破損を抑えることができ、これによって容量低下を防ぐことができるとされている。
Moreover, the electrode material described in JP-A-4-237971 is a mixture of mesocarbon microbeads and vapor-grown carbon fibers, which is also used as a negative electrode of a lithium ion secondary battery.
In these prior inventions, it is possible to prevent expansion of graphite powder, which is an electrode active material, which is generated by repeatedly charging and discharging the secondary battery, and to suppress deformation and breakage of the electrode material, thereby reducing the capacity. It can be prevented.
しかしながら、これらの従来の電極材にあっては、黒鉛粉末等と気相成長炭素繊維とが単に混合された状態にあるだけであるため、黒鉛粉末等の膨潤を気相成長炭素繊維で十分抑えることができず、容量低下を防止する効果は十分とは言えない不都合がある。
よって、本発明における課題は、充放電の繰り返しによる黒鉛粉末等の電極活物質の膨張、変形等をより完全に抑えることができ、電池容量の低下を高度に防止することができる電池用電極材を得ることにある。 Therefore, the problem in the present invention is that the electrode material for a battery that can more fully suppress the expansion, deformation, etc. of the electrode active material such as graphite powder due to repeated charge and discharge, and can highly prevent a decrease in battery capacity. There is in getting.
かかる課題を解決するため、
請求項１にかかる発明は、気相成長炭素繊維が絡み合って形成され、その繊維相互の接点の一部が固着され、大きさ５〜５００μｍの凝集体の微細空洞内に黒鉛粉末が包含された複合体からなる電池用電極材であって、凝集体と黒鉛粉末との混合比は、凝集体が混合物の全量の３〜２０重量％である電池用電極材である。
請求項２にかかる発明は、気相成長炭素繊維が絡み合って形成され、その繊維相互の接点の一部が固着され、大きさ５〜５００μｍの凝集体の微細空洞内にリチウム含有複合酸化物粉末が包含された複合体からなる電池用電極材であって、凝集体の混合割合は、リチウム複合酸化物と凝集体との混合物全量の５〜２０重量％である電池用電極材である。
To solve this problem,
In the invention according to claim 1, vapor-grown carbon fibers are entangled with each other, a part of contact points between the fibers are fixed, and graphite powder is included in a fine cavity of an aggregate having a size of 5 to 500 μm. It is a battery electrode material made of a composite, and the mixing ratio of the aggregate and the graphite powder is a battery electrode material in which the aggregate is 3 to 20% by weight of the total amount of the mixture.
According to a second aspect of the present invention, there is provided a lithium-containing composite oxide powder in which vapor-grown carbon fibers are entangled with each other, a part of a contact point between the fibers is fixed, and a fine cavity of an aggregate having a size of 5 to 500 μm. Is an electrode material for a battery comprising a composite in which the mixing ratio of the aggregate is 5 to 20% by weight of the total amount of the mixture of the lithium composite oxide and the aggregate.
請求項３にかかる発明は、上記凝集体が気相成長樹枝状炭素繊維を圧縮し、加熱し、さらに解砕したものである請求項１または２に記載の電池用電極材である。
請求項４にかかる発明は、上記複合体には同時に炭素粉末が包含されている請求項１記載の電池用電極材である。
請求項５にかかる発明は、請求項１ないし４のいずれか一項に記載の電池用電極材を用いてなる二次電池である。
請求項６にかかる発明は、請求項１ないし４のいずれか一項に記載の電池用電極材を用いてなるリチウム二次電池である。
The invention according to claim 3 is the battery electrode material according to claim 1 or 2, wherein the aggregate is obtained by compressing, heating, and further crushing vapor-grown dendritic carbon fibers.
The invention according to claim 4 is the battery electrode material according to claim 1, wherein the composite includes carbon powder at the same time.
The invention according to claim 5 is a secondary battery using the battery electrode material according to any one of claims 1 to 4.
A sixth aspect of the present invention is a lithium secondary battery using the battery electrode material according to any one of the first to fourth aspects.
