JP4061743B2 - Battery electrode, battery, battery electrode active material modification method and electrode active material - Google Patents
Battery electrode, battery, battery electrode active material modification method and electrode active material Download PDFInfo
- Publication number
- JP4061743B2 JP4061743B2 JP30738198A JP30738198A JP4061743B2 JP 4061743 B2 JP4061743 B2 JP 4061743B2 JP 30738198 A JP30738198 A JP 30738198A JP 30738198 A JP30738198 A JP 30738198A JP 4061743 B2 JP4061743 B2 JP 4061743B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode active
- electrode
- battery
- transition metal
- 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.)
- Expired - Lifetime
Links
Images
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)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は電池用電極および電池に関し、より詳しくは、電極および電池の電気化学的性能を高めるための改質した固有面を有する電極材料に関する。本発明はまた、電池に使用される表面改質化電極材料の製造方法および電池用電極活物質の固有面を改質する方法に関する。
【０００２】
【従来の技術】
リチウムイオンバッテリは、当該技術分野において、ここ数年来知られてきている。このバッテリは工業用途で直ちに利用され、更に高性能で再充電可能なバッテリに対する消費者の要求により、その電気化学的性能特性は高められつつある。実際に、従来技術において、リチウムイオンバッテリの容量最適化に関する文献が数多く存在する。例えば、米国特許第５，４４９，５７７号（以下、Ｄａｈｎ特許’５７７と称する）公報は、電極活物質の「バルク」形態（”ｂｕｌｋ”ｍｏｒｐｈｏｌｏｇｙ）を変更することによってリチウムイオンバッテリの可逆容量を増加させる方法を開示している。Ｄａｈｎ特許’５７７公報は、熱と還元性の雰囲気を組合せた状態に電極活物質を曝すことによって、電極活物質を形式的に還元することを開示している。Ｄａｈｎ特許’５７７の方法において、電極活物質の陰イオン種（通常は酸素）を除去することにより、電池の充放電サイクル中に、より多数の陽イオン（通常はリチウム）を挿入／着脱（ｉｎｔｅｒｃａｌａｔｅ／ｄｅｉｎｔｅｒｃａｌａｔｅ）することが可能となる。
【０００３】
米国特許第５，２４０，７９４号（以下、Ｔｈａｃｋｅｒａｙ特許’７９４ と称する）公報には、電極活物質としてＬｉＭｎ2Ｏ4を含有する電池の容量を増加させるための方法が開示されている。このＴｈａｃｋｅｒａｙ特許’７９４には、電極活物質を還元性雰囲気中で熱に曝す−Ｄａｈｎ特許’５７７と類似−ことによって電極活物質の「バルク」形態を変化させる方法が開示されている。
【０００４】
プラズマ処理を施すことにより、電極活物質の表面から、そのバルク形態に影響を及ぼすことなく非固有の不純物を除去することにより、バッテリの電気化学的性能特性を高める試みが行なわれた。（参照：Ｊｏｕｒｎａｌ ｏｆ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ， Ｂｉｎｄｅｒ他、第１４０巻、１２号、１９９３年１２月）しかし、この従来技術には電極活物質の固有面の「改質」を開示してはいない。
【０００５】
本明細書で使用する「改質された」及び「改質する」の語の意味は、電極活物質の固有面を、その物質のバルク形態を変えずに変更することを意味する。それは、必ずしも電極活物質から原子を形式的に除去することを意味しない。更に、「バルク形態」改質は、特定の電極活物質の結晶格子からの原子の除去を意味する。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、電気化学的性能を高め、改質した電極活物質の固有面を有する電極および電池を提供することにある。
