JP2003068301A - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary batteryInfo
- Publication number
- JP2003068301A JP2003068301A JP2001255463A JP2001255463A JP2003068301A JP 2003068301 A JP2003068301 A JP 2003068301A JP 2001255463 A JP2001255463 A JP 2001255463A JP 2001255463 A JP2001255463 A JP 2001255463A JP 2003068301 A JP2003068301 A JP 2003068301A
- Authority
- JP
- Japan
- Prior art keywords
- graphite particles
- negative electrode
- secondary battery
- graphite
- aqueous secondary
- 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.)
- Withdrawn
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水二次電池に関
し、さらに詳しくは、負荷特性にすぐれた非水二次電池
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery, and more particularly to a non-aqueous secondary battery having excellent load characteristics.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池に代表される非
水二次電池では、負極活物質として、黒鉛材料を使用し
ている。とくに最近では、高容量化の要請から、黒鉛材
料の中でも、リチウムイオンを吸蔵・放出できる容量が
大きな天然黒鉛や、これと同じような形態を持たせた人
造黒鉛が用いられている。2. Description of the Related Art In a non-aqueous secondary battery represented by a lithium ion secondary battery, a graphite material is used as a negative electrode active material. In recent years, in particular, due to a demand for higher capacity, among graphite materials, natural graphite having a large capacity for occluding and releasing lithium ions and artificial graphite having a similar shape to this have been used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
ような従来の黒鉛粒子は、一般に、粒子形状が鱗片状と
なるものであり、このような黒鉛粒子を使用すると、電
池の負荷特性が悪くなることが知られており、使用上の
問題となっていた。However, the conventional graphite particles as described above generally have a scaly particle shape, and the use of such graphite particles deteriorates the load characteristics of the battery. It was known that this was a problem in use.
【０００４】本発明は、このような事情に照らして、負
極活物質である黒鉛粒子として上記従来のものとは異な
る特定のものを使用することにより、負荷特性にすぐれ
た非水二次電池を提供することを目的としている。In view of such circumstances, the present invention provides a non-aqueous secondary battery having excellent load characteristics by using graphite particles as a negative electrode active material, which are different from the conventional ones. It is intended to be provided.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するため、鋭意検討した結果、負極活物質とし
て、円形度の高い黒鉛粒子を主体とし、これに上記以外
の黒鉛粒子、たとえばメソフェーズカーボン黒鉛化品や
繊維状黒鉛などを混合使用して、集電体上に形成される
負極合剤層における黒鉛粒子のＸ線回折による配向度が
一定値以上となるように構成したときには、非水二次電
池の負荷特性が顕著に改善されたものとなることを知
り、本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, as a negative electrode active material, graphite particles having high circularity were mainly contained, and graphite particles other than the above , A mixture of, for example, mesophase carbon graphitized product and fibrous graphite was used so that the degree of orientation by X-ray diffraction of the graphite particles in the negative electrode mixture layer formed on the current collector was a certain value or more. At times, it was found that the load characteristics of the non-aqueous secondary battery were remarkably improved, and the present invention was completed.
【０００６】すなわち、本発明は、リチウムイオンを吸
蔵・放出可能な正極活物質を用いた正極と負極と非水系
の電解質を有する非水二次電池において、負極は、集電
体とこの上に形成された負極活物質として平均円形度が
０．９３以上の黒鉛粒子とそれ以外の黒鉛粒子とを含む
負極合剤層とからなり、この負極合剤層のＸ繰回折によ
る黒鉛粒子の配向度が０．００１以上であることを特徴
とする非水二次電池に係るものであり、とくに上記の平
均円形度が０．９３以上の黒鉛粒子が天然黒鉛からなる
上記構成の非水二次電池に係るものである。また、本発
明は、上記の平均円形度が０．９３以上の黒鉛粒子以外
の黒鉛粒子がメソフェーズカーボン黒鉛化品および繊維
状黒鉛の中から選ばれる少なくともひとつである上記構
成の非水二次電池、とくに、メソフェーズカーボン黒鉛
化品が黒鉛粒子全体の３〜２５重量％である、あるいは
繊維状黒鉛が黒鉛粒子全体の０．１〜３重量％である上
記構成の非水二次電池に係るものである。That is, the present invention is a non-aqueous secondary battery having a positive electrode and a negative electrode using a positive electrode active material capable of inserting and extracting lithium ions, and a non-aqueous electrolyte. The formed negative electrode active material comprises a negative electrode mixture layer containing graphite particles having an average circularity of 0.93 or more and other graphite particles, and the degree of orientation of the graphite particles by X diffraction of the negative electrode mixture layer. Is 0.001 or more, and particularly relates to a non-aqueous secondary battery having the above-mentioned configuration, in which the graphite particles having an average circularity of 0.93 or more are natural graphite. It is related to. The present invention also provides the non-aqueous secondary battery having the above-mentioned configuration, in which the graphite particles other than the above-mentioned graphite particles having an average circularity of 0.93 or more are at least one selected from mesophase carbon graphitized products and fibrous graphite. In particular, the non-aqueous secondary battery having the above structure in which the mesophase carbon graphitized product is 3 to 25% by weight of the entire graphite particles, or the fibrous graphite is 0.1 to 3% by weight of the entire graphite particles. Is.
【０００７】[0007]
【発明の実施の形態】本発明に用いられる平均円形度が
０．９３以上の黒鉛粒子（以下、単に円形黒鉛粒子とい
う）は、粒子形状が鱗片状の黒鉛粒子に比べて、電池の
負荷特性の向上に寄与するものであり、天然黒鉛、人造
黒鉛のいずれでもよい。人造黒鉛は、一般に、放電容量
が天然黒鉛に比べて小さく、また製造時に膨大なエネル
ギーと長時間を要して、高価となるため、天然黒鉛がよ
り好ましい。平均円形度が０．９３未満となると、電池
の負荷特性の向上に好結果を得にくい。BEST MODE FOR CARRYING OUT THE INVENTION Graphite particles having an average circularity of 0.93 or more (hereinafter simply referred to as circular graphite particles) used in the present invention have a load characteristic of a battery higher than that of graphite particles having a scaly particle shape. Any of natural graphite and artificial graphite may be used because it contributes to the improvement of Artificial graphite generally has a smaller discharge capacity than natural graphite, requires enormous energy and a long time at the time of production, and is expensive. Therefore, natural graphite is more preferable. If the average circularity is less than 0.93, it is difficult to obtain good results in improving the load characteristics of the battery.