請求項７にかかる発明は、請求項１ないし４のいずれか一項に記載の電池用電極材と結着剤とを含む電極ペーストである。
請求項８にかかる発明は、請求項７に記載の電極ペーストの成形体からなる電極である。
The invention according to claim 7 is an electrode paste comprising the battery electrode material according to any one of claims 1 to 4 and a binder.
The invention according to claim 8 is an electrode comprising the molded article of the electrode paste according to claim 7.
本発明によれば、電極活物質が凝集体の微細空洞内に取り込まれるために、電極活物質の充放電による膨張が制限され、電極体自体の変形、破壊が防止できる。また、凝集体は、炭素繊維相互の接触が単なる機械的接触ではなく、炭素繊維が部分的に化学的に結合して繊維が絡みあっているので、凝集体の電気抵抗が低く、得られる電極材の内部抵抗も低くなる。
このため、本発明の電極材にあっては、電極活物質の粒子が凝集体の微細空洞内に取り込まれたり、粒子が炭素繊維に絡み付いたりして、粒子と炭素繊維との接触確率が増加して粒子と炭素繊維との電気的接触が多くなり、かつ凝集体自体の電気抵抗も低いので、内部抵抗が小さく、活物質の無駄がなく、有効に電解反応に関与するので、電池容量が増大する。
また、黒鉛粉末を活物質とした場合には、黒鉛粒子の充放電に起因する膨張が抑えられ、電極材の膨張、変形が防止されて充放電可能な回数が増し、長寿命となる。
According to the present invention, since the electrode active material is taken into the fine cavities of the aggregate, expansion due to charge and discharge of the electrode active material is limited, and deformation and destruction of the electrode body itself can be prevented. In addition, the agglomerates are not merely mechanical contacts between carbon fibers, but the carbon fibers are partially chemically bonded and the fibers are intertwined. The internal resistance of the material is also lowered.
For this reason, in the electrode material of the present invention, the contact probability between the particles and the carbon fibers increases because the particles of the electrode active material are taken into the fine cavities of the aggregates or the particles are entangled with the carbon fibers. Since the electrical contact between the particles and the carbon fibers increases and the electrical resistance of the aggregate itself is low, the internal resistance is small, there is no waste of the active material, and it effectively participates in the electrolytic reaction. Increase.
In addition, when graphite powder is used as an active material, expansion due to charging / discharging of the graphite particles is suppressed, expansion and deformation of the electrode material are prevented, and the number of charge / discharge can be increased, resulting in a long life.
以下、本発明を詳しく説明する。
本発明で使用される凝集体は、繊維径が０．０１〜５μｍの気相法炭素繊維が凝集し、その繊維相互の接点の一部がタール、ピッチなどの炭素物質の炭化物によって化学的に結合して固着された大きさが５〜５００μｍのフロック状または糸鞠状の構造体であり、その内部には種々の大きさの微細空洞が形成されているものである。
このような凝集体は、繊維径０．０５〜５μｍの気相成長炭素繊維を圧縮成形し、嵩密度０．０２ｇ／ｃｍ３以上の成形体とし、これを６００℃、好ましくは８００℃以上で加熱し、さらに機械的に解砕する方法や、該気相成長炭素繊維を０．１ｋｇ／ｃｍ２以上で圧縮しながら６００℃以上好ましくは８００℃以上で加熱し、さらに解砕する方法などによって製造できる（特願平７−３０８４０６号、平成７年１１月１日出願、参照）。
The present invention will be described in detail below.
In the agglomerates used in the present invention, vapor-grown carbon fibers having a fiber diameter of 0.01 to 5 μm are aggregated, and some of the contact points between the fibers are chemically formed by carbonaceous carbides such as tar and pitch. It is a flock-like or string-like structure having a size of 5 to 500 μm bonded and fixed, and various sizes of fine cavities are formed inside.