【０００７】
【課題を解決するための手段】
上記課題を解決するために、本発明者らは鋭意検討した結果、特定の処理を電極活物質の固有面に施すことにより、上記目的を達成出来ることを見い出し、本発明を達成するに至った。
【０００８】
本発明の第一の要旨は、集電基板および電極活物質から成る電池用電極であって、上記電極活物質がリチウム遷移金属酸化物から成り、当該リチウム遷移金属酸化物がアルゴンと酸素との混合ガス雰囲気下で予めプラズマ処理されたものであることを特徴とする電池用電極に存する。
【０００９】
第一の要旨の好ましい実施態様では、前記リチウム遷移金属酸化物が、ＬｉＣｏＯ ２ 、ＬｉＮｉＯ ２ 及びＬｉＭｎ ２ Ｏ ４ から成るグループの中から選択される一つ以上である。
【００１０】
本発明の第二の要旨は、電解液、第１電極および第２電極から成る電池であって、上記第１電極と第２電極の少なくとも一方が集電基板および電極活物質から成り、当該電極活物質がリチウム遷移金属酸化物から成り、当該リチウム遷移金属酸化物がアルゴンと酸素との混合ガス雰囲気下で予めプラズマ処理されたものであることを特徴とする電池に存する。
【００１１】
第二の要旨の好ましい実施態様では、前記リチウム遷移金属酸化物が、ＬｉＣｏＯ ２ 、ＬｉＮｉ ２ 及びＬｉＭｎ ２ Ｏ ４ から成るグループの中から選択される一つ以上である。
【００１２】
本発明の第三の要旨は、リチウム遷移金属酸化物から成る電池用電極活物質の固有面を改質する方法であって、電極活物質をチャンバー内に配置する工程と、上記電極活物質をアルゴンと酸素との混合ガス雰囲気下でプラズマ処理する工程とから成ることを特徴とする方法に存する。
【００１３】
第三の要旨の好ましい実施態様では、前記リチウム遷移金属酸化物が、ＬｉＣｏＯ ２ 、ＬｉＮｉＯ ２ 及びＬｉＭｎ ２ Ｏ ４ から成るグループの中から選択される一つ以上である
【００１４】
本発明の第四の要旨は、リチウム遷移金属酸化物から成る電極活物質であって、当該電極活物質がアルゴンと酸素との混合ガス雰囲気下でプラズマ処理されたものであることを特徴とする電極活物質に存する。
【００１５】
第四の要旨の好ましい実施態様では、前記リチウム遷移金属酸化物が、ＬｉＣｏＯ ２ 、ＬｉＮｉＯ ２ 及びＬｉＭｎ ２ Ｏ ４ から成るグループの中から選択される一つ以上である
【００１９】
【発明の実施の態様】
以下、本発明を詳細に説明する。尚、以下に記載する実施例は本発明の原理の例示であるが、本発明は種々の実施態様を取り得るため、本発明は以下の実施態様に限定されない。
【００２０】
本発明は、電極活物質の固有面を、そのバルク形態に影響を及ぼすことなく制御可能に改質することによって、電池の容量とレート容量の両者を増加させることに関する。以下に説明する図７〜図１１で明らかなように、電池のレート容量を増加させる本発明の何れの方法においても、電極活物質の結晶格子に対して影響を与えない。すなわち、これらの方法により、表面改質される材料のバルク形態が変えられることはない。
【００２１】
従来技術においては、電極活物質のバルク形態を改質することによって、リチウムイオンバッテリの電気化学的性能を最大化する試みがなされた。バルク形態の改質（すなわち、格子内の原子を取り除いて他の原子と任意に置換すること）は、電気化学的性能を増加させた電池を製造するための手順の一つである。しかしながら、本発明においては、バルク形態を改質せずに電気化学的性能を高めることを特徴とする電極および電池を開示する。以下に説明するように、（材料のバルク形態を変えることなく）固有面を変えたり／改質することは、本発明による改質化固有面を有する電極を利用しない電池に比べて、容量とレート容量が著しく増加した電池が得られる。
【００２２】
【実施例】
本発明を裏付けるために、プラズマ処理の表面処理方法により、電極活物質の固有面の改質を行った。それぞれの実験手順を以下に説明する。
【００２３】
＜雰囲気制御プラズマ処理＞
電極活物質の固有面層を改質するためにプラズマ処理を利用して次の手順で実験を行なった。以下の実施例においては、単にＬｉＣｏＯ２について説明しただけであり、ＬｉＮｉＯ２やＬｉＭｎ２Ｏ４の様な電池用の電極活物質として適当な他の金属酸化物とリチウム遷移金属酸化物も同様に使用できる。
【００２４】
実施例１
