JPH0992286A - Graphitized vapor phase epitaxy carbon fiber for lithium ion secondary battery and lithium ion secondary battery - Google Patents
Graphitized vapor phase epitaxy carbon fiber for lithium ion secondary battery and lithium ion secondary batteryInfo
- Publication number
- JPH0992286A JPH0992286A JP8187677A JP18767796A JPH0992286A JP H0992286 A JPH0992286 A JP H0992286A JP 8187677 A JP8187677 A JP 8187677A JP 18767796 A JP18767796 A JP 18767796A JP H0992286 A JPH0992286 A JP H0992286A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- ion secondary
- lithium ion
- carbon fiber
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明はリチウムイオン二
次電池負極用黒鉛化気相成長炭素繊維、およびリチウム
イオン二次電池に関し、さらに詳しくは、電気特性に優
れ、リチウムイオン二次電池負極用として好適なリチウ
ムイオン二次電池負極用黒鉛化気相成長炭素繊維、およ
び充放電効率に優れ、かつサイクル寿命の長いリチウム
イオン二次電池に関する。TECHNICAL FIELD The present invention relates to a graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery and a lithium ion secondary battery. More specifically, it is excellent in electrical characteristics and used as a negative electrode of a lithium ion secondary battery. The present invention relates to a suitable graphitized vapor-grown carbon fiber for a negative electrode of a lithium ion secondary battery, and a lithium ion secondary battery having excellent charge / discharge efficiency and a long cycle life.
【０００２】[0002]
【従来の技術】気相成長炭素繊維は、超微粒子状の鉄や
ニッケルなどの金属を触媒として炭素化合物を８００〜
１，３００℃に加熱することによりこれを熱分解して製
造することができる。この気相成長炭素繊維は熱処理す
ることにより容易に黒鉛構造に転化する特長を有してい
る。例えば２，８００℃以上で加熱処理した黒鉛化気相
成長炭素繊維は、結晶欠陥の少ない黒鉛網面が繊維軸に
平行して発達している。それ故にこの黒鉛化気相成長炭
素繊維は、高強度かつ高弾性であり、しかも高い熱伝導
性や電気導電性を有している。2. Description of the Related Art A vapor-grown carbon fiber is prepared by using a metal such as iron or nickel in the form of ultra-fine particles as a catalyst to form a carbon compound in an amount of 800 to 800 nm.
It can be produced by pyrolyzing it by heating it to 1,300 ° C. This vapor grown carbon fiber has a feature that it can be easily converted to a graphite structure by heat treatment. For example, in the graphitized vapor grown carbon fiber that has been heat-treated at 2,800 ° C. or higher, the graphite network surface with few crystal defects develops parallel to the fiber axis. Therefore, the graphitized vapor-grown carbon fiber has high strength and elasticity, and also has high thermal conductivity and electrical conductivity.
【０００３】この黒鉛化気相成長炭素繊維の特性を利用
した応用例として、黒鉛化気相成長炭素繊維を電極活物
質として用いたリチウムイオン二次電池が挙げられる。An example of application utilizing the characteristics of the graphitized vapor grown carbon fiber is a lithium ion secondary battery using the graphitized vapor grown carbon fiber as an electrode active material.
【０００４】通常、このリチウムイオン二次電池は、電
極および電解液を有してなる。前記電極および電解液に
用いられる物質として下記のような具体例が挙げられ
る。Usually, this lithium ion secondary battery comprises an electrode and an electrolytic solution. Specific examples of the substance used for the electrode and the electrolytic solution are as follows.
【０００５】正極に用いられる物質としては、リチウム
含有複合酸化物たとえば、コバルト酸リチウム（ＬｉＣ
ｏＯ2 ）、マンガン酸リチウム（ＬｉＭｎ2 Ｏ4 ）、ニ
ッケル酸リチウム（ＬｉＮｉＯ2 ）などが挙げられる。Materials used for the positive electrode include lithium-containing composite oxides such as lithium cobalt oxide (LiC).
oO 2 ), lithium manganate (LiMn 2 O 4 ), lithium nickel oxide (LiNiO 2 ) and the like.
【０００６】負極に用いられる物質としては、炭素材料
たとえば、天然黒鉛、人造黒鉛、難黒鉛性炭素、メソカ
ーボンマイクロビーズ、ピッチ系炭素繊維、気相成長炭
素繊維などが挙げられる。Examples of the substance used for the negative electrode include carbon materials such as natural graphite, artificial graphite, non-graphitizable carbon, mesocarbon microbeads, pitch-based carbon fiber and vapor grown carbon fiber.
【０００７】電解液に用いられる物質としては、リチウ
ム塩と有機溶媒を混合した非水電解液が挙げられる。前
記リチウム塩としてはＬｉＣｌＯ4 ，ＬｉＰＦ6 ，Ｌｉ
ＢＦ4 ，ＬｉＡｓＦ6 ，ＬｉＣＦ3 ＳＯ3 などが挙げら
れる。前記有機溶媒としてはプロピレンカーボネート、
エチレンカーボネート、ジメチルカーボネート、ジエチ
ルカーボネートなどが挙げられる。Examples of the substance used in the electrolytic solution include a non-aqueous electrolytic solution in which a lithium salt and an organic solvent are mixed. Examples of the lithium salt include LiClO 4 , LiPF 6 , Li
BF 4, LiAsF 6, such as LiCF 3 SO 3 and the like. As the organic solvent, propylene carbonate,
Examples thereof include ethylene carbonate, dimethyl carbonate and diethyl carbonate.
【０００８】上述の物質で構成されたリチウムイオン二
次電池は、他の電池と比較して、エネルギー密度が高い
こと、サイクル特性に優れていることおよび安全性が高
いことを特長としている。The lithium ion secondary battery composed of the above-mentioned substances is characterized by having a high energy density, excellent cycle characteristics and high safety as compared with other batteries.