Such an aggregate is obtained by compression-molding vapor-grown carbon fibers having a fiber diameter of 0.05 to 5 μm to form a compact having a bulk density of 0.02 g / cm 3 or more, which is 600 ° C., preferably 800 ° C. or more. By heating and further mechanically pulverizing, or by compressing the vapor-grown carbon fiber at 0.1 kg / cm 2 or higher and heating at 600 ° C. or higher, preferably 800 ° C. or higher, and further pulverizing It can be manufactured (see Japanese Patent Application No. 7-308406, filed on Nov. 1, 1995).
また、上記凝集体に使われる気相成長炭素繊維としては、特に限定されず、分岐を有しない単繊維でも、また分岐を有する繊維でもよく、これらを混合したものでもよい。また、生成したままの熱処理されていない粗製の繊維が好ましい。粗製の炭素繊維には、約５〜２０重量％のタール、ピッチ等が吸着されており、これが圧縮成形時の繊維間を結合するバインダーとして機能し、さらに熱処理すると容易に炭化して繊維同士を接着する炭化物となる。
もし、熱処理後の気相成長炭素繊維を使用するのであれば、ピッチ等を添加して成形することが望ましい。
The vapor growth carbon fiber used for the aggregate is not particularly limited, and may be a single fiber having no branch, a fiber having a branch, or a mixture thereof. Moreover, the crude fiber which has not been heat-processed as it is produced | generated is preferable. About 5 to 20% by weight of tar, pitch, etc. are adsorbed to the crude carbon fiber, which functions as a binder that bonds the fibers during compression molding, and is further carbonized easily by heat treatment. It becomes the carbide to adhere.
If the vapor-grown carbon fiber after heat treatment is used, it is desirable to form by adding pitch or the like.
また、本発明で用いられる電極活物質としては、本発明の電極材をリチウムイオン二次電池の負極とする場合には、黒鉛粉末が用いられる。ここでの黒鉛粉末としては、リチウムイオンをインターカレーションできる層状結晶構造を有するものが用いられ、００２面の面間隔（ｄ００２）が０．３４ｍｍ以下のものが好ましい。黒鉛粉末の粒径は平均粒径１〜３０μｍ、好ましくは２〜１０μｍである。 As the electrode active material used in the present invention, graphite powder is used when the electrode material of the present invention is used as the negative electrode of a lithium ion secondary battery. As the graphite powder, one having a layered crystal structure capable of intercalating lithium ions is used, and one having a 002 plane spacing (d002) of 0.34 mm or less is preferable. The particle size of the graphite powder is 1 to 30 μm, preferably 2 to 10 μm, with an average particle size.
上記凝集体と黒鉛粉末との混合比は、凝集体が混合物の全量の３〜２０重量％となるようにされる。３重量％未満では、凝集体を使用した効果が得られず、２０重量％を越えると黒鉛粉末の量が減少し、電池容量が低下する。
黒鉛粉末と凝集体とは、十分に混合することが重要であり、混合後の状態において黒鉛粒子が凝集体の炭素繊維に絡み付いた状態、凝集体の内部の空洞に黒鉛粒子が取り込まれた状態あるいはこれがさらに絡み合った状態となっていることが必要である。
このための混合には、混合物に十分な剪断力を作用させうるヘンシェルミキサーやスパルタンリューザなどが用いられる。
The mixing ratio of the aggregate and the graphite powder is set so that the aggregate is 3 to 20% by weight of the total amount of the mixture. If the amount is less than 3% by weight, the effect of using the aggregate cannot be obtained. If the amount exceeds 20% by weight, the amount of the graphite powder decreases, and the battery capacity decreases.
It is important that the graphite powder and the agglomerate are sufficiently mixed. In the state after mixing, the graphite particles are entangled with the carbon fibers of the agglomerates, and the graphite particles are taken into the cavities inside the agglomerates. Or it must be in an intertwined state.
For this purpose, a Henschel mixer, a Spartan luzer or the like capable of applying a sufficient shearing force to the mixture is used.