【０００８】このような円形黒鉛粒子は、たとえば天然
黒鉛の場合、以下のように製造できる。すなわち、黒鉛
鉱山より産出した天然黒鉛を精製し、ジェットミルなど
の汎用の乾式粉砕機で粉砕して、所望の円形度を持つ天
然黒鉛とすればよい。また、この乾式粉砕の前か後に、
サンドミルなどの湿式粉砕を併用してもよい。さらに適
当な粉砕助剤を加えてもよく、乾式、湿式の分級機を使
用して、円形度を低下させるフラクションを除くように
してもよい。Such circular graphite particles can be produced, for example, in the case of natural graphite as follows. That is, natural graphite produced from a graphite mine may be purified and crushed by a general-purpose dry crusher such as a jet mill to obtain natural graphite having a desired circularity. Also, before or after this dry grinding,
You may use together wet grinding, such as a sand mill. Further, a suitable grinding aid may be added, and a dry or wet classifier may be used to remove the fraction that reduces the circularity.
【０００９】本発明に用いられる円形黒鉛粒子以外の黒
鉛粒子（以下、単に他種黒鉛粒子という）は、円形黒鉛
粒子単独では負極合剤層中での黒鉛粒子の配向度が小さ
くなり、黒鉛粒子が過度に配向して負荷特性の改善を妨
げるため、これに他種黒鉛粒子を混合して上記配向度を
大きくし、負荷特性のさらなる改善をはかるものであ
る。このような他種黒鉛粒子としては、メソフェーズカ
ーボン黒鉛化品や繊維状黒鉛がとくに好ましいが、これ
以外のものであってもよい。Graphite particles other than the circular graphite particles used in the present invention (hereinafter simply referred to as other-type graphite particles) have a low degree of orientation of the graphite particles in the negative electrode mixture layer when the circular graphite particles are used alone. Excessively orients and hinders the improvement of the load characteristics. Therefore, graphite particles of other species are mixed with the particles to increase the degree of orientation and further improve the load characteristics. As such other-type graphite particles, mesophase carbon graphitized products and fibrous graphite are particularly preferable, but other particles may be used.
【００１０】上記の他種黒鉛粒子は、これが少なすぎる
と上記効果が得られず、多すぎると配向度が大きくなっ
ても放電量の低下が顕著となり、いずれも、好ましくな
い。他種黒鉛粒子の種類に応じて最適使用量を選択すべ
きであり、メソフェーズカーボン黒鉛化品の場合は、黒
鉛粒子全体の３〜２５重量％、繊維状黒鉛の場合は、黒
鉛粒子全体の０．１〜３重量％とするのが望ましい。If the amount of the other type of graphite particles is too small, the above effect cannot be obtained, and if the amount is too large, the discharge amount is remarkably decreased even if the degree of orientation is increased, which is not preferable. The optimum amount to be used should be selected according to the type of other type of graphite particles. In the case of mesophase carbon graphitized product, it is 3 to 25% by weight of the whole graphite particles, and in the case of fibrous graphite, it is 0 It is desirable to be 0.1 to 3% by weight.
【００１１】本発明においては、負極活物質として、上
記の円形黒鉛粒子と他種黒鉛粒子を混合して使用する
が、両黒鉛粒子の混合は、通常の粉体混合機としてプラ
ネタリーミキサーやヘンシェルミキサーなどを用いて、
行うことができる。繊維状黒鉛の場合は、粒子凝集を防
ぐために、ヘンシェルミキサーのような凝集粒子に強い
せん断力を与えられる混合機を使用するのが望ましい。In the present invention, the above-mentioned circular graphite particles and other-type graphite particles are mixed and used as the negative electrode active material, and both graphite particles are mixed by a planetary mixer or a Henschel as a usual powder mixer. Using a mixer, etc.
It can be carried out. In the case of fibrous graphite, in order to prevent particle agglomeration, it is desirable to use a mixer such as a Henschel mixer capable of imparting a strong shearing force to agglomerated particles.
【００１２】本発明において、負極は、たとえば、以下
のように作製できる。まず、上記の円形黒鉛粒子と他種
黒鉛粒子との混合物を負極活物質とし、これに必要によ
り、ポリフッ化ビニリデン、ポリテトラフルオロエチレ
ンなどのバインダーなどを混合し、これらを溶剤に分散
させて負極合剤ペーストを調製する。バインダーはあら
かじめ溶剤に溶解させておいてから負極活物質などと混
合してもよい。つぎに、この負極合剤ペーストを基体を
兼ねる集電体上に塗布し、乾燥して、負極合剤層を形成
することにより、負極が作製される。In the present invention, the negative electrode can be manufactured, for example, as follows. First, a mixture of the above-mentioned circular graphite particles and other types of graphite particles is used as a negative electrode active material, and if necessary, polyvinylidene fluoride, a binder such as polytetrafluoroethylene are mixed, and these are dispersed in a solvent to form a negative electrode. Prepare a mixture paste. The binder may be dissolved in a solvent in advance and then mixed with the negative electrode active material or the like. Next, this negative electrode mixture paste is applied onto a current collector that also serves as a substrate, and dried to form a negative electrode mixture layer, whereby a negative electrode is produced.
【００１３】バインダーには、スチレン−ブタジェン共
重合体（ＳＢＲ）／カルボキシメチルセルロ−ス（ＣＭ
Ｃ）系などの水系バインダーを用いてもよい。負極合剤
ペーストを集電体上に塗布するには、押出しコーター、
リバースローラー、ドクターブレードなどの塗布方法が
用いられる。集電体には、アルミニウム、ニッケル、ス
テンレス鋼、チタン、銅などの金属の網、パンチドメタ
ル、エキスパンドメタル、フォームメタル、箔などが用
いられるが、とくに銅箔が適している。なお、負極の作
製は、上記方法に限られず、他の方法によってもよい。The binder is a styrene-butadiene copolymer (SBR) / carboxymethyl cellulose (CM).