第１に、ガス流量コントローラを備えた回転式プラズマリアクタに、１００グラムのＬｉＣｏＯ2 を充填した。第２に、プラズマリアクタを約１０ｒｐｍで回転させながら、真空下でそのＬｉＣｏＯ2 を乾燥させた。第３に、アルゴンを使った５回にわたるパージ／減圧排気サイクルによりプラズマリアクタのチャンバ内から「空気」を排気した。第４に、アルゴンガスと酸素ガスを、それぞれ１．８ｍｌ／分と１．９ｍｌ／分の流量でプラズマリアクタ内に導入した。第５に、システムの真空度を１６０ミリｔｏｒｒに維持してプラズマの発生を開始し、１００Ｗで２時間、プラズマを連続して発生させた。第６に、プラズマ処理を終了した後、リアクターをアルゴンでパージして、チャンバー内の温度と圧力を周囲温度と周囲圧力同化させた。ＬｉＣｏＯ2 のサンプルを取り出して、バルク形態特性と容量特性の両者を評価した。
【００３１】
比較例１
電極活物質の固有表面の改質処理を行わなかった以外は実施例１と同様の操作を行った
【００３２】
＜特性評価＞
上記実施例および比較例の各サンプルの容量とレート容量を、次の手順を使用して決定した。第１に、表面改質された遷移金属酸化物に、結合剤（ＰＶＤＦ）とカーボンブラックとを添加してペースト状に混合した。第２に、その電極ペーストをアルミニウムメッシュ上に加圧成形した。第３に、３個の電池（表面改質した各サンプル毎に新しい電池を製作した）を作製し、加圧成形された表面改質化電極活物質を持つ電極を作動電極とした。対向電極と基準電極は共にリチウムから作製した。各電池に使用される電解液、すなわち、各実験で使用した電解液の構成は、１モルのＬｉＡｓＦ6 を溶解させたプロピレンカーボネート溶液であった。次に、完全に組み立てた電池を、３．２Ｖと４．２Ｖの間で、電池を繰り返し充放電サイクルを行なってその容量を判定した。得られた結果を下記表１に示す。
【００３３】
【表１】
表１から明らかなように、本発明の処理を施した実施例１の電極は、無処理の比較例１の基準電極に対して、表面改質された電極の容量が大幅に増加した。更に、各表面改質化電極活物質の熱安定性は、特にＣ／２サイクル中、無処理電極に比べて劇的に向上した。
【００３５】
図１には、４時間の充放電レート（Ｃ／４）での無処理の電極材料とプラズマ処理を施した電極材料の容量を示す電圧−容量の二次元プロットを、図２には、２時間の充放電レート（Ｃ／２）での無処理の電極材料とプラズマ処理を施した電極材料の容量を示す電圧−容量の二次元プロットを、図３には、無処理の電極材料とプラズマ処理を施した電極材料のサイクル中の保持容量を示す電圧−サイクルの２次元プロットを、図４には、２時間の充放電レート（Ｃ／２）での無処理の電極材料と超音波処理を施した電極材料の容量を示す電圧−容量の二次元プロットをそれぞれ示す。
【００３６】
図１のプラズマ処理ＬｉＣｏＯ２（Ｃ／４レート）に関する特性データから明らかなように、処理された電極材料（△：（Ａｒ／Ｏ ２ ）プラズマ処理されたＬｉＣｏＯ ２ ）が、無処理材料（○）に比べて容量が増加していることが解る。更に、図２〜図４から明らかなように、プラズマ処理された電極材料は、Ｃ／１、Ｃ／２、およびＣ／４の全てにおいて、容量の増加を示している。
【００３８】
表面改質化電極活物質のバルク形態には実際に変化がないことを証明するために、Ｘ線回折トレースを行なった。図７に無改質の電極活物質の形態（ａ）と、プラズマ処理による改質化面を有する電極活物質（ｂ）とを比較したＸ線回折チャートを示す。
【００３９】
図７に示すように、プラズマによって改質された電極活物質のチャートは、無改質の電極活物質のＸ線回折チャートのそれと同一であった。特に、ピーク位置とピーク強さは変化しなかった。図７から解るように、表面改質化サンプルのいずれにもピーク移動は認められなかった。従って、本発明の表面改質処理は、電極活物質の固有面を単に改質するだけで、そのバルク形態を変化させることはなく、更に容量／レート容量を増加し得ることを証明している。
【００４０】
図１０に無改質のＬｉＭｎ2 Ｏ4の形態とそれぞれ超音波処理したＬｉＭｎ2 Ｏ4とを比較したＸ線回折チャートを、図１１に無改質のＬｉＭｎ2 Ｏ4の形態と熱処理したＬｉＭｎ2 Ｏ4 とを比較したＸ線回折チャートを示す。図１０及び１１から解るように、表面改質化サンプルのいずれにもピーク移動は認められなかった。従って、本発明の表面改質処理は、ＬｉＣｏＯ2 だけでなく、ＬｉＭｎ2 Ｏ4のような電池用の電極活物質として適当な他の金属酸化物とリチウム遷移金属酸化物についても同様の効果が得られることが解る。
【００４１】
上記の記載と図面は、単に発明の例示であり、本発明はその要旨を逸脱することなく、種々の修正と変更を行なうことが可能である。