この例での電極材を用いた合剤の具体的構造としては、凝集体と黒鉛粉末とを混合し、これに必要に応じて導電性付与剤としてのカーボンブラック等を添加し、これに結着剤としてのフッ素樹脂などを加えてよく混合してペースト状となし、このものを集電体となる銅箔、ステンレス鋼ネットなどの金属材に塗布、乾燥したシート状のものや集電体となる金属材上に塗布、成形したブロック状のものなどがある。 As a specific structure of the mixture using the electrode material in this example, an agglomerate and graphite powder are mixed, and if necessary, carbon black or the like as a conductivity-imparting agent is added to the mixture. Add a fluororesin as an adhesive and mix well to form a paste, which is applied to a metal material such as copper foil or stainless steel net as a current collector, and then dried into a sheet or current collector There are block-like ones coated and molded on the metal material to be used.
この例の電極活物質として黒鉛粉末を用いる電極材では、負極に限らず、正極に用いることもできる。この場合には、負極には金属リチウムが用いられる。 The electrode material using graphite powder as the electrode active material in this example can be used not only for the negative electrode but also for the positive electrode. In this case, metallic lithium is used for the negative electrode.
また、リチウムイオン二次電池の正極とする場合には、電極活物質として、ＬｉＣｏＯ２、ＬｉＭｎＯ２あるいはこれらのＣｏ、Ｍｎの一部をＣｏ、Ｍｎ、Ｆｅ、Ｎｉ等で置換したリチウム複合酸化物の粉末が用いられる。
これらのリチウム複合酸化物は、Ｌｉ、Ｃｏ、Ｍｎ、Ｆｅ、Ｎｉなどの炭酸塩や酸化物を混合し、焼成することによって得られ、焼成物を粉砕して粉末とする。
In the case of a positive electrode of a lithium ion secondary battery, LiCoO 2 , LiMnO 2 or a lithium composite oxide obtained by substituting a part of these Co and Mn with Co, Mn, Fe, Ni, etc. as an electrode active material The powder is used.
These lithium composite oxides are obtained by mixing and firing carbonates and oxides such as Li, Co, Mn, Fe, and Ni, and the fired product is pulverized into powder.
リチウム複合酸化物粉末を活物質とした場合には、導電性付与剤として、カーボンブラック、黒鉛粉末が添加され、これに上記凝集体を加えて混合することにより、電極材となる。
ここでの混合も先の例と同様でリチウム酸化物粉末と凝集体を十分に剪断力を作用させて混合することが必要となる。
凝集体の混合割合は、リチウム複合酸化物と凝集体との混合物全量の５〜２０重量％とされ、５重量％未満では凝集体添加効果が発現せず、２０重量％を越えると活物質が減少し、電池容量が低下する。
この例での電極材を用いた合剤の具体的な構造は、先の例と同様である。
When the lithium composite oxide powder is used as an active material, carbon black and graphite powder are added as conductivity-imparting agents, and the above-mentioned aggregate is added to and mixed with this to form an electrode material.
The mixing here is the same as the previous example, and it is necessary to mix the lithium oxide powder and the aggregate by sufficiently applying a shearing force.
The mixing ratio of the agglomerates is 5 to 20% by weight of the total amount of the lithium composite oxide and the agglomerates. If the amount is less than 5% by weight, the effect of adding the agglomerates is not manifested. The battery capacity decreases.
The specific structure of the mixture using the electrode material in this example is the same as in the previous example.
また、本発明の電極材は、密閉形の鉛二次電池（鉛蓄電池）の電極材として使用できる。
この場合の正極用電極材を用いた合剤の具体的構造は、例えば活物質としての二酸化鉛粉末と上記凝集体とを混合し、これに硫酸水溶液を加えてペースト状とし、このペーストを鉛合金などからなる格子状の集電体に塗布、充填し、乾燥したものなどがある。
Moreover, the electrode material of this invention can be used as an electrode material of a sealed lead secondary battery (lead storage battery).
The specific structure of the mixture using the electrode material for the positive electrode in this case is, for example, mixing lead dioxide powder as an active material and the above agglomerates, adding an aqueous sulfuric acid solution to this to form a paste, and this paste is lead For example, a grid-like current collector made of an alloy or the like is applied, filled, and dried.