An aqueous binder such as C) may be used. To apply the negative electrode mixture paste onto the current collector, use an extrusion coater,
A coating method such as a reverse roller or a doctor blade is used. A metal net such as aluminum, nickel, stainless steel, titanium, or copper, punched metal, expanded metal, foam metal, or foil is used for the current collector, and copper foil is particularly suitable. Note that the negative electrode is not limited to the above method and may be manufactured by another method.
【００１４】このように作製される負極は、負極合剤層
のＸ線回折による黒鉛粒子の配向度が０．００１以上で
あることを特徴とする。この配向度が０．００１未満で
あると負極合剤中で黒鉛が過度に配向するため十分な負
荷特性が得られない。配向度は以下のように測定する。
Ｘ線回折装置のガラスフォルダーに集電体上に負極合剤
層を形成した試料を両面テープで貼り付け、Ｘ繰回折装
置によって黒鉛の（００２）面の回折ピーク強度（Ｉ
002 ）と（１１０）面の回折ピーク強度（Ｉ110）を求
める。この強度比Ｉ110 ／Ｉ002 を配向度とする。The negative electrode thus produced is characterized in that the degree of orientation of graphite particles by X-ray diffraction of the negative electrode mixture layer is 0.001 or more. If this degree of orientation is less than 0.001, the graphite is excessively oriented in the negative electrode mixture, and sufficient load characteristics cannot be obtained. The degree of orientation is measured as follows.
A sample having a negative electrode material mixture layer formed on a current collector was attached to a glass folder of an X-ray diffractometer with a double-sided tape, and the diffraction peak intensity (I
002 ) and diffraction peak intensities (I 110 ) of the (110) plane are obtained. The intensity ratio I 110 / I 002 is the degree of orientation.
【００１５】本発明において、正極活物質はリチウムイ
オンの吸蔵・放出が可能なものであればよく、非水二次
電池の正極活物質として公知のものをいずれも使用でき
る。好適な例として、ＬｉＣｏＯ2 、ＬｉＭｎ2 Ｏ4 、
ＬｉＮｉＯ2 、ＬｉｘＮｉｙＭｎｚＯａなどのリチウム
含有複合金属酸化物が挙げられる。In the present invention, any positive electrode active material may be used as long as it can store and release lithium ions, and any known positive electrode active material for non-aqueous secondary batteries can be used. Suitable examples include LiCoO 2 , LiMn 2 O 4 ,
Examples thereof include lithium-containing composite metal oxides such as LiNiO 2 and LixNiyMnzOa.
【００１６】正極は、たとえば、以下のように作製でき
る。まず、上記の正極活物質に、必要により鱗片状黒
鉛、アセチレンブラック、カーボンブラックなどの導電
助剤や、負極の場合と同様のバインダーを混合し、これ
らを溶剤に分散させて、正極合剤ペーストを調製する。
バインダーはあらかじめ溶剤に溶解させておいてから正
極活物質などと混合してもよい。つぎに、この正極合剤
ペーストを基体を兼ねる集電体上に塗布し、乾燥して、
正極合剤層を形成することにより、正極が作製される。The positive electrode can be manufactured, for example, as follows. First, the above-mentioned positive electrode active material, if necessary, flaky graphite, acetylene black, a conductive aid such as carbon black, or a binder similar to the case of the negative electrode is mixed, these are dispersed in a solvent, the positive electrode mixture paste To prepare.
The binder may be dissolved in a solvent in advance and then mixed with the positive electrode active material or the like. Next, this positive electrode material mixture paste is applied onto a current collector that also serves as a substrate and dried,
A positive electrode is produced by forming a positive electrode mixture layer.
【００１７】正極合剤ペーストを集電体上に塗布するに
は、負極の場合と同様の各種の塗布方法を採用できる。
また、集電体には、アルミニウム、ニッケル、ステンレ
ス鋼、チタン、銅などの金属の網、パンチドメタル、エ
キスパンドメタル、フォームメタル、箔などが用いられ
るが、とくにアルミニウム箔が適している。正極の作製
は、上記方法に限られず、他の方法によってもよい。To apply the positive electrode mixture paste onto the current collector, various coating methods similar to those for the negative electrode can be adopted.
Further, as the current collector, a mesh of metal such as aluminum, nickel, stainless steel, titanium and copper, punched metal, expanded metal, foam metal, foil and the like are used, but aluminum foil is particularly suitable. The production of the positive electrode is not limited to the above method, and may be another method.
【００１８】本発明において、非水系の電解質には、一
般に電解液と呼ばれる液状電解質、これをゲル化剤でゲ
ル化したゲル状ポリマー電解質、無機系や有機系の固体
電解質などがあるが、液状電解質やゲル状ポリマー電解
質が好ましい。液状電解質は、最も多用されており、以
下「電解液」という表現で説明する。電解液は、有機溶
媒などの非水溶媒にリチウム塩などの電解質塩を溶解さ
せることにより、調製される。非水溶媒は、とくに限定
されないが、鎖状エステルを主溶媒とするのが望まし
い。鎖状エステルには、ジエチルカーボネート、ジメチ
ルカーボネート、エチルメチルカーボネート、酢酸エチ
ル、プロピオン酸メチルなどの鎖状のＣＯＯ−結合を有
する有機溶媒が用いられる。In the present invention, the non-aqueous electrolyte includes a liquid electrolyte generally called an electrolytic solution, a gel polymer electrolyte obtained by gelling this with a gelling agent, an inorganic or organic solid electrolyte, and the like. Electrolytes and gel polymer electrolytes are preferred. The liquid electrolyte is most frequently used, and will be described below by the expression "electrolytic solution". The electrolytic solution is prepared by dissolving an electrolyte salt such as a lithium salt in a non-aqueous solvent such as an organic solvent. The non-aqueous solvent is not particularly limited, but it is desirable to use a chain ester as the main solvent. As the chain ester, an organic solvent having a chain COO-bond such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, ethyl acetate, methyl propionate, etc. is used.