【０００９】さらに上記リチウムイオン二次電池におい
て、特開平６−７３６１５号公報に記載されたように、
従来から公知の気相成長炭素繊維、特に短い繊維長の気
相成長炭素繊維を負極に用いた場合には、初期容量は高
いが二次電池として十分なサイクル寿命を得ることがで
きなかった。一方、長い繊維長の気相成長炭素繊維を負
極に用いた場合には、集電体たとえば金属シートに気相
成長炭素繊維含有塗布液を塗布すると、気相成長炭素繊
維が剥離し、たとえ接着性良く気相成長炭素繊維含有塗
布液を塗布することができたとしても、形成された負極
の表面が平滑ではなくなる。Further, in the above lithium ion secondary battery, as described in JP-A-6-73615,
When a conventionally known vapor-grown carbon fiber, in particular, a vapor-grown carbon fiber having a short fiber length is used for the negative electrode, the initial capacity is high, but a sufficient cycle life as a secondary battery cannot be obtained. On the other hand, when the vapor growth carbon fiber having a long fiber length is used for the negative electrode, when the coating liquid containing the vapor growth carbon fiber is applied to the current collector, for example, the metal sheet, the vapor growth carbon fiber is peeled off, and Even if the vapor-grown carbon fiber-containing coating liquid can be applied with good properties, the surface of the formed negative electrode is not smooth.
【００１０】[0010]
【発明が解決しようとする課題】この発明の目的は、リ
チウムイオン二次電池における集電体から容易に剥離す
ることがなく、また負極の表面を平滑なものとすること
ができて、電気特性の優れたリチウムイオン二次電池負
極用黒鉛化気相成長炭素繊維を提供することにある。こ
の発明の他の目的は充放電効率およびサイクル寿命の長
いリチウムイオン二次電池の負極を好適に形成すること
のできる二次電池負極用黒鉛化気相成長炭素繊維を提供
することにある。この発明の他の目的は、充放電効率お
よびサイクル寿命の長いリチウムイオン二次電池を提供
することにある。DISCLOSURE OF THE INVENTION The object of the present invention is to prevent the surface of the negative electrode from being easily peeled off from the current collector in the lithium ion secondary battery, and to make the surface of the negative electrode smooth, thereby improving the electrical characteristics. Another object of the present invention is to provide graphitized vapor-grown carbon fiber for a lithium ion secondary battery negative electrode. Another object of the present invention is to provide a graphitized vapor-grown carbon fiber for a secondary battery negative electrode, which can favorably form a negative electrode of a lithium ion secondary battery having long charge / discharge efficiency and long cycle life. Another object of the present invention is to provide a lithium ion secondary battery having long charge / discharge efficiency and long cycle life.
【００１１】[0011]
【課題を解決するための手段】前記課題を解決するため
の請求項１に記載の発明は、平均直径が１〜１０μｍで
あり、平均繊維長が１５〜２５μｍであることを特徴と
するリチウムイオン二次電池負極用黒鉛化気相成長炭素
繊維であり、請求項２に記載の発明は、前記請求項１に
記載のリチウムイオン二次電池用黒鉛化気相成長炭素繊
維から得られた負極を有してなることを特徴とするリチ
ウムイオン二次電池である。The invention according to claim 1 for solving the above problems has an average diameter of 1 to 10 μm and an average fiber length of 15 to 25 μm. A graphitized vapor-grown carbon fiber for a secondary battery negative electrode, wherein the invention according to claim 2 provides a negative electrode obtained from the graphitized vapor-grown carbon fiber for a lithium ion secondary battery according to claim 1. A lithium-ion secondary battery characterized by having.
【００１２】[0012]
【発明の実施の形態】−リチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維−この発明のリチウムイオン二
次電池負極用黒鉛化気相成長炭素繊維は、その平均直径
が１〜１０μｍであり、好ましくは１．５〜５μｍであ
り、さらに好ましくは２〜３μｍである。BEST MODE FOR CARRYING OUT THE INVENTION Graphitized vapor grown carbon fiber for negative electrode of lithium ion secondary battery-The graphitized vapor grown carbon fiber for negative electrode of lithium ion secondary battery of the present invention has an average diameter of 1 to 10 µm. Yes, it is preferably 1.5 to 5 μm, and more preferably 2 to 3 μm.
【００１３】この発明のリチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維は、その平均繊維長が１５〜２
５μｍの範囲内、好ましくは１６〜２３μｍ、さらに好
ましくは１８〜２２μｍの範囲内にある。The graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention has an average fiber length of 15 to 2
It is in the range of 5 μm, preferably 16 to 23 μm, more preferably 18 to 22 μm.
【００１４】リチウムイオン二次電池負極用黒鉛化気相
成長炭素繊維の平均直径および平均繊維長が、前記範囲
内にあると、リチウムイオン二次電池負極用黒鉛化気相
成長炭素繊維の分散が容易に実現され、繊維同士の接触
も良好になる。When the average diameter and the average fiber length of the graphitized vapor grown carbon fiber for the negative electrode of the lithium ion secondary battery are within the above ranges, the dispersion of the graphitized vapor grown carbon fiber for the negative electrode of the lithium ion secondary battery is dispersed. It is easily realized and the contact between fibers is good.
【００１５】なお、リチウムイオン二次電池負極用黒鉛
化気相成長炭素繊維の平均直径および平均繊維長は、リ
チウムイオン二次電池負極用黒鉛化気相成長炭素繊維を
走査型電子顕微鏡写真に撮り、走査型電子顕微鏡写真を
観察し、走査型電子顕微鏡写真に写されたリチウムイオ
ン二次電池負極用黒鉛化気相成長炭素繊維から１，００
０のサンプルを無作為に選択し、選択したリチウムイオ
ン二次電池負極用黒鉛化気相成長炭素繊維の直径および
長さを測定し、１，０００のサンプルについての値を平
均することにより、求められる。The average diameter and average fiber length of the graphitized vapor-grown carbon fiber for negative electrode of lithium ion secondary battery are the same as those of the graphitized vapor-grown carbon fiber for negative electrode of lithium ion secondary battery taken by scanning electron microscope. The scanning electron micrograph was observed, and the graphitized vapor-grown carbon fiber for negative electrode of the lithium-ion secondary battery, which was photographed in the scanning electron micrograph, was used to form 1,00
0 sample was randomly selected, the diameter and length of the selected graphitized vapor-grown carbon fiber for lithium ion secondary battery negative electrode were measured, and the values for 1,000 samples were averaged to obtain To be
【００１６】この発明のリチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維は、その平均アスペクト比が５
〜１５であると好ましく、さらに７．０〜１２．５であ
るのが好ましい。リチウムイオン二次電池負極用黒鉛化
気相成長炭素繊維の平均アスペクト比が５〜１５である
とこの発明の目的をさらに良く達成することができる。The average aspect ratio of the graphitized vapor-grown carbon fiber for negative electrode of lithium ion secondary battery of the present invention is 5
It is preferable that it is -15, and it is more preferable that it is 7.0-12.5. If the average aspect ratio of the graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery is 5 to 15, the object of the present invention can be further achieved.