また、負極用電極材を用いた合剤の具体的構造としては、例えば活物質としての金属鉛粉末と上記凝集体とを混合し、これに硫酸水溶液を添加してペーストとし、このペーストを鉛又は鉛合金からなる格子状の集電体に塗布、充填し、乾燥したものなどが挙げられる。 In addition, as a specific structure of the mixture using the electrode material for the negative electrode, for example, metallic lead powder as an active material and the above-mentioned aggregate are mixed, and an aqueous sulfuric acid solution is added thereto to form a paste. Or what apply | coated to the grid | lattice-shaped electrical power collector which consists of lead alloys, filled, and dried is mentioned.
このような構造の電極材にあっては、電極活物質の粒子が凝集体の微細空洞内に取り込まれ、あるいは粒子が凝集体の炭素繊維に絡み付くので、個々の粒子と炭素繊維との接触確率が増加し、電気的接触点が大幅に増大する。このため、電流が極めて流れ易くなり、内部抵抗が低下し、かつ活物質が無駄なく有効に電解反応に関与し、電池容量も増大する。 In the electrode material having such a structure, since the particles of the electrode active material are taken into the fine cavities of the aggregate or the particles are entangled with the carbon fibers of the aggregate, the probability of contact between the individual particles and the carbon fibers And the electrical contact point is greatly increased. For this reason, it becomes easy to flow an electric current, internal resistance falls, an active material participates in an electrolytic reaction effectively without waste, and battery capacity also increases.
さらに、電極活物質が黒鉛粉末の場合には、上記作用効果に加えて、黒鉛粒子の大部分が凝集体内の微細空洞に取り込まれるため、充放電による黒鉛粒子の膨張が抑えられる。
このため、電極材自体が膨潤し、変形することがなく、充放電の繰り返しによる電池容量の低下が防止され、長寿命となる。
Further, when the electrode active material is graphite powder, in addition to the above-described effects, most of the graphite particles are taken into the fine cavities in the agglomerate, so that the expansion of the graphite particles due to charge / discharge can be suppressed.
For this reason, the electrode material itself does not swell and deform, and a decrease in battery capacity due to repeated charge and discharge is prevented, resulting in a long life.
本発明の電極材を用いて二次電池を構成するには、リチウムイオン二次電池の場合では、例えば上述した正極用のシート状電極合剤と負極用のシート状電極合剤との間にポリプロピレン不織布などからなるシート状のセパレータを挟み込み、この積層物を渦巻状に巻回する。このもののそれぞれの合剤の集電体にリード線を取り付けて、缶体に収容し、過塩素酸リチウムなどのリチウム塩を溶解したエチレンカーボネート、プロピレンカーボネートなどの電解液を注入するなどの方法で行われる。
勿論、これ以外の種々の形態を取りうることは説明するまでもない。
In order to configure a secondary battery using the electrode material of the present invention, in the case of a lithium ion secondary battery, for example, between the above-described positive electrode sheet electrode mixture and negative electrode sheet electrode mixture. A sheet-like separator made of polypropylene nonwoven fabric or the like is sandwiched, and the laminate is wound in a spiral shape. A lead wire is attached to the current collector of each mixture of this material, accommodated in a can, and injected with an electrolytic solution such as ethylene carbonate or propylene carbonate in which a lithium salt such as lithium perchlorate is dissolved. Done.
Of course, it goes without saying that various other forms can be adopted.
以下、具体例を示す。
（実施例１）
本実施例では、図１に示す構造のコイン型リチウムイオン電池を作成した。図中符号１は電池ケース、２は封口板であり、これらは、耐電解液性のステンレス鋼板からなるものである。電池ケース１内には、ステンレス鋼ネットからなる正極集電体３がスポット溶接によって取り付けられている。この正極集電体３には正極電極材４が設けられて、正極となっている。
この正極電極材４は、黒鉛粉末９５重量部と上記凝集体５重量部とを混合し、この混合物８重量部に対してフッ素樹脂結着剤２重量部を加え、ヘンシェルミキサーによって混合した合剤０．２ｇを正極集電体３上に充填、成形したものである。
Specific examples are shown below.