【００１９】上記の主溶媒とともに、誘電率の高いエス
テルが好ましく用いられる。具体的には、エチレンカー
ボネート、プロピレンカーボネート、プチレンカーボネ
ート、γ−ブチロラクトン、エチレングリコールサルフ
ァイトなどであり、とくに、エチレンカーボネートやプ
ロピレンカーボネートなどの環状構造のものが好まし
い。また、このような誘電率の高いエステル以外に、
１，２−ジメトキシエタン、１，３−ジオキソラン、テ
トラヒドロフラン、２−メチルーテトラヒドロフラン、
ジエチルエーテルなどや、その他、アミン系やイミド系
有機溶媒、含イオウ系や含フッ素系有機溶媒なども使用
することができる。An ester having a high dielectric constant is preferably used together with the above main solvent. Specifically, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, ethylene glycol sulfite and the like are preferable, and those having a cyclic structure such as ethylene carbonate and propylene carbonate are particularly preferable. In addition to such a high dielectric constant ester,
1,2-dimethoxyethane, 1,3-dioxolane, tetrahydrofuran, 2-methyl-tetrahydrofuran,
Diethyl ether and the like, as well as amine-based and imide-based organic solvents, sulfur-containing and fluorine-containing organic solvents, and the like can be used.
【００２０】電解液の調製にあたり、上記の非水溶媒に
溶解させる電解質塩には、たとえば、ＬｉＣｌＯ4 、Ｌ
ｉＰＦ6 、ＬｉＢＦ4 、ＬｉＡｓＦ6 、ＬｉＣＦ3 ＳＯ
3 、ＬｉＣ4 Ｆ9 ＳＯ3 、ＬｉＣＦ3 ＣＯ2 、Ｌｉ2 Ｃ
2 Ｆ4 （ＳＯ3 ）2 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、Ｌｉ
Ｃ（ＣＦ3 ＳＯ2 ）3 、ＬｉＣｎＦ2n+1ＳＯ3 （ｎ≧
２）、ＬｉＮ（ＲｆＯＳＯ2 ）2 （ここで、Ｒｆはフル
オロアルキル基〕などが単独でまたは２種以上混合して
用いられる。これらの中でも、ＬｉＰＦ6 やＬｉＣ4 Ｆ
9 ＳＯ3 などが好ましく用いられる。電解液における電
解質塩の濃度は、とくに限定されないが、通常、０．８
モル／リットル以上であるのが好ましく、また１．３モ
ル／リットル以下であるのが好ましい。In preparing the electrolytic solution, examples of the electrolyte salt to be dissolved in the above non-aqueous solvent include LiClO 4 and L.
iPF 6, LiBF 4, LiAsF 6 , LiCF 3 SO
3 , LiC 4 F 9 SO 3 , LiCF 3 CO 2 , Li 2 C
2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , Li
C (CF 3 SO 2 ) 3 , LiCnF 2n + 1 SO 3 (n ≧
2) and LiN (RfOSO 2 ) 2 (where Rf is a fluoroalkyl group) and the like are used alone or in combination of two or more. Among these, LiPF 6 and LiC 4 F
9 SO 3 and the like are preferably used. The concentration of the electrolyte salt in the electrolytic solution is not particularly limited, but is usually 0.8.
It is preferably not less than mol / liter and not more than 1.3 mol / liter.
【００２１】ゲル状ポリマー電解質は、上記の電解液を
ゲル化剤によってゲル化したものに相当するが、ゲル化
に際しては、ポリフツ化ビニリデン、ポリエチレンオキ
サイド、ポリアクリロニトリルなどの直鎖状ポリマーま
たはそれらのコポリマー、紫外線や電子線などの活性光
線の照射によりポリマー化する多官能モノマー（たとえ
ば、ペンタエリスリトールテトラアクリレート、ジトリ
メチロールプロパンテトラアクリレート、エトキシ化ペ
ンタエリスリトールテトラアクリレート、ジペンタエリ
スリトールヒドロキシペンタアクリレート、ジペンタエ
リスリトールヘキサアクリレートなどの四官能以上のア
クリレートまたは上記アクリレートと同様の四官能以上
のメタクリレートなど）が用いられる。The gel-like polymer electrolyte corresponds to a gelled product of the above-mentioned electrolytic solution with a gelling agent. Upon gelling, a linear polymer such as polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or a linear polymer thereof is used. Copolymers, polyfunctional monomers that are polymerized by irradiation with actinic rays such as ultraviolet rays and electron beams (for example, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, dipentaerythritol. A tetrafunctional or higher acrylate such as hexaacrylate or a tetrafunctional or higher methacrylate similar to the above acrylate) is used.
【００２２】上記の多官能モノマーの場合、モノマーそ
のものが電解液をゲル化させるのではなく、これをポリ
マー化したポリマーがゲル化剤として作用する。このよ
うに多官能モノマーを用いて電解液をゲル化させる場
合、必要により、重合開始剤として、ベンゾイル類、ベ
ンゾインアルキルエーテル類、ベンゾフェノン類、ベン
ゾイルフェニルフォスフィンオキサイド類、アセトフェ
ノン類、チオキサントン類、アントラキノン類などを使
用してもよい。また、重合開始剤の増惑剤としてアルキ
ルアミン類、アミノエステル類などを併用してもよい。In the case of the above polyfunctional monomer, the monomer itself does not gelate the electrolytic solution, but the polymer obtained by polymerizing the electrolytic solution acts as a gelling agent. When gelling an electrolytic solution using a polyfunctional monomer in this way, if necessary, as a polymerization initiator, benzoyls, benzoin alkyl ethers, benzophenones, benzoylphenylphosphine oxides, acetophenones, thioxanthones, anthraquinone Classes and the like may be used. In addition, alkylamines, aminoesters and the like may be used in combination as a pacing agent for the polymerization initiator.