【００１７】この発明のリチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維は、高度に発達した黒鉛構造を
有し、縮合環状の黒鉛網面の発達度合いの点から、黒鉛
網面間距離（ｄoo2 ）は通常大きくとも０．３３８ｎ
ｍ、好ましくは、大きくとも０．３３７ｎｍ、更に好ま
しくは、０．３３５５〜０．３３６５ｎｍである。The graphitized vapor-grown carbon fiber for a lithium ion secondary battery negative electrode of the present invention has a highly developed graphite structure, and in view of the degree of development of a condensed ring-shaped graphite network surface, the distance between graphite network surfaces is (D oo2 ) is usually at most 0.338n
m, preferably at most 0.337 nm, more preferably 0.3355 to 0.3365 nm.
【００１８】この黒鉛網面間距離は、「炭素技術Ｉ」
（科学技術社出版、１９７０年発行）の第５５頁に記載
のＸ線回折から求める学振法により、測定可能である。The distance between the graphite mesh planes is "Carbon Technology I".
It can be measured by the Gakushin method, which is obtained from X-ray diffraction as described on page 55 of (Science and Technology Publishing, published in 1970).
【００１９】また、この発明のリチウムイオン二次電池
負極用黒鉛化気相成長炭素繊維は、その縮合環状の黒鉛
網面が重なった厚さすなわち黒鉛結晶子の厚さ（Ｌc ）
が通常小さくとも４０ｎｍ、好ましくは小さくとも６０
ｎｍ、更に好ましくは小さくとも８０ｎｍである。Further, the graphitized vapor-grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention has a thickness in which the condensed ring-shaped graphite network surfaces are superposed, that is, the thickness of the graphite crystallite (L c ).
Is usually at least 40 nm, preferably at least 60 nm
nm, and more preferably at least 80 nm.
【００２０】この黒鉛結晶子の厚さは、「炭素技術Ｉ」
（科学技術社出版、１９７０年発行）の第５５頁に記載
のＸ線回折から求める学振法により、測定可能である。The thickness of this graphite crystallite is "Carbon Technology I".
It can be measured by the Gakushin method, which is obtained from X-ray diffraction as described on page 55 of (Science and Technology Publishing, published in 1970).
【００２１】この発明のリチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維は、電子スピン共鳴吸収法によ
り測定したその好ましいスピン密度が大きくとも８×１
０18spins/g 、さらに好ましくは大きくとも７×１０18
spins/g である。The graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention has a preferable spin density of at most 8 × 1 as measured by an electron spin resonance absorption method.
0 18 spins / g, more preferably at most 7 × 10 18
It is spins / g.
【００２２】このスピン密度は、電子スピン共鳴吸収法
により測定することができる。This spin density can be measured by the electron spin resonance absorption method.
【００２３】この発明のリチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維は、以下のようにして、好適に
製造することができる。The graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention can be suitably manufactured as follows.
【００２４】すなわち、この発明のリチウムイオン二次
電池負極用黒鉛化気相成長炭素繊維は、特定の長さを有
する黒鉛化気相成長炭素繊維を、適宜の切断手段で切断
することにより製造されることができる。That is, the graphitized vapor-grown carbon fiber for lithium ion secondary battery negative electrode of the present invention is produced by cutting the graphitized vapor-grown carbon fiber having a specific length by an appropriate cutting means. You can
【００２５】ここで前記黒鉛化気相成長炭素繊維は、気
相成長炭素繊維を黒鉛化処理することにより得ることが
できる。The graphitized vapor grown carbon fiber can be obtained by subjecting the vapor grown carbon fiber to graphitization.
【００２６】前記気相成長炭素繊維は、気相成長法によ
り製造することができる。The vapor grown carbon fiber can be produced by a vapor growth method.
【００２７】気相成長法により気相成長炭素繊維を製造
する方法としては、いわゆる基板成長法と流動気相法と
がある。基板成長法は、基板に触媒金属例えば遷移金属
もしくは遷移金属化合物を担持させ、高温度に加熱しな
がら、その基板上に炭素源ガスたとえば炭化水素ガスを
流通させることにより、基板表面に炭素繊維を生成させ
る方法であり、流動気相法は、基板を使用せず、触媒金
属源たとえば触媒金属を提供することのできる金属化合
物と炭素源たとえば炭素化合物たとえば炭化水素とを気
化して高温の反応管中に流通させることにより、空間中
に炭素繊維を生成させる方法である。なお、炭素源と触
媒金属源とは同一の化合物であっても良く、そのような
好適な化合物としてフェロセンのようなメタロセンが挙
げられる。As a method for producing a vapor grown carbon fiber by the vapor growth method, there are a so-called substrate growth method and a fluidized vapor phase method. In the substrate growth method, a catalyst metal such as a transition metal or a transition metal compound is supported on the substrate, and a carbon source gas such as a hydrocarbon gas is circulated on the substrate while being heated to a high temperature, whereby carbon fibers are formed on the substrate surface. The fluidized vapor phase method is a method of producing a high temperature reaction tube without using a substrate by vaporizing a metal compound capable of providing a catalyst metal source such as a catalyst metal and a carbon source such as a carbon compound such as a hydrocarbon. This is a method of generating carbon fibers in the space by circulating the carbon fibers inside. The carbon source and the catalyst metal source may be the same compound, and such a suitable compound includes metallocene such as ferrocene.
【００２８】具体的には、特開昭５２−１０７３２０
号、特開昭５７−１１７６２２号、特開昭５８−１５６
５１２号、特開昭５８−１８０６１５号、特開昭６０−
１８５８１８号、特開昭６０−２２４８１５号、特開昭
６０−２３１８２１号、特開昭６１−１３２６３０号、
特開昭６１−１３２６００号、特開昭６１−１３２６６
３号、特開昭６１−２２５３１９号、特開昭６１−２２
５３２２号、特開昭６１−２２５３２５号、特開昭６１
−２２５３２７号、特開昭６１−２２５３２８号、特開
昭６１−２２７５４２５号、特開昭６１−２８２４２７
号、特開平５−２２２６１９号の各公報に記載の方法に
より製造される気相成長炭素繊維を黒鉛化気相成長炭素
繊維の原料として使用することができる。Specifically, Japanese Patent Laid-Open No. 52-107320
No. 57-176622 and 58-156.