(Example 1)
In this example, a coin-type lithium ion battery having the structure shown in FIG. 1 was produced. In the figure, reference numeral 1 denotes a battery case, and 2 denotes a sealing plate, which are made of an electrolytic solution-resistant stainless steel plate. A positive electrode current collector 3 made of a stainless steel net is attached in the battery case 1 by spot welding. The positive electrode current collector 3 is provided with a positive electrode material 4 to form a positive electrode.
This positive electrode material 4 is a mixture in which 95 parts by weight of graphite powder and 5 parts by weight of the above-mentioned aggregate are mixed, 2 parts by weight of a fluororesin binder is added to 8 parts by weight of this mixture, and mixed by a Henschel mixer. 0.2 g is filled and molded on the positive electrode current collector 3.
上記黒鉛粉末には、温度３０００℃で加熱処理した人造黒鉛電極（ｄ００２＝０．３３８ｎｍ）を粉砕して平均粒径５μｍとしたものを用いた。
上記凝集体には、分枝状の気相成長炭素繊維を圧縮成形し、嵩密度０．０６ｇ／ｃｍ２とした成形体を１３００℃で熱処理し、さらに２８００℃で５分間加熱し黒鉛化したものを解砕して大きさが１００〜３００μｍのフロック状のもの（ｄ００２＝０．３３９ｎｍ）を用いた。
As the graphite powder, an artificial graphite electrode (d002 = 0.338 nm) heat-treated at a temperature of 3000 ° C. was pulverized to have an average particle diameter of 5 μm.
The aforementioned aggregates, compression molded branched vapor-grown carbon fiber, a molded body with a bulk density of 0.06 g / cm 2 was heat-treated at 1300 ° C., was further graphitized by heating for 5 minutes at 2800 ° C. The material was crushed and a floc material (d002 = 0.339 nm) having a size of 100 to 300 μm was used.
正極電極体４上には微孔性のポリプロピレン製セパレータ５が設けられ、このセパレータ５上には円板状の金属リチウムの負極６が設けられ、この負極６は封口板２に接合されている。符号７は、ポリプロピレン製のパッキングである。
電解液には、エチレンカーボネートとジエチルカーボネートとの等容積混合溶媒にＬｉＰＦ６を１モル／リットルの濃度となるように溶解した溶液を用いた。
このコイン型電池の寸法は、直径２０ｍｍ、厚さ１６ｍｍであった。
A microporous polypropylene separator 5 is provided on the positive electrode body 4, and a disk-shaped negative electrode 6 of metallic lithium is provided on the separator 5. The negative electrode 6 is joined to the sealing plate 2. . Reference numeral 7 is a packing made of polypropylene.
As the electrolytic solution, a solution in which LiPF6 was dissolved in an equal volume mixed solvent of ethylene carbonate and diethyl carbonate to a concentration of 1 mol / liter was used.
The coin type battery had a diameter of 20 mm and a thickness of 16 mm.
（比較例１）
実施例１において、人造黒鉛電極粉砕粉末８重量部に対してフッ素樹脂結着剤２重量部を加え、ヘンシェルミキサーで混合した合剤０．２ｇを正極集電体３上に充填、成形した以外は同様にしてコイン型電池を作成した。
(Comparative Example 1)
In Example 1, 2 parts by weight of a fluororesin binder was added to 8 parts by weight of the artificial graphite electrode pulverized powder, and 0.2 g of the mixture mixed with a Henschel mixer was filled on the positive electrode current collector 3 and molded. Made a coin-type battery in the same way.