【００２３】本発明の非水二次電池においては、通常、
正極と負極との問にセパレータを介在させる。セパレー
タは、とくに限定されないが、強度が十分で電解液を多
く保持できるものがよく、このような観点から、厚さが
１０〜５０μｍで、開孔率が３０〜７０％のポリプロピ
レン製、ポリエチレン製、プロピレンとエチレンとのコ
ポリマー製の微孔性フィルムや不織布などが好ましい。In the non-aqueous secondary battery of the present invention, normally,
A separator is interposed between the positive electrode and the negative electrode. The separator is not particularly limited, but is preferably one having sufficient strength and capable of holding a large amount of electrolytic solution. From this viewpoint, the thickness is 10 to 50 μm, and the porosity is made of polypropylene or polyethylene of 30 to 70%. A microporous film or a non-woven fabric made of a copolymer of propylene and ethylene is preferable.
【００２４】本発明の非水二次電池は、たとえば、正極
および負極をセパレータを介して積層または巻回して電
極体を作製し、これを金属製の電池ケース内あるいはア
ルミニウム箔などの金属箔を芯材とするラミネートフィ
ルムで構成される外装材内に収容し、電解液の注入後、
密閉することにより、作製される．また、上記電極体を
電池ケースに収容して非水二次電池を構成する場合、電
池ケースの封口に際して使用する封口体には、開裂ベン
トを設けておくのが望ましい。In the non-aqueous secondary battery of the present invention, for example, a positive electrode and a negative electrode are laminated or wound with a separator interposed therebetween to produce an electrode body, which is then placed in a metal battery case or a metal foil such as an aluminum foil. It is housed in an exterior material composed of a laminated film as a core material, and after injection of an electrolytic solution,
It is produced by sealing. Moreover, when the above-mentioned electrode body is housed in a battery case to form a non-aqueous secondary battery, it is desirable to provide a cleavage vent in the sealing body used for sealing the battery case.
【００２５】[0025]
【実施例】つぎに、本発明の実施例を記載して、より具
体的に説明する．ただし、本発明は以下の実施例のみに
限定されるものではない。なお、以下において、部とあ
るのは重量部を意味するものとする。EXAMPLES Next, examples of the present invention will be described to more specifically describe. However, the present invention is not limited to the following examples. In the following, "parts" means "parts by weight".
【００２６】実施例１
黒鉛原料として薬剤精製済みの天然黒鉛を使用し、乾式
粉砕機（ジェットミル、特開平１１−２６３６１２号公
報に記載されているのと同様のもの）により、空気圧
２．２Kg、空気量３．５m3／分、空気速度１．２ｍ／
秒、操作時間４５分の条件で、平均円形度が０．９３５
である円形天然黒鉛粒子を製造した。Example 1 Natural graphite, which has been subjected to chemical purification, was used as a graphite raw material, and an air pressure of 2.2 Kg was obtained by a dry pulverizer (jet mill, similar to that described in JP-A-11-263612). , Air volume 3.5m 3 / min, air velocity 1.2m /
The average circularity is 0.935 under the condition of seconds and operating time of 45 minutes.
To produce circular natural graphite particles.
【００２７】上記の円形天然黒鉛粒子７５部と、他種黒
鉛粒子としてメソフェーズカーボン黒鉛化品２５部と
を、プラネタリーミキサーで混合した。これにバインダ
ーとしてのポリフッ化ビニリデンを、混合黒鉛粒子とバ
インダーとの重量比が９０：１０となるように混合し、
これらをＮ−メチル−２−ピロリドンに分散させて負極
合剤ペーストを調製した。この負極合剤ペーストを、厚
さが１０μｍの銅箔からなる集電体の両面に塗布し、乾
燥して、集電体の両面に負極合剤層を形成したのち、カ
レンダーでプレスして、シート状の負極を作製した。75 parts of the above-mentioned circular natural graphite particles and 25 parts of mesophase carbon graphitized product as other-type graphite particles were mixed by a planetary mixer. Polyvinylidene fluoride as a binder was mixed in this so that the weight ratio of the mixed graphite particles and the binder was 90:10,
These were dispersed in N-methyl-2-pyrrolidone to prepare a negative electrode mixture paste. This negative electrode mixture paste is applied to both sides of a current collector made of a copper foil having a thickness of 10 μm, dried to form a negative electrode mixture layer on both sides of the current collector, and then pressed with a calendar, A sheet-shaped negative electrode was produced.
【００２８】つぎに、この負極を用いて、非水二次電池
としての「１４５００型電池」を作製した。この非水二
次電池は、正極として、アルミニウム箔からなる集電体
の両面に正極活物質であるＬｉＣｏＯ2 とバインダーと
してのポリフッ化ビニリデンを含む正極合剤層を設けた
ものを使用し、また電解液として、エチレンカーボネー
ト／エチルメチルカーボネート＝１／２（体積比）の混
合溶剤に電解質塩としてＬｉＰＦ6 を１．２モル／リッ
トル溶解させたものを使用し、さらにセパレータとし
て、ポリプロピレン製の微孔性フィルムを使用したもの
である。Next, using this negative electrode, a "14500 type battery" as a non-aqueous secondary battery was produced. This non-aqueous secondary battery uses, as a positive electrode, a positive electrode mixture layer containing LiCoO 2 as a positive electrode active material and polyvinylidene fluoride as a binder on both sides of a current collector made of aluminum foil, and As the electrolytic solution, a solution obtained by dissolving 1.2 mol / liter of LiPF 6 as an electrolyte salt in a mixed solvent of ethylene carbonate / ethyl methyl carbonate = 1/2 (volume ratio) was used. A porous film is used.
【００２９】実施例２
円形天然黒鉛粒子とメソフェーズカーボン黒鉛化品との
混合割合を、円形天然黒鉛粒子が９７部、メソフェーズ
カーボン黒鉛化品が３部となるように変更した以外は、
実施例１と同様にして、負極を作製した。この負極を用
い、実施例１と同様にして、非水二次電池（１４５００
型電池）を作製した。Example 2 Except that the mixing ratio of the circular natural graphite particles and the mesophase carbon graphitized product was changed to 97 parts for the circular natural graphite particles and 3 parts for the mesophase carbon graphitized product.