【００４２】
【発明の効果】
以上説明した本発明の電極は、電気化学的性能を高め、改質した電極活物質の固有面を有するため、そのバルク形態を変化させることはなく、電池の容量／レート容量を増加できるため、その工業的価値は高い。
【図面の簡単な説明】
【図１】４時間の充放電レート（Ｃ／４）での無処理の電極材料とプラズマ処理を施した電極材料の電圧−容量の二次元プロット
【図２】２時間の充放電レート（Ｃ／２）での無処理の電極材料とプラズマ処理を施した電極材料の電圧−容量の二次元プロット
【図３】２時間の充放電レート（Ｃ／２）及び１時間の充放電レート（１Ｃ）での無処理の電極材料とプラズマ処理を施した電極材料の容量−サイクルの２次元プロット
【図４】４時間の充放電レート（Ｃ／４）での無処理の電極材料とプラズマ処理を施した電極材料の容量−サイクルの２次元プロット
【図５】無改質の電極活物質の形態（ａ）と、プラズマ処理による改質化面を有する電極活物質（ｂ）とを比較したＸ線回折チャート [0001]
BACKGROUND OF THE INVENTION
The present invention relates to a battery electrode and a battery, and more particularly to an electrode material having a modified intrinsic surface for enhancing the electrochemical performance of the electrode and battery. The present invention also relates to a method for producing a surface-modified electrode material used for a battery and a method for modifying a specific surface of a battery electrode active material.
[0002]
[Prior art]
Lithium ion batteries have been known in the art for several years. This battery is immediately utilized in industrial applications, and its electrochemical performance characteristics are being enhanced by consumer demand for higher performance, rechargeable batteries. In fact, in the prior art, there are many documents regarding the capacity optimization of lithium ion batteries. For example, US Pat. No. 5,449,577 (hereinafter referred to as Dahn patent '577) discloses the reversible capacity of a lithium ion battery by changing the “bulk” morphology of the electrode active material. A method of increasing is disclosed. The Dahn patent '577 discloses formally reducing the electrode active material by exposing the electrode active material to a combination of heat and a reducing atmosphere. In the method of Dahn patent '577, by removing the anionic species (usually oxygen) of the electrode active material, a larger number of cations (usually lithium) are inserted / removed (intercalated) during the charge / discharge cycle of the battery. / Deintercalate).