（比較例２）
実施例１において、人造黒鉛電極粉砕粉末９５重量部と、特公昭６２−４９３６３号公報に示された方法で合成された平均繊維径０．２μｍ、平均繊維長さ３０μｍの気相成長炭素繊維をアルゴン中で２８００℃で５分間加熱して部分的に黒鉛化した炭素繊維５重量部とを混合し、この混合物８重量部に対してフッ素樹脂結着剤２重量部を加え、ヘンシェルミキサーで混合した合剤０．２ｇを正極集電体３上に充填、成形した以外は同様にしてコイン型電池を作成した。
(Comparative Example 2)
In Example 1, 95 parts by weight of artificial graphite electrode pulverized powder and vapor grown carbon fiber having an average fiber diameter of 0.2 μm and an average fiber length of 30 μm synthesized by the method disclosed in Japanese Patent Publication No. 62-49363 Mix 5 parts by weight of partially graphitized carbon fiber by heating at 2800 ° C. for 5 minutes in argon, add 2 parts by weight of fluororesin binder to 8 parts by weight of this mixture, and mix with a Henschel mixer A coin-type battery was prepared in the same manner except that 0.2 g of the mixture was filled and molded on the positive electrode current collector 3.
これら３種のコイン型電池について、１００ｍＨｚ時の内部抵抗値、正極黒鉛粉末の重量エネルギー密度、充放電回数を測定した。
充放電条件は、電流密度０．３ｍＡ／ｃｍ２、充電終止電圧３．０Ｖ、放電終止電圧０Ｖで、定電流充放電を行った。
結果を表１、表２、表３に示す。
For these three types of coin-type batteries, the internal resistance value at 100 mHz, the weight energy density of the positive electrode graphite powder, and the number of charge / discharge cycles were measured.
The charge / discharge conditions were constant current charge / discharge at a current density of 0.3 mA / cm 2 , a charge end voltage of 3.0 V, and a discharge end voltage of 0 V.
The results are shown in Table 1, Table 2, and Table 3.
（実施例２）
実施例１で使用した正極を負極とし、集電体のステンレス鋼ネットを封口板にスポット溶接した。
正極として、ＬｉＣｏＯ２ ８０重量部と実施例１での凝集体１０重量部とフッ素樹脂結着剤１００重量部とをヘンシェルミキサーで混合した合剤０．４ｇをチタン製ネットの正極集電体とともにケース内に充填、成形したものを用いた以外は実施例１と同様にしてボタン電池を作成した。
(Example 2)
The positive electrode used in Example 1 was used as a negative electrode, and a stainless steel net as a current collector was spot welded to a sealing plate.
As a positive electrode, 0.4 g of a mixture obtained by mixing 80 parts by weight of LiCoO 2 , 10 parts by weight of the aggregate in Example 1 and 100 parts by weight of a fluororesin binder with a Henschel mixer, together with a positive electrode current collector made of titanium net. A button battery was made in the same manner as in Example 1 except that a case filled and molded was used.
このボタン電池について、充放電電流密度２．０ｍＡ／ｃｍ２、充電終止電圧４．０Ｖ、放電終止電圧２．７Ｖの条件下で定電流充放電試験を行った。
その結果、重量エネルギー密度は１４０ｍＡｈ／ｇであり、５００サイクルの充放電後において初期エネルギー密度の９４％を維持していた。
This button battery was subjected to a constant current charge / discharge test under the conditions of a charge / discharge current density of 2.0 mA / cm 2 , a charge end voltage of 4.0 V, and a discharge end voltage of 2.7 V.
As a result, the weight energy density was 140 mAh / g, and 94% of the initial energy density was maintained after 500 cycles of charge and discharge.
（比較例３）
実施例２において、正極として、ＬｉＣｏＯ２ ８重量部とアセチレンブラック１重量部とフッ素樹脂結着剤１重量部とをヘンシェルミキサーで混合した合剤０．４ｇを用いた以外は同様にして、ボタン電池を作成した。
このものについて、実施例２と同様の試験条件で充放電試験を行ったところ、重量エネルギー密度は１２０ｍＡｈ／ｇであり、５００サイクルの充放電後において初期エネルギー密度の７０％を維持していた。
(Comparative Example 3)
In Example 2, the button was similarly used except that 0.4 g of a mixture in which 8 parts by weight of LiCoO 2, 1 part by weight of acetylene black and 1 part by weight of a fluororesin binder were mixed with a Henschel mixer was used as the positive electrode. A battery was created.