A negative electrode was produced in the same manner as in Example 1. Using this negative electrode, in the same manner as in Example 1, a non-aqueous secondary battery (14500
Type battery) was produced.
【００３０】実施例３
他種黒鉛粒子として繊維状黒鉛を使用し、これと円形天
然黒鉛粒子を、円形天然黒鉛粒子が９７部、繊維状黒鉛
が３部となるように混合使用し、混合にヘンシェルミキ
サーを使用した以外は、実施例１と同様にして、負極を
作製した。この負極を用い、実施例１と同様にして、非
水二次電池（１４５００型電池）を作製した。Example 3 Fibrous graphite was used as another kind of graphite particles, and this and circular natural graphite particles were mixed and used so that 97 parts of circular natural graphite particles and 3 parts of fibrous graphite were mixed and used. A negative electrode was produced in the same manner as in Example 1 except that a Henschel mixer was used. Using this negative electrode, a nonaqueous secondary battery (14500 type battery) was produced in the same manner as in Example 1.
【００３１】実施例４
円形天然黒鉛粒子と繊維状黒鉛との混合割合を、円形天
然黒鉛粒子が９９．９部、繊維状黒鉛が０．１部となる
ように変更した以外は、実施例３と同様にして、負極を
作製した。この負極を用い、実施例１と同様にして、非
水二次電池（１４５００型電池）を作製した。Example 4 Example 3 was repeated except that the mixing ratio of the circular natural graphite particles and the fibrous graphite was changed to 99.9 parts for the circular natural graphite particles and 0.1 parts for the fibrous graphite. A negative electrode was prepared in the same manner as in. Using this negative electrode, a nonaqueous secondary battery (14500 type battery) was produced in the same manner as in Example 1.
【００３２】実施例５
他種黒鉛粒子として、メソフェーズカーボン黒鉛化品と
繊維状黒鉛を併用し、これと円形天然黒鉛粒子を、円形
天然黒鉛粒子が８４部、メソフェーズカーボン黒鉛化品
が１５部、繊維状黒鉛が１部となるように混合使用し、
混合にヘンシェルミキサーを使用した以外は、実施例１
と同様にして、負極を作製した。この負極を用い、実施
例１と同様にして、非水二次電池（１４５００型電池）
を作製した。Example 5 As another kind of graphite particles, a mesophase carbon graphitized product and fibrous graphite were used in combination, and the circular natural graphite particles were 84 parts, and the mesophase carbon graphitized product was 15 parts. Mix and use so that fibrous graphite becomes 1 part,
Example 1 except that a Henschel mixer was used for mixing
A negative electrode was prepared in the same manner as in. Using this negative electrode, in the same manner as in Example 1, non-aqueous secondary battery (14500 type battery)
Was produced.
【００３３】比較例１
メソフェーズカーボン黒鉛化品を使用せず、円形天然黒
鉛粒子を１００部使用した以外は、実施例１と同様にし
て、負極を作製した。この負極を用い、実施例１と同様
にして、非水二次電池（１４５００型電池）を作製し
た。Comparative Example 1 A negative electrode was prepared in the same manner as in Example 1 except that 100 parts of circular natural graphite particles were used without using the mesophase carbon graphitized product. Using this negative electrode, a nonaqueous secondary battery (14500 type battery) was produced in the same manner as in Example 1.
【００３４】比較例２
平均円形度が０．９３５である円形天然黒鉛粒子に代え
て、平均円形度が０．８６８である天然黒鉛粒子（実施
例１における粉砕条件を変更して製造した黒鉛粒子）を
用いた以外は、実施例１と同様にして、負極を作製し
た。この負極を用い、実施例１と同様にして、非水二次
電池（１４５００型電池）を作製した。Comparative Example 2 Instead of circular natural graphite particles having an average circularity of 0.935, natural graphite particles having an average circularity of 0.868 (graphite particles produced by changing the grinding conditions in Example 1) A negative electrode was produced in the same manner as in Example 1 except that (1) was used. Using this negative electrode, a nonaqueous secondary battery (14500 type battery) was produced in the same manner as in Example 1.
【００３５】比敦例３
平均円形度が０．９３５である円形天然黒鉛粒子に代え
て、平均円形度が０．８６８である天然黒鉛粒子（実施
例１における粉砕条件を変更して製造した黒鉛粒子）を
用いた以外は、実施例３と同様にして、負極を作製し
た。この負極を用い、実施例１と同様にして、非水二次
電池（１４５００型電池）を作製した。Hidatsu Example 3 Instead of circular natural graphite particles having an average circularity of 0.935, natural graphite particles having an average circularity of 0.868 (graphite produced by changing the grinding conditions in Example 1) A negative electrode was produced in the same manner as in Example 3 except that the particles were used. Using this negative electrode, a nonaqueous secondary battery (14500 type battery) was produced in the same manner as in Example 1.
【００３６】上記の実施例１〜５および比較例１〜３の
非水二次電池について、使用した負極の負極合剤層中の
黒鉛粒子の配向度の測定と、電池の放電特性試験とを、
下記の方法により、行った。これらの結果を、負極に使
用した他種黒鉛粒子の種類と量（黒鉛粒子全体中の重量
％）とともに、表１に示した。表１中、他種黒鉛粒子を
示す「Ａ」はメソフェーズカーボン黒鉛化品、「Ｂ」は
繊維状黒鉛である。For the non-aqueous secondary batteries of Examples 1 to 5 and Comparative Examples 1 to 3 described above, the degree of orientation of graphite particles in the negative electrode mixture layer of the negative electrode used and the discharge characteristic test of the battery were tested. ,
The following method was used. These results are shown in Table 1 together with the type and amount of other-type graphite particles used in the negative electrode (% by weight in the whole graphite particles). In Table 1, "A" indicating other-type graphite particles is a mesophase carbon graphitized product, and "B" is fibrous graphite.