512, JP-A-58-180615, JP-A-60-
185818, JP-A-60-224815, JP-A-60-231821, JP-A-61-132630,
JP-A-61-132600, JP-A-61-132666
3, JP-A-61-225319, JP-A-61-222.
5322, JP-A-61-225325, JP-A-61
-225327, JP-A-61-225328, JP-A-61-2275425, and JP-A-61-282427.
The vapor-grown carbon fibers produced by the method described in JP-A-5-222619 can be used as a raw material for the graphitized vapor-grown carbon fibers.
【００２９】黒鉛化気相成長炭素繊維は、前記気相成長
炭素繊維を２，０００℃以上、好ましくは２，０００℃
〜３，０００℃の範囲に加熱処理することにより黒鉛化
することにより製造されることができる。The graphitized vapor-grown carbon fiber is obtained by adding the vapor-grown carbon fiber to 2,000 ° C. or higher, preferably 2,000 ° C.
It can be produced by graphitizing by heat treatment in the range of up to 3,000 ° C.
【００３０】加熱処理の雰囲気としては不活性ガス雰囲
気が通常採用される。加熱処理時間は通常５分以上であ
る。An inert gas atmosphere is usually adopted as the atmosphere for the heat treatment. The heat treatment time is usually 5 minutes or longer.
【００３１】この発明においては、前記のようにして得
られた黒鉛化気相成長炭素繊維の平均繊維長が２０〜１
００μｍ、好ましくは３０〜７０μｍである黒鉛化気相
成長炭素繊維を適宜の切断手段により切断することによ
り、この発明のリチウムイオン二次電池負極用黒鉛化気
相成長炭素繊維を得ることができる。In the present invention, the average fiber length of the graphitized vapor grown carbon fiber obtained as described above is 20 to 1
The graphitized vapor grown carbon fiber having a size of 00 μm, preferably 30 to 70 μm is cut by an appropriate cutting means to obtain the graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention.
【００３２】前記切断手段としては、高衝撃力をもって
繊維を破断することのできるハイブリダイザ、あるいは
高圧縮力をもって繊維塊を加圧圧縮するプレス機、静水
圧等方加圧装置（ＣＩＰ）、加圧ロール装置等を挙げる
ことができる。As the cutting means, a hybridizer capable of breaking the fibers with a high impact force, a press machine for pressurizing and compressing the fiber mass with a high compressive force, a hydrostatic isotropic pressure device (CIP), a pressurizing device A roll device or the like can be used.
【００３３】ハイブリダイザを採用する場合、その回転
数を２，０００〜６，０００ｒｐｍにして、１〜５分間
の処理条件を採用するのが好ましい。When the hybridizer is used, it is preferable to set the rotation speed to 2,000 to 6,000 rpm and to adopt the processing condition for 1 to 5 minutes.
【００３４】加圧圧縮による場合、その加圧圧縮力は、
１００〜３，０００ｋｇ／ｃｍ2 であり、好ましくは３
００〜２，０００ｋｇ／ｃｍ2 であり、さらに好ましく
は５００〜１，５００ｋｇ／ｃｍ2 である。In the case of pressure compression, the pressure compression force is
100 to 3,000 kg / cm 2 , preferably 3
It is from 00 to 2,000 kg / cm 2 , and more preferably from 500 to 1,500 kg / cm 2 .
【００３５】この発明のリチウムイオン二次電池負極用
黒鉛化気相成長炭素繊維は、リチウムイオン二次電池負
極として好適である。The graphitized vapor-grown carbon fiber for a lithium ion secondary battery negative electrode of the present invention is suitable as a lithium ion secondary battery negative electrode.
【００３６】−リチウムイオン二次電池− この発明のリチウムイオン二次電池は正極、負極および
電解液を有する。-Lithium Ion Secondary Battery- The lithium ion secondary battery of the present invention has a positive electrode, a negative electrode and an electrolytic solution.
【００３７】正極に用いられる物質としては、リチウム
イオン二次電池の正極として用いられることのできる物
質を制限なく挙げることができ、好適例としてリチウム
含有複合酸化物たとえば、コバルト酸リチウム（ＬｉＣ
ｏＯ2 ）、マンガン酸リチウム（ＬｉＭｎ2 Ｏ4 ）、ニ
ッケル酸リチウム（ＬｉＮｉＯ2 ）などが挙げられる。Examples of the substance used for the positive electrode include substances that can be used for the positive electrode of a lithium ion secondary battery without any limitation. Suitable examples are lithium-containing composite oxides such as lithium cobalt oxide (LiC).
oO 2 ), lithium manganate (LiMn 2 O 4 ), lithium nickel oxide (LiNiO 2 ) and the like.
【００３８】負極に用いられる物質は、この発明のリチ
ウムイオン二次電池負極用黒鉛化気相成長炭素繊維であ
る。The substance used for the negative electrode is the graphitized vapor grown carbon fiber for negative electrode of the lithium ion secondary battery of the present invention.
【００３９】電解液に用いられる物質としては、リチウ
ムイオン二次電池の電解液として用いられることのでき
る物質を制限なく挙げることができ、具体的にはリチウ
ム塩と有機溶媒とを混合した非水電解液などが挙げられ
る。前記リチウム塩としてはＬｉＣｌＯ4 ，ＬｉＰＦ
6 ，ＬｉＢＦ4 ，ＬｉＡｓＦ6 ，ＬｉＣＦ3 ＳＯ3 など
が挙げられる。前記有機溶媒としてはプロピレンカーボ
ネート、エチレンカーボネート、ジメチルカーボネー
ト、ジエチルカーボネートなどの有機炭酸化合物、これ
らの混合物、および有機炭酸化合物とその他の添加剤と
の混合物などが挙げられる。これらの中でも好ましいの
は、エチレンカーボネート、ジメチルカーボネート、ジ
エチルカーボネートなどの有機炭酸化合物である。Examples of the substance used in the electrolytic solution include substances that can be used as the electrolytic solution of a lithium ion secondary battery without any limitation, and specifically, non-aqueous substances obtained by mixing a lithium salt and an organic solvent. Examples include electrolytes. Examples of the lithium salt include LiClO 4 and LiPF
6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 and the like can be mentioned. Examples of the organic solvent include organic carbonate compounds such as propylene carbonate, ethylene carbonate, dimethyl carbonate, and diethyl carbonate, mixtures thereof, and mixtures of organic carbonate compounds with other additives. Among these, organic carbonate compounds such as ethylene carbonate, dimethyl carbonate and diethyl carbonate are preferable.