[0003]
US Pat. No. 5,240,794 (hereinafter referred to as “Tackeray Patent '794”) discloses a method for increasing the capacity of a battery containing LiMn 2 O 4 as an electrode active material. The Thackeray patent '794 discloses a method for changing the “bulk” morphology of an electrode active material by exposing the electrode active material to heat in a reducing atmosphere—similar to the Dahn patent' 577 ”.
[0004]
Attempts have been made to enhance the electrochemical performance characteristics of the battery by applying plasma treatment to remove non-specific impurities from the surface of the electrode active material without affecting its bulk morphology. (Reference: Journal of Electrochemical Society, Binder et al., Vol. 140, No. 12, December 1993) However, this prior art does not disclose “modification” of the inherent surface of the electrode active material.
[0005]
As used herein, the terms “modified” and “modify” refer to changing the intrinsic surface of an electrode active material without changing the bulk form of the material. It does not necessarily mean formally removing atoms from the electrode active material. Furthermore, “bulk form” modification means the removal of atoms from the crystal lattice of a particular electrode active material.
[0006]
[Problems to be solved by the invention]
It is an object of the present invention to provide an electrode and a battery that have improved electrochemical performance and have an intrinsic surface of a modified electrode active material.
[0007]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors diligently studied and found that the above object can be achieved by applying a specific treatment to the specific surface of the electrode active material, thereby achieving the present invention. .
[0008]
A first aspect of the present invention is a battery electrode comprising a current collecting substrate and an electrode active material, wherein the electrode active material comprises a lithium transition metal oxide, and the lithium transition metal oxide comprises argon and oxygen. It exists in the electrode for batteries characterized by having been plasma-treated previously in mixed gas atmosphere.
[0009]
In a preferred embodiment of the first aspect, the lithium transition metal oxide is one or more selected from the group consisting of LiCoO 2 , LiNiO 2 and LiMn 2 O 4 .
[0010]
The second gist of the present invention is a battery comprising an electrolytic solution, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode comprises a current collecting substrate and an electrode active material. The battery is characterized in that the active material is composed of a lithium transition metal oxide, and the lithium transition metal oxide is previously plasma-treated in a mixed gas atmosphere of argon and oxygen.
[0011]
In a preferred embodiment of the second aspect, the lithium transition metal oxide is one or more selected from the group consisting of LiCoO 2 , LiNi 2 and LiMn 2 O 4 .
[0012]
A third aspect of the present invention is a method for modifying the intrinsic surface of a battery electrode active material comprising a lithium transition metal oxide, the step of arranging the electrode active material in a chamber, and the electrode active material comprising: And a plasma processing step in a mixed gas atmosphere of argon and oxygen.
[0013]
In a preferred embodiment of the third aspect, the lithium transition metal oxide is one or more selected from the group consisting of LiCoO 2 , LiNiO 2 and LiMn 2 O 4.
According to a fourth aspect of the present invention, there is provided an electrode active material comprising a lithium transition metal oxide, wherein the electrode active material is plasma-treated in a mixed gas atmosphere of argon and oxygen. It exists in the electrode active material.
[0015]
In a preferred embodiment of the fourth aspect, the lithium transition metal oxide is one or more selected from the group consisting of LiCoO 2 , LiNiO 2 and LiMn 2 O 4.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail. In addition, although the Example described below is the illustration of the principle of this invention, since this invention can take a various embodiment, this invention is not limited to the following embodiment.