【００３７】＜負極合剤層中の黒鉛粒子の配向度の測定
＞負極をＸＲＤ用ガラスセルに両面テープで貼り付け、
（００２）面と（１１０）面との回折強度を、リガク社
製Ｘ線回折装置「ＲＩＮＴ２５００」を用いて、
電圧：５０ＫＶ
電流：２００ｍＡ
操作角：２５．５〜２７．５度および７６．５〜７８．
５度
走査速度：６度／分（２５．５〜２７．５度）
０．２度／分（７６．５〜７８．５度）
の条件で求めた。また、データ処理は、積分強度比、平
均化点数９点、自動バックグランド除去で行った。配向
度は、（００２）面の回折ピーク（２６．５度）強度
（Ｉ002 ）と、（１１０）面の回折ピーク（７７．５
度）強度（Ｉ110 ）とから、Ｉ110 ／Ｉ002 として、求
めた。<Measurement of degree of orientation of graphite particles in negative electrode mixture layer> The negative electrode was attached to a glass cell for XRD with a double-sided tape,
The diffraction intensity of the (002) plane and the (110) plane was measured using an X-ray diffractometer "RINT2500" manufactured by Rigaku Corporation. Voltage: 50 KV Current: 200 mA Operating angle: 25.5 to 27.5 degrees and 76.5 ~ 78.
5 ° scanning speed: 6 ° / min (25.5 to 27.5 °) 0.2 ° / min (76.5 to 78.5 °). The data processing was performed by the integrated intensity ratio, the averaging score of 9 points, and the automatic background removal. The degree of orientation is the diffraction peak (26.5 degrees) of the (002) plane (I 002 ) and the diffraction peak of the (110) plane (77.5).
Degree) intensity (I 110 ) and determined as I 110 / I 002 .
【００３８】＜電池の放電特性試験＞電池を６２０ｍＡ
で４．２Ｖまで充電したのち、４．２Ｖで合計充電時間
が２．５時間となるまでさらに充電を行い、その後、１
２４ｍＡで３Ｖまで放電した（この放電強度を０．２Ｃ
と表現する）。ついで、６２０ｍＡで４．２Ｖまで充電
したのち、６２０ｍＡで３Ｖまで放電した（この放電強
度を１Ｃと表現する）。さらに、６２０ｍＡで４．２Ｖ
まで充電したのち、４．２Ｖで合計充電時間が２．５時
間となるまでさらに充電を行い、その後、１，２４０ｍ
Ａで３Ｖまで放電した（この放電強度を２Ｃと表現す
る）。これらの放電容量の測定結果から、０．２Ｃの放
電強度時の放電容量に対する２Ｃの放電強度時の放電容
量の割合〔（２Ｃの放電強度時の放電容量／０．２Ｃの
放電強度時の放電容量）×１００（％）〕を求め、その
結果を２Ｃ／０．２Ｃとして表１に示した。この２Ｃ／
０．２Ｃの値が大きいほど、負荷特性として、大電流時
の放電特性が良いことを示している。<Battery Discharge Characteristic Test> A battery of 620 mA was used.
After charging to 4.2V at 4.2V, further charge at 4.2V until the total charging time reaches 2.5 hours, then 1
Discharged up to 3V at 24mA (this discharge strength is 0.2C
Express). Then, the battery was charged to 4.2 V at 620 mA and then discharged to 3 V at 620 mA (this discharge intensity is expressed as 1 C). Furthermore, 4.2V at 620mA
After charging up to 4.2V, the battery is further charged at 4.2V until the total charging time reaches 2.5 hours, then 1,240m
A was discharged to 3 V (this discharge intensity is expressed as 2C). From the measurement results of these discharge capacities, the ratio of the discharge capacity at 2C discharge strength to the discharge capacity at 0.2C discharge strength [(discharge capacity at 2C discharge strength / discharge at 0.2C discharge strength) Capacity) × 100 (%)] was obtained, and the result is shown in Table 1 as 2C / 0.2C. This 2C /
The larger the value of 0.2 C, the better the load characteristic is the discharge characteristic at the time of large current.
【００３９】 [0039]
【００４０】上記の表１の結果から、本発明の実施例１
〜５の非水二次電池は、負極活物質として、平均円形度
が０．９３以上である円形天然黒鉛粒子と、他種黒鉛粒
子としてメソフェーズカーボン黒鉛化品または／および
繊維状黒鉛とを、混合使用し、負極合剤層中の黒鉛粒子
の配向度が０．００１以上となるようにしたことによ
り、負荷特性（大電流時の放電特性）にすぐれているこ
とがわかる。From the results of Table 1 above, Example 1 of the present invention
In the non-aqueous secondary batteries of Nos. 5 to 5, circular natural graphite particles having an average circularity of 0.93 or more as the negative electrode active material, and mesophase carbon graphitized product or / and fibrous graphite as the other type graphite particles, It can be seen that the load characteristics (the discharge characteristics at the time of large current) are excellent because the graphite particles in the negative electrode mixture layer were mixed and used so that the degree of orientation of the graphite particles was 0.001 or more.
【００４１】これに対し、他種黒鉛粒子を使用しない比
較例１の非水二次電池、平均円形度が０．９３に満たな
い天然黒鉛粒子を使用した比較例２，３の非水二次電池
は、いずれも、負荷特性に明らかに劣っていることがわ
かる。On the other hand, the non-aqueous secondary battery of Comparative Example 1 using no other type of graphite particles and the non-aqueous secondary battery of Comparative Examples 2 and 3 using natural graphite particles having an average circularity of less than 0.93. It can be seen that the batteries are clearly inferior in load characteristics.