【００４０】リチウムイオン二次電池としては、ボタン
型二次電池、円筒型二次電池、角型二次電池、コイン型
二次電池等の形態を挙げることができる。The lithium ion secondary battery may be in the form of a button type secondary battery, a cylindrical type secondary battery, a square type secondary battery, a coin type secondary battery or the like.
【００４１】この発明のリチウムイオン二次電池は、こ
の発明のリチウムイオン二次電池用黒鉛化気相成長炭素
繊維を負極として組み込んでなる限り、その構造には特
に制限がなく、従来から公知の構造を採用することがで
きる。The lithium-ion secondary battery of the present invention is not particularly limited in its structure as long as it incorporates the graphitized vapor-grown carbon fiber for lithium-ion secondary battery of the present invention as a negative electrode, and has been conventionally known. A structure can be adopted.
【００４２】[0042]
（実施例１） （１）リチウムイオン二次電池用黒鉛化気相成長炭素繊
維の製造 平均直径２μｍおよび平均繊維長５０μｍの気相成長炭
素繊維を、アルゴンガス雰囲気下に２，８００℃に３０
分かけて黒鉛化処理をすることにより、黒鉛化気相成長
炭素繊維を製造した。この黒鉛化気相成長炭素繊維は、
平均アスペクト比が２５であり、黒鉛網面間距離（ｄ
oo2 ）が０．３３６１ｎｍであり、黒鉛結晶子の厚さ
（Ｌc ）が１３０ｎｍであった。Example 1 (1) Production of Graphitized Vapor-Grown Carbon Fiber for Lithium-Ion Secondary Battery Vapor-grown carbon fiber having an average diameter of 2 μm and an average fiber length of 50 μm was heated to 2,800 ° C. under an argon gas atmosphere at 30 ° C.
Graphitized vapor-grown carbon fibers were produced by performing graphitization treatment over a period of time. This graphitized vapor grown carbon fiber is
The average aspect ratio is 25, and the distance between graphite network planes (d
oo2 ) was 0.3361 nm, and the thickness of graphite crystallite (L c ) was 130 nm.
【００４３】この黒鉛化気相成長炭素繊維４０ｇをハイ
ブリダイザー（ＮＨＳ−１、（株）奈良機械製作所製）
に装填して、４，０００ｒｐｍ（周速５０ｍ／ｓ）にて
２分間高衝撃処理をした。高衝撃処理をして得られた炭
素繊維からランダムに選ばれた１，０００本の繊維を走
査型電子顕微鏡写真に撮り、その平均繊維長および平均
直径を既述した方法により測定したところ、平均繊維長
は２０．４μｍであり、平均直径は２μｍであった。よ
って、この切断処理により得られたものは、この発明の
リチウムイオン二次電池負極用黒鉛化気相成長炭素繊維
であった。40 g of this graphitized vapor grown carbon fiber was used as a hybridizer (NHS-1, manufactured by Nara Machinery Co., Ltd.).
And subjected to high impact treatment at 4,000 rpm (peripheral speed 50 m / s) for 2 minutes. 1,000 fibers randomly selected from the carbon fibers obtained by the high impact treatment were taken on a scanning electron micrograph, and the average fiber length and average diameter were measured by the method described above. The fiber length was 20.4 μm and the average diameter was 2 μm. Therefore, what was obtained by this cutting treatment was the graphitized vapor-grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention.
【００４４】（２）リチウムイオン二次電池負極用黒鉛
化気相成長炭素繊維の評価 充放電試験による評価 以下のようにして負極である作用極を作製した。すなわ
ち、ポリフッ化ビニリデン（ＰＶＤＦ）０．１ｇをＮ−
メチル−２−ピロリドン０．８ミリリットルに溶解し
た。得られた溶液に前記（１）のリチウムイオン二次電
池負極用黒鉛化気相成長炭素繊維０．９ｇを加え、乳鉢
で混合した。(2) Evaluation of Graphitized Vapor-Grown Carbon Fiber for Lithium Ion Secondary Battery Negative Electrode Evaluation by Charge and Discharge Test A negative electrode working electrode was prepared as follows. That is, 0.1 g of polyvinylidene fluoride (PVDF) is N-
It was dissolved in 0.8 ml of methyl-2-pyrrolidone. 0.9 g of the graphitized vapor-grown carbon fibers for lithium ion secondary battery negative electrode of the above (1) was added to the obtained solution and mixed in a mortar.
【００４５】さらに、上記混合物を１×５ｃｍのニッケ
ルメッシュに、塗布面積が１×１ｃｍとなるように、塗
布し、１１０℃で２４時間かけて乾燥することによっ
て、負極（作用極）を得た。このとき、塗布層は容易に
剥離することがなく、しかも負極の表面は平滑であっ
た。Further, the above mixture was applied to a nickel mesh of 1 × 5 cm so that the coating area was 1 × 1 cm, and dried at 110 ° C. for 24 hours to obtain a negative electrode (working electrode). . At this time, the coating layer was not easily peeled off, and the surface of the negative electrode was smooth.
【００４６】前記作用極、金属リチウムである対極、金
属リチウムである参照極および１モルのＬｉＣｌＯ4 を
エチレンカーボネート（ＥＣ）およびジエチルカーボネ
ート（ＤＥＣ）の混合溶媒（ＥＣ／ＤＥＣ＝１／１容積
比）に溶解してなる電解液を有する三電極式ビーカセル
を、組み立てた。電流密度を２５ｍＡ／カーボン１ｇに
し、作用極と参照極間電圧（充放電電圧）を０〜２．５
Ｖにして、充電容量、放電容量および充放電効率を測定
した。結果を表１に示した。The working electrode, the counter electrode which is metallic lithium, the reference electrode which is metallic lithium and 1 mol of LiClO 4 are mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC / DEC = 1/1 volume ratio). A three-electrode type beaker cell having an electrolyte solution dissolved therein was assembled. The current density is 25 mA / g of carbon, and the voltage between the working electrode and the reference electrode (charge / discharge voltage) is 0 to 2.5.
The charging capacity, the discharging capacity, and the charging / discharging efficiency were measured at V. The results are shown in Table 1.