When this was subjected to a charge / discharge test under the same test conditions as in Example 2, the weight energy density was 120 mAh / g, and 70% of the initial energy density was maintained after 500 cycles of charge / discharge.
（比較例４）
実施例２において、正極としてＬｉＣｏＯ２ ８重量部と、比較例２で使用した気相炭素繊維１重量部とフッ素樹脂結着剤１重量部をヘンシェルミキサーで混合した合剤０．４ｇを用いた以外は同様にしてボタン電池を作成した。
このものについて、実施例２と同様の試験条件で充放電試験を行ったところ、重量エネルギー密度は１３０ｍＡｈ／ｇであり、５００サイクルの充放電後において初期エネルギー密度の７８％を維持していた。
(Comparative Example 4)
In Example 2, 8 parts by weight of LiCoO 2 as a positive electrode, 0.4 g of a mixture in which 1 part by weight of vapor-phase carbon fiber used in Comparative Example 2 and 1 part by weight of a fluororesin binder were mixed with a Henschel mixer were used. A button battery was made in the same manner except for the above.
When this was subjected to a charge / discharge test under the same test conditions as in Example 2, the weight energy density was 130 mAh / g, and 78% of the initial energy density was maintained after 500 cycles of charge / discharge.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014073470A1 (en) * | 2012-11-07 | 2014-05-15 | 株式会社 村田製作所 | Positive electrode material, secondary battery, method for producing positive electrode material, and method for manufacturing secondary battery |
| WO2014073468A1 (en) * | 2012-11-07 | 2014-05-15 | 株式会社 村田製作所 | All-solid-state battery and method for producing same |
| WO2014073469A1 (en) * | 2012-11-07 | 2014-05-15 | 株式会社 村田製作所 | Positive electrode material, all-solid-state battery, and method for producing positive electrode material and all-solid-state battery |
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| JPH0765862A (en) * | 1993-08-24 | 1995-03-10 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
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| JPH04248268A (en) * | 1991-01-25 | 1992-09-03 | Mitsui Eng & Shipbuild Co Ltd | Electrode of battery |
| JPH0765862A (en) * | 1993-08-24 | 1995-03-10 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014073470A1 (en) * | 2012-11-07 | 2014-05-15 | 株式会社 村田製作所 | Positive electrode material, secondary battery, method for producing positive electrode material, and method for manufacturing secondary battery |
| WO2014073468A1 (en) * | 2012-11-07 | 2014-05-15 | 株式会社 村田製作所 | All-solid-state battery and method for producing same |
| WO2014073469A1 (en) * | 2012-11-07 | 2014-05-15 | 株式会社 村田製作所 | Positive electrode material, all-solid-state battery, and method for producing positive electrode material and all-solid-state battery |
| JP5796687B2 (en) * | 2012-11-07 | 2015-10-21 | 株式会社村田製作所 | Positive electrode material, secondary battery and manufacturing method thereof |
| JP5796686B2 (en) * | 2012-11-07 | 2015-10-21 | 株式会社村田製作所 | All-solid battery and method for manufacturing the same |
| JP5796798B2 (en) * | 2012-11-07 | 2015-10-21 | 株式会社村田製作所 | Positive electrode material, all solid state battery, and manufacturing method thereof |
| JPWO2014073470A1 (en) * | 2012-11-07 | 2016-09-08 | 株式会社村田製作所 | Positive electrode material, secondary battery and manufacturing method thereof |
| JPWO2014073469A1 (en) * | 2012-11-07 | 2016-09-08 | 株式会社村田製作所 | Positive electrode material, all solid state battery, and manufacturing method thereof |
| JPWO2014073468A1 (en) * | 2012-11-07 | 2016-09-08 | 株式会社村田製作所 | All-solid battery and method for manufacturing the same |
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