[0020]
The present invention relates to increasing both battery capacity and rate capacity by controllably modifying the intrinsic surface of an electrode active material without affecting its bulk morphology. As will be apparent from FIGS. 7 to 11 described below, any of the methods of the present invention for increasing the rate capacity of the battery does not affect the crystal lattice of the electrode active material. That is, these methods do not change the bulk form of the surface-modified material.
[0021]
In the prior art, attempts have been made to maximize the electrochemical performance of lithium ion batteries by modifying the bulk morphology of the electrode active material. Bulk form modification (i.e., removing atoms in the lattice and optionally substituting other atoms) is one of the procedures for manufacturing batteries with increased electrochemical performance. However, the present invention discloses electrodes and batteries that are characterized by enhancing electrochemical performance without modifying the bulk morphology. As will be explained below, changing / modifying the specific surface (without changing the bulk form of the material) can be compared to capacity and capacity compared to a battery that does not utilize an electrode with a modified specific surface according to the present invention. A battery with significantly increased rate capacity is obtained.
[0022]
【Example】
In order to support the present invention, the specific surface of the electrode active material was modified by a surface treatment method of plasma treatment . Each experimental procedure is described below.
[0023]
<Atmosphere control plasma treatment>
In order to modify the specific surface layer of the electrode active material , an experiment was performed by the following procedure using plasma treatment. In the following examples, only LiCoO 2 has been described, and other metal oxides and lithium transition metal oxides suitable as electrode active materials for batteries such as LiNiO 2 and LiMn 2 O 4 are similarly used. Can be used.
[0024]
Example 1
First, a rotary plasma reactor equipped with a gas flow controller was charged with 100 grams of LiCoO 2 . Second, the LiCoO 2 was dried under vacuum while rotating the plasma reactor at about 10 rpm. Third, “air” was evacuated from within the chamber of the plasma reactor by five purge / evacuation cycles using argon. Fourth, argon gas and oxygen gas were introduced into the plasma reactor at a flow rate of 1.8 ml / min and 1.9 ml / min, respectively. Fifth, the generation of plasma was started while maintaining the vacuum degree of the system at 160 millitorr, and plasma was continuously generated at 100 W for 2 hours. Sixth, after finishing the plasma treatment, the reactor was purged with argon to assimilate the temperature and pressure in the chamber to ambient and ambient pressure. A sample of LiCoO 2 was taken and evaluated for both bulk morphology and capacity characteristics.
[0031]
Comparative Example 1
The same operation as in Example 1 was performed except that the modification treatment of the specific surface of the electrode active material was not performed.
<Characteristic evaluation>
The capacity and rate capacity of each sample of the above examples and comparative examples was determined using the following procedure. First, a binder (PVDF) and carbon black were added to the surface-modified transition metal oxide and mixed in a paste form. Second, the electrode paste was pressure formed on an aluminum mesh. Third, three batteries (a new battery was manufactured for each surface-modified sample) were prepared, and an electrode having a surface-modified electrode active material that was pressure-formed was used as the working electrode. Both the counter electrode and the reference electrode were made of lithium. The electrolyte solution used in each battery, that is, the electrolyte solution used in each experiment was a propylene carbonate solution in which 1 mol of LiAsF 6 was dissolved. Next, the fully assembled battery was repeatedly charged / discharged between 3.2 V and 4.2 V to determine its capacity. The obtained results are shown in Table 1 below.
[0033]
[Table 1]
As is apparent from Table 1, the capacity of the electrode whose surface was modified was significantly increased in the electrode of Example 1 subjected to the treatment of the present invention compared to the reference electrode of Comparative Example 1 which was not treated. Furthermore, the thermal stability of each surface modified electrode active material was dramatically improved compared to the untreated electrode, especially during the C / 2 cycle.