【００４７】円筒型電池によるサイクル試験 以下のようにして負極を作製した。すなわち、ポリフッ
化ビニリデン（ＰＶＤＦ）３０ｇをＮ−メチル−２−ピ
ロリドン４２０ミリリットルに溶解した。得られた溶液
に前記（１）のリチウムイオン二次電池負極用黒鉛化気
相成長炭素繊維２７０ｇを加え、超音波分散機で十分に
分散した。得られた分散液を銅製シート（厚み１０μ
ｍ、縦３ｍ、横２００ｍｍ）に塗布し、乾燥後に電極を
プレス機で加圧成形した。成形後、幅３９ｍｍ、長さ４
５０ｍｍにカットし、これを負極とした。得られた負極
においては、繊維が剥離することもなく、負極の表面は
平滑であった。Cycle test using a cylindrical battery A negative electrode was prepared as follows. That is, 30 g of polyvinylidene fluoride (PVDF) was dissolved in 420 ml of N-methyl-2-pyrrolidone. 270 g of the graphitized vapor-grown carbon fiber for lithium ion secondary battery negative electrode of the above (1) was added to the obtained solution and sufficiently dispersed by an ultrasonic disperser. A copper sheet (thickness 10 μ
m, length 3 m, width 200 mm), and after drying, the electrode was pressure-molded by a press machine. After molding, width 39mm, length 4
It was cut into 50 mm and used as a negative electrode. In the obtained negative electrode, the fiber was not peeled off, and the surface of the negative electrode was smooth.
【００４８】正極を以下のようにして作製した。ＰＶＤ
Ｆ２０ｇをＮ−メチル−２−ピロリドン３５０ミリリッ
トル中に溶解して溶液を得た。A positive electrode was produced as follows. PVD
A solution was obtained by dissolving 20 g of F in 350 ml of N-methyl-2-pyrrolidone.
【００４９】次に、ＬｉＣｏＯ2 ４４５ｇと、人造黒鉛
２０ｇと、アセチレンブラック１５ｇとをボールミル中
に入れて混合し、混合物を得た。Next, 445 g of LiCoO 2 , 20 g of artificial graphite and 15 g of acetylene black were put in a ball mill and mixed to obtain a mixture.
【００５０】前記混合物と前記溶液とを混合し、超音波
分散機により十分に分散させて分散液を得た。The above mixture and the above solution were mixed and sufficiently dispersed by an ultrasonic disperser to obtain a dispersion liquid.
【００５１】前記分散液をアルミニウムシート（厚さ２
０μｍ）に塗布した。このときの塗布面積は３００×１
５ｃｍであった。An aluminum sheet (thickness 2
0 μm). The application area at this time is 300 × 1
5 cm.
【００５２】塗布後、前記アルミニウムシートに電極を
プレス機で加圧成形した。成形後、幅３８ｍｍ、長さ４
３０ｍｍにカットし、これを正極とした。After coating, the aluminum sheet was pressure-molded with an electrode using a pressing machine. Width 38mm, length 4 after molding
It was cut into 30 mm and used as a positive electrode.
【００５３】以下のようにしてリチウムイオン二次電池
を作製した。前記正極および前記負極を、多孔質ポリプ
ロピレンシートのセパレータを介してロール状に巻き上
げた。このロール状の巻物を直径１６ｍｍおよび高さ５
０ｍｍの円筒型電池缶に納め、負極リード線を缶底に溶
接した。次いで、破裂板と閉塞蓋とガスケットとを有し
てなる正極キャップに正極リード線を溶接した。前記電
池缶内に、ＬｉＰＦ6を１モルの濃度になるようにエチ
レンカーボネート（ＥＣ）とプロピレンカーボネート
（ＰＣ）とジエチルカーボネート（ＤＥＣ）との混合溶
媒（容積比；ＥＣ／ＰＣ／ＤＥＣ＝２／１／２）に溶解
してなる電解液を入れ、前記正極キャップを負極缶の開
口部にかしめた。これにより、円筒型リチウムイオン二
次電池が得られた。A lithium ion secondary battery was manufactured as follows. The positive electrode and the negative electrode were wound up in a roll shape via a porous polypropylene sheet separator. This roll-shaped roll has a diameter of 16 mm and a height of 5
It was placed in a 0 mm cylindrical battery can and the negative electrode lead wire was welded to the bottom of the can. Next, a positive electrode lead wire was welded to a positive electrode cap having a rupture disk, a closing lid, and a gasket. Wherein in the battery can, a mixed solvent (volume ratio of the LiPF 6 1 mol of ethylene carbonate to a concentration of (EC) and propylene carbonate (PC) and diethyl carbonate (DEC); EC / PC / DEC = 2 / The electrolyte solution dissolved in (1/2) was put into the positive electrode cap, and the positive electrode cap was caulked in the opening of the negative electrode can. As a result, a cylindrical lithium ion secondary battery was obtained.
【００５４】充放電電流を６００ｍＡ、充放電電圧（負
極−正極間電圧）を２．５〜４．１Ｖとして、前記円筒
型リチウムイオン二次電池の充放電を１００サイクル行
った。１サイクル目、５０サイクル目および１００サイ
クル目の放電容量を測定し、その結果を表２に示した。
また、１００サイクル目放電容量と５０サイクル目放電
容量との比（１００サイクル目放電容量／５０サイクル
目放電容量）を放電容量比として表２に示した。The cylindrical lithium ion secondary battery was charged and discharged 100 cycles by setting the charge / discharge current to 600 mA and the charge / discharge voltage (voltage between the negative electrode and the positive electrode) to 2.5 to 4.1 V. The discharge capacities at the first cycle, the 50th cycle and the 100th cycle were measured, and the results are shown in Table 2.
Table 2 shows the ratio of the 100th cycle discharge capacity to the 50th cycle discharge capacity (100th cycle discharge capacity / 50th cycle discharge capacity) as the discharge capacity ratio.