【００４２】[0042]
【発明の効果】以上のように、本発明は、負極活物質と
して、円形度の高い黒鉛粒子を主体とし、これに上記以
外の黒鉛粒子、たとえばメソフェーズカーボン黒鉛化品
や繊維状黒鉛などを混合使用して、集電体上に形成され
る負極合剤層における黒鉛粒子のＸ線回折による配向度
が一定値以上となるようにしたことにより、負荷特性に
すぐれた非水二次電池を提供することができる。As described above, according to the present invention, graphite particles having high circularity are mainly used as the negative electrode active material, and graphite particles other than the above, for example, mesophase carbon graphitized product and fibrous graphite are mixed. A non-aqueous secondary battery having excellent load characteristics is provided by using the negative electrode mixture layer formed on the current collector so that the degree of orientation of the graphite particles by X-ray diffraction becomes a certain value or more. can do.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 和田 秀一 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 Ｆターム(参考） 5H029 AJ02 AK03 AL07 AM03 AM04 AM05 AM07 DJ05 DJ07 HJ00 HJ01 5H050 AA02 BA17 CA07 CA08 CA09 CB08 DA04 HA00 HA01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Shuichi Wada Hitachima, 1-88, Torora, Ibaraki City, Osaka Prefecture Within Kucsel Co., Ltd. F term (reference) 5H029 AJ02 AK03 AL07 AM03 AM04 AM05 AM07 DJ05 DJ07 HJ00 HJ01 5H050 AA02 BA17 CA07 CA08 CA09 CB08 DA04 HA00 HA01
Claims (5)
活物質を用いた正極と負極と非水系の電解質を有する非
水二次電池において、負極は、集電体とこの上に形成さ
れた負極活物質として平均円形度が０．９３以上の黒鉛
粒子とそれ以外の黒鉛粒子とを含む負極合剤層とからな
り、この負極合剤層のＸ繰回折による黒鉛粒子の配向度
が０．００１以上であることを特徴とする非水二次電
池。1. In a non-aqueous secondary battery having a positive electrode using a positive electrode active material capable of inserting and extracting lithium ions, a negative electrode, and a non-aqueous electrolyte, the negative electrode is a current collector and a negative electrode formed thereon. A negative electrode mixture layer containing graphite particles having an average circularity of 0.93 or more as an active material and other graphite particles, and the degree of orientation of the graphite particles by X diffraction of the negative electrode mixture layer is 0.001. The non-aqueous secondary battery characterized by the above.
は、天然黒鉛からなる請求項１に記載の非水二次電池。2. The non-aqueous secondary battery according to claim 1, wherein the graphite particles having an average circularity of 0.93 or more are made of natural graphite.
外の黒鉛粒子は、メソフェーズカーボン黒鉛化品および
繊維状黒鉛の中から選ばれる少なくともひとつである請
求項１または２に記載の非水二次電池。3. The non-aqueous water according to claim 1, wherein the graphite particles other than the graphite particles having an average circularity of 0.93 or more are at least one selected from mesophase carbon graphitized products and fibrous graphite. Secondary battery.
粒子全体の３〜２５重量％である請求項３に記載の非水
二次電池。4. The non-aqueous secondary battery according to claim 3, wherein the mesophase carbon graphitized product is 3 to 25 wt% of the entire graphite particles.
３重量％である請求項３に記載の非水二次電池。5. The fibrous graphite is 0.1 to 0.1% of the whole graphite particles.
The non-aqueous secondary battery according to claim 3, which is 3% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001255463A JP2003068301A (en) | 2001-08-27 | 2001-08-27 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001255463A JP2003068301A (en) | 2001-08-27 | 2001-08-27 | Non-aqueous secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003068301A true JP2003068301A (en) | 2003-03-07 |
Family
ID=19083428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001255463A Withdrawn JP2003068301A (en) | 2001-08-27 | 2001-08-27 | Non-aqueous secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP2003068301A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008016456A (en) * | 2004-01-05 | 2008-01-24 | Showa Denko Kk | Negative electrode material for lithium battery and lithium battery |
| US7976984B2 (en) * | 2004-09-17 | 2011-07-12 | Sony Corporation | Powdered graphite and nonaqueous electrolyte secondary battery |
| US8388922B2 (en) | 2004-01-05 | 2013-03-05 | Showa Denko K.K. | Negative electrode material for lithium battery, and lithium battery |
| US20130130117A1 (en) * | 2010-03-31 | 2013-05-23 | Sumitomo Metal Industries, Ltd. | Modified Natural Graphite Particle and Method for Producing the Same |
| WO2013128829A1 (en) * | 2012-03-02 | 2013-09-06 | Ｊｆｅケミカル株式会社 | Nagative electrode material for lithium ion secondary batteries, nagative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| US9054364B2 (en) | 2012-03-30 | 2015-06-09 | Sony Corporation | Battery, negative electrode for battery, battery pack, electronic apparatus, electric vehicle, electricity storage apparatus and electric power system |
| CN107112536A (en) * | 2015-01-16 | 2017-08-29 | 三菱化学株式会社 | Carbon material and the non-aqueous secondary battery for having used carbon material |
-
2001
- 2001-08-27 JP JP2001255463A patent/JP2003068301A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008016456A (en) * | 2004-01-05 | 2008-01-24 | Showa Denko Kk | Negative electrode material for lithium battery and lithium battery |
| US8388922B2 (en) | 2004-01-05 | 2013-03-05 | Showa Denko K.K. | Negative electrode material for lithium battery, and lithium battery |
| US7976984B2 (en) * | 2004-09-17 | 2011-07-12 | Sony Corporation | Powdered graphite and nonaqueous electrolyte secondary battery |
| US20130130117A1 (en) * | 2010-03-31 | 2013-05-23 | Sumitomo Metal Industries, Ltd. | Modified Natural Graphite Particle and Method for Producing the Same |
| WO2013128829A1 (en) * | 2012-03-02 | 2013-09-06 | Ｊｆｅケミカル株式会社 | Nagative electrode material for lithium ion secondary batteries, nagative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| JP2013211254A (en) * | 2012-03-02 | 2013-10-10 | Jfe Chemical Corp | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| US9054364B2 (en) | 2012-03-30 | 2015-06-09 | Sony Corporation | Battery, negative electrode for battery, battery pack, electronic apparatus, electric vehicle, electricity storage apparatus and electric power system |
| US9508979B2 (en) | 2012-03-30 | 2016-11-29 | Sony Corporation | Battery, negative electrode for battery, battery pack, electronic apparatus, electric vehicle, electricity storage apparatus and electric power system |
| CN107112536A (en) * | 2015-01-16 | 2017-08-29 | 三菱化学株式会社 | Carbon material and the non-aqueous secondary battery for having used carbon material |
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