[0035]
FIG. 1 shows a voltage-capacity two-dimensional plot showing the capacities of an untreated electrode material and a plasma-treated electrode material at a charge / discharge rate (C / 4) of 4 hours, and FIG. A voltage-capacity two-dimensional plot showing the capacity of the untreated electrode material and the plasma-treated electrode material at the time charge / discharge rate (C / 2) is shown in FIG. FIG. 4 shows a two-dimensional plot of voltage-cycle showing the retention capacity during the cycle of the treated electrode material. FIG. 4 shows an untreated electrode material and ultrasonic treatment at a charge / discharge rate (C / 2) of 2 hours. 2 shows a two-dimensional plot of voltage-capacitance indicating the capacity of the electrode material subjected to.
[0036]
As is clear from the characteristic data on the plasma-treated LiCoO 2 (C / 4 rate) in FIG. 1, the treated electrode material (Δ: (Ar / O 2 ) plasma-treated LiCoO 2 ) is an untreated material (◯ It can be seen that the capacity has increased compared to). Furthermore, as is apparent from FIGS. 2 to 4, the plasma-treated electrode material shows an increase in capacity at all of C / 1, C / 2, and C / 4.
[0038]
In order to prove that there is no actual change in the bulk form of the surface-modified electrode active material, an X-ray diffraction trace was performed. FIG. 7 shows an X-ray diffraction chart comparing the form (a) of the unmodified electrode active material and the electrode active material (b) having a modified surface by plasma treatment.
[0039]
As shown in FIG. 7, the chart of the electrode active material modified by plasma was the same as that of the X-ray diffraction chart of the unmodified electrode active material. In particular, the peak position and peak intensity did not change. As can be seen from FIG. 7, no peak shift was observed in any of the surface-modified samples. Therefore, it has been proved that the surface modification treatment of the present invention can further increase the capacity / rate capacity by simply modifying the intrinsic surface of the electrode active material without changing its bulk form. .
[0040]
FIG. 10 shows an X-ray diffraction chart comparing the form of unmodified LiMn 2 O 4 and each of ultrasonically treated LiMn 2 O 4, and FIG. 11 shows the form of unmodified LiMn 2 O 4 and heat-treated LiMn. 2 shows an X-ray diffraction chart comparing 2 O 4 . As can be seen from FIGS. 10 and 11, no peak shift was observed in any of the surface-modified samples. Therefore, the surface modification treatment of the present invention has the same effect not only for LiCoO 2 but also for other metal oxides and lithium transition metal oxides suitable as electrode active materials for batteries such as LiMn 2 O 4. You can see that
[0041]
The above description and drawings are merely illustrative of the invention, and the present invention can be modified and changed in various ways without departing from the gist thereof.
[0042]
【The invention's effect】
The electrode of the present invention described above has improved electrochemical performance and has an inherent surface of a modified electrode active material, so that its bulk form is not changed and the capacity / rate capacity of the battery can be increased. Its industrial value is high.
[Brief description of the drawings]
FIG. 1 is a two-dimensional plot of voltage-capacity of an untreated electrode material and a plasma-treated electrode material at a charge / discharge rate of 4 hours (C / 4). FIG. 2) Two-dimensional plot of voltage-capacitance of untreated electrode material and plasma-treated electrode material in FIG. 3 [FIG. 3] 2 hour charge / discharge rate (C / 2) and 1 hour charge / discharge rate (1C 2) Plot of capacity-cycle of untreated electrode material and plasma-treated electrode material in FIG. 4 [FIG. 4] Untreated electrode material and plasma treatment at a charge / discharge rate (C / 4) of 4 hours. Capacity-cycle two-dimensional plot of applied electrode material. FIG. 5 is a comparison X of unmodified electrode active material form (a) and electrode active material (b) having a modified surface by plasma treatment. Line diffraction chart
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96240397A | 1997-10-31 | 1997-10-31 | |
| US08/962403 | 1997-10-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11250899A JPH11250899A (en) | 1999-09-17 |
| JP4061743B2 true JP4061743B2 (en) | 2008-03-19 |
Family
ID=25505809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30738198A Expired - Lifetime JP4061743B2 (en) | 1997-10-31 | 1998-10-28 | Battery electrode, battery, battery electrode active material modification method and electrode active material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4061743B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101249974B1 (en) | 2010-04-01 | 2013-04-03 | 한국기초과학지원연구원 | An elecltrod for lithium secondary battery processed in reducing atmospheres, method for fabricating the same, and lithium secondary battery containing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100341407B1 (en) * | 2000-05-01 | 2002-06-22 | 윤덕용 | A Crystall ization method of lithium transition metal oxide thin films by plasma treatm ent |