【００５５】（実施例２） （１）リチウムイオン二次電池用黒鉛化気相成長炭素繊
維の製造 平均直径３μｍおよび平均繊維長５０μｍの気相成長炭
素繊維を、アルゴンガス雰囲気下に２，８００℃に３０
分かけて黒鉛化処理をすることにより、黒鉛化気相成長
炭素繊維を製造した。この黒鉛化気相成長炭素繊維は、
平均アスペクト比が１７であり、黒鉛網面間距離（ｄ
oo2 ）が０．３３６４ｎｍであり、黒鉛結晶子の厚さ
（Ｌc ）が９０ｎｍであった。Example 2 (1) Production of Graphitized Vapor-Grown Carbon Fiber for Lithium-Ion Secondary Battery Vapor-grown carbon fiber having an average diameter of 3 μm and an average fiber length of 50 μm was charged in an argon gas atmosphere at 2,800. 30 to ℃
Graphitized vapor-grown carbon fibers were produced by performing graphitization treatment over a period of time. This graphitized vapor grown carbon fiber is
The average aspect ratio is 17, and the distance between graphite mesh planes (d
oo2 ) was 0.3364 nm, and the thickness (L c ) of the graphite crystallite was 90 nm.
【００５６】この黒鉛化気相成長炭素繊維４０ｇをハイ
ブリダイザー（ＮＨＳ−１、（株）奈良機械製作所製）
に装填して、４，０００ｒｐｍ（周速５０ｍ／ｓ）にて
２分間高衝撃処理をした。高衝撃処理をして得られた炭
素繊維からランダムに選ばれた１，０００本の繊維を走
査型電子顕微鏡写真に撮り、その平均繊維長および平均
直径を既述した方法により測定したところ、平均繊維長
は２１．８μｍであり、平均直径は３μｍであった。よ
って、この切断処理により得られたものは、この発明の
リチウムイオン二次電池負極用黒鉛化気相成長炭素繊維
であった。40 g of this graphitized vapor grown carbon fiber was hybridized (NHS-1, manufactured by Nara Machinery Co., Ltd.)
And subjected to high impact treatment at 4,000 rpm (peripheral speed 50 m / s) for 2 minutes. 1,000 fibers randomly selected from the carbon fibers obtained by the high impact treatment were taken on a scanning electron micrograph, and the average fiber length and average diameter were measured by the method described above. The fiber length was 21.8 μm and the average diameter was 3 μm. Therefore, what was obtained by this cutting treatment was the graphitized vapor-grown carbon fiber for a negative electrode of a lithium ion secondary battery of the present invention.
【００５７】（２）リチウムイオン二次電池負極用黒鉛
化気相成長炭素繊維の評価 このリチウムイオン二次電池負極用黒鉛化気相成長炭素
繊維を用いて前記実施例１におけるのと同様の三電極式
ビーカセルを、組み立てた。前記実施例１におけるのと
同様にして、充填容量、放電容量、および充放電効率を
測定した。結果を表１に示した。また、前記実施例１に
おけるのと同様にして円筒型リチウムイオン二次電池を
組み立ててサイクル試験を行い、その結果を表２に示し
た。(2) Evaluation of Graphitized Vapor Growth Carbon Fiber for Lithium Ion Secondary Battery Negative Electrode Using this graphitized vapor phase grown carbon fiber for lithium ion secondary battery negative electrode, the same three steps as in Example 1 were performed. An electrode type beaker cell was assembled. The filling capacity, the discharge capacity, and the charging / discharging efficiency were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, a cylindrical lithium ion secondary battery was assembled and a cycle test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
【００５８】（比較例１）前記実施例１で使用されたの
と同じ黒鉛化気相成長炭素繊維を、ハイブリダイザー
（ＮＨＳ−１、（株）奈良機械製作所製）に装填して、
８，０００ｒｐｍ（周速１００ｍ／ｓ）にて２分間高衝
撃処理をした。高衝撃処理をして得られた炭素繊維から
ランダムに選ばれた１，０００本の繊維を電子顕微鏡写
真に撮り、その平均繊維長および平均直径を既述した方
法により測定したところ、平均繊維長は１１．６μｍで
あり、平均直径は２μｍであった。Comparative Example 1 The same graphitized vapor-grown carbon fiber used in Example 1 was loaded into a hybridizer (NHS-1, manufactured by Nara Machinery Co., Ltd.),
A high impact treatment was performed for 2 minutes at 8,000 rpm (peripheral speed 100 m / s). 1,000 fibers randomly selected from the carbon fibers obtained by high impact treatment were taken on an electron micrograph and the average fiber length and average diameter were measured by the method described above. Was 11.6 μm and the average diameter was 2 μm.
【００５９】このリチウムイオン二次電池負極用黒鉛化
気相成長炭素繊維を用いて前記実施例１におけるのと同
様の三電極式ビーカセルを、組み立てた。前記実施例１
におけるのと同様にして、充電容量、放電容量および充
放電効率を測定した。結果を表１に示した。また前記実
施例１におけるのと同様に円筒型リチウムイオン二次電
池を組み立ててサイクル試験を行い、その結果を表２に
示した。Using this graphitized vapor-grown carbon fiber for negative electrode of lithium ion secondary battery, a three-electrode type beaker cell similar to that in Example 1 was assembled. Example 1
The charge capacity, discharge capacity, and charge / discharge efficiency were measured in the same manner as in. The results are shown in Table 1. Further, a cylindrical lithium ion secondary battery was assembled and a cycle test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
【００６０】（比較例２）前記実施例２で使用されたの
と同じ黒鉛化気相成長炭素繊維を、ハイブリダイザー
（ＮＨＳ−１、（株）奈良機械製作所製）に装填して、
８，０００ｒｐｍ（周速１００ｍ／ｓ）にて２分間高衝
撃処理をした。高衝撃処理をして得られた炭素繊維から
ランダムに選ばれた１，０００本の繊維を走査型電子顕
微鏡写真に撮り、その平均繊維長および平均直径を既述
した方法により測定したところ、平均繊維長は１３．７
μｍであり、平均直径は３μｍであった。Comparative Example 2 The same graphitized vapor-grown carbon fiber used in Example 2 was loaded into a hybridizer (NHS-1, manufactured by Nara Machinery Co., Ltd.),
A high impact treatment was performed for 2 minutes at 8,000 rpm (peripheral speed 100 m / s). 1,000 fibers randomly selected from the carbon fibers obtained by the high impact treatment were taken on a scanning electron micrograph, and the average fiber length and average diameter were measured by the method described above. Fiber length is 13.7
The average diameter was 3 μm.
【００６１】このリチウムイオン二次電池負極用黒鉛化
気相成長炭素繊維を用いて前記実施例１におけるのと同
様の三電極式ビーカセルを、組み立てた。前記実施例１
におけるのと同様にして、充電容量、放電容量および充
放電効率を測定した。結果を表１に示した。また前記実
施例１におけるのと同様に円筒型リチウムイオン二次電
池を組み立ててサイクル試験を行い、その結果を表２に
示した。A three-electrode type beaker cell similar to that in Example 1 was assembled using this graphitized vapor-grown carbon fiber for negative electrode of lithium ion secondary battery. Example 1
The charge capacity, discharge capacity, and charge / discharge efficiency were measured in the same manner as in. The results are shown in Table 1. Further, a cylindrical lithium ion secondary battery was assembled and a cycle test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
【００６２】（比較例３）前記実施例１で使用されたの
と同じ黒鉛化気相成長炭素繊維を、ハイブリダイザー
（ＮＨＳ−１、（株）奈良機械製作所製）に装填して、
４，０００ｒｐｍ（周速５０ｍ／ｓ）にて３０秒間高衝
撃処理をした。高衝撃処理をして得られた炭素繊維から
ランダムに選ばれた１，０００本の繊維を走査型電子顕
微鏡写真に撮り、その平均繊維長および平均直径を既述
した方法により測定したところ、平均繊維長は３１．３
μｍであり、平均直径は２μｍであった。(Comparative Example 3) The same graphitized vapor grown carbon fiber used in Example 1 was loaded into a hybridizer (NHS-1, manufactured by Nara Machinery Co., Ltd.),
High impact treatment was performed for 30 seconds at 4,000 rpm (peripheral speed 50 m / s). 1,000 fibers randomly selected from the carbon fibers obtained by the high impact treatment were taken on a scanning electron micrograph, and the average fiber length and average diameter were measured by the method described above. Fiber length is 31.3
The average diameter was 2 μm.
【００６３】このリチウムイオン二次電池負極用黒鉛化
気相成長炭素繊維を用いて前記実施例１におけるのと同
様の三電極式ビーカセルを、組み立てた。なお、負極の
表面は平滑ではなかった。前記実施例１におけるのと同
様にして、充電容量、放電容量および充放電効率を測定
した。結果を表１に示した。Using this graphitized vapor-grown carbon fiber for negative electrode of lithium ion secondary battery, a three-electrode type beaker cell similar to that in Example 1 was assembled. The surface of the negative electrode was not smooth. The charge capacity, discharge capacity and charge / discharge efficiency were measured in the same manner as in Example 1. The results are shown in Table 1.
【００６４】[0064]
【表１】 [Table 1]
【００６５】[0065]
【表２】 [Table 2]
【００６６】[0066]
【発明の効果】この発明によると、負極から剥離するこ
とがなく、しかも負極の平面を平滑にすることができ、
さらには初回の充放電効率を大幅に改善し、サイクル特
性の向上したリチウムイオン二次電池を形成するのに好
適なリチウムイオン二次電池用黒鉛化気相成長炭素繊維
を提供することができる。According to the present invention, the plane of the negative electrode can be smoothed without peeling from the negative electrode.
Furthermore, it is possible to provide a graphitized vapor-grown carbon fiber for a lithium-ion secondary battery, which is suitable for forming a lithium-ion secondary battery with improved cycle characteristics by significantly improving the initial charge / discharge efficiency.
【００６７】この発明によると、充放電効率が高く、し
かもサイクル特性の優れたリチウムイオン二次電池を提
供することができる。According to the present invention, it is possible to provide a lithium ion secondary battery having high charge / discharge efficiency and excellent cycle characteristics.
Claims (2)
維長が１５〜２５μｍであることを特徴とするリチウム
イオン二次電池負極用黒鉛化気相成長炭素繊維。1. A graphitized vapor grown carbon fiber for a negative electrode of a lithium ion secondary battery, having an average diameter of 1 to 10 μm and an average fiber length of 15 to 25 μm.
次電池用黒鉛化気相成長炭素繊維から得られた負極を有
してなることを特徴とするリチウムイオン二次電池。2. A lithium-ion secondary battery comprising a negative electrode obtained from the graphitized vapor-grown carbon fiber for a lithium-ion secondary battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8187677A JPH0992286A (en) | 1995-07-18 | 1996-07-17 | Graphitized vapor phase epitaxy carbon fiber for lithium ion secondary battery and lithium ion secondary battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-181798 | 1995-07-18 | ||
| JP18179895 | 1995-07-18 | ||
| JP8187677A JPH0992286A (en) | 1995-07-18 | 1996-07-17 | Graphitized vapor phase epitaxy carbon fiber for lithium ion secondary battery and lithium ion secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0992286A true JPH0992286A (en) | 1997-04-04 |
Family
ID=26500823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8187677A Abandoned JPH0992286A (en) | 1995-07-18 | 1996-07-17 | Graphitized vapor phase epitaxy carbon fiber for lithium ion secondary battery and lithium ion secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0992286A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109594A (en) * | 2001-10-01 | 2003-04-11 | Showa Denko Kk | Electrode material, manufacturing method of the same, electrode for battery using the same, and battery using the electrode |
| JP2008112734A (en) * | 2007-11-30 | 2008-05-15 | Hitachi Chem Co Ltd | Carbon powder for lithium secondary battery negative electrode, manufacturing method therefor, negative electrode for the lithium secondary battery, and the lithium secondary battery |
| JP2011181524A (en) * | 2011-06-06 | 2011-09-15 | Hitachi Chem Co Ltd | Carbon powder for lithium secondary battery negative electrode, method of manufacturing the same, negative electrode for lithium secondary battery, and lithium secondary battery |
| CN114835111A (en) * | 2022-05-30 | 2022-08-02 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
| CN114835111B (en) * | 2022-05-30 | 2024-04-30 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
-
1996
- 1996-07-17 JP JP8187677A patent/JPH0992286A/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109594A (en) * | 2001-10-01 | 2003-04-11 | Showa Denko Kk | Electrode material, manufacturing method of the same, electrode for battery using the same, and battery using the electrode |
| JP2008112734A (en) * | 2007-11-30 | 2008-05-15 | Hitachi Chem Co Ltd | Carbon powder for lithium secondary battery negative electrode, manufacturing method therefor, negative electrode for the lithium secondary battery, and the lithium secondary battery |
| JP2011181524A (en) * | 2011-06-06 | 2011-09-15 | Hitachi Chem Co Ltd | Carbon powder for lithium secondary battery negative electrode, method of manufacturing the same, negative electrode for lithium secondary battery, and lithium secondary battery |
| CN114835111A (en) * | 2022-05-30 | 2022-08-02 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
| CN114835111B (en) * | 2022-05-30 | 2024-04-30 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
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