| TWI365562B (en) * | 2008-10-03 | 2012-06-01 | Ind Tech Res Inst | Positive electrode and method for manufacturing the same and lithium battery utilizing the same |
-
1998
- 1998-10-28 JP JP30738198A patent/JP4061743B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101249974B1 (en) | 2010-04-01 | 2013-04-03 | 한국기초과학지원연구원 | An elecltrod for lithium secondary battery processed in reducing atmospheres, method for fabricating the same, and lithium secondary battery containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11250899A (en) | 1999-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210313557A1 (en) | Negative electrode active material for lithium secondary battery and method of preparing the same | |
| US20220255069A1 (en) | Negative electrode active material for lithium secondary battery and method of preparing the same | |
| JP6177345B2 (en) | Negative electrode active material for lithium secondary battery and method for producing the same | |
| JP7198736B2 (en) | Positive electrode active material for lithium secondary battery and lithium secondary battery containing the same | |
| JP2020504416A (en) | Positive active material for lithium secondary battery, method for producing the same, electrode including the same, and lithium secondary battery including the electrode | |
| JPH11317217A (en) | Fluorinated battery electrode, battery comprising the electrodes, and manufacture of them | |
| JP2000164218A (en) | Negative electrode active material for lithium secondary battery, and manufacture thereof, and lithium secondary battery including the same | |
| EP2765636B1 (en) | Cathode material for lithium secondary battery, method for manufacturing same and lithium secondary battery comprising same | |
| WO2014104466A1 (en) | Anode active material coated with manganese potassium oxide for lithium secondary battery and method for manufacturing same | |
| JP4206267B2 (en) | Composite electrode material and electrochemical device using the same | |
| JP3609377B2 (en) | Cathode thin film for lithium secondary battery and method for producing the same | |
| JP2023534982A (en) | Method for producing positive electrode active material | |
| WO2024146611A1 (en) | Lithium ion battery | |
| KR20240095131A (en) | Method for manufacturing a positive electrode active material surface-modified using sericin, and a positive electrode active material and lithium secondary battery manufactured using the same | |
| CN1866586A (en) | Non-aqueous electrolyte rechargeable battery | |
| JP3257350B2 (en) | Non-aqueous electrolyte secondary battery and method for producing its positive electrode active material | |
| JP4061743B2 (en) | Battery electrode, battery, battery electrode active material modification method and electrode active material | |
| CN113939930A (en) | Composite anode active material, method for preparing same, anode comprising same, and secondary battery | |
| JP7515954B2 (en) | Method for producing positive electrode active material | |
| JP2001257003A (en) | Lithium secondary battery | |
| KR20070059829A (en) | Novel anode active material, producing method thereof, and lithium secondary battery comprising the same | |
| JP7099033B2 (en) | Method for manufacturing positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode active material for non-aqueous electrolyte secondary battery | |
| JP2003317708A (en) | Method of manufacturing electrode | |
| JP2005187326A (en) | Method for producing lithium nickelate | |
| KR102663399B1 (en) | Negative electrode active material, negative electrode comprising same, secondary battery comprising same and method for manufacturing negative electrode active material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040722 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060727 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060802 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060914 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070711 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070830 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070926 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071107 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20071204 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20071217 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110111 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110111 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120111 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130111 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130111 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140111 Year of fee payment: 6 |
|
| EXPY | Cancellation because of completion of term |