JP3179434B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary batteryInfo
- Publication number
- JP3179434B2 JP3179434B2 JP05064499A JP5064499A JP3179434B2 JP 3179434 B2 JP3179434 B2 JP 3179434B2 JP 05064499 A JP05064499 A JP 05064499A JP 5064499 A JP5064499 A JP 5064499A JP 3179434 B2 JP3179434 B2 JP 3179434B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- secondary battery
- silicon
- hydrogen fluoride
- 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.)
- Expired - Fee Related
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ケイ素を活物質と
する負極を備えた非水系二次電池に関する。The present invention relates to a non-aqueous secondary battery provided with a negative electrode containing silicon as an active material.
【０００２】[0002]
【従来の技術】携帯型電子機器の小型軽量化に伴い、よ
りエネルギー密度の高い二次電池が要望されている。非
水系二次電池、中でもリチウム二次電池はかかる要望に
応えるものとして期待されるが、従来用いられている黒
鉛等の炭素材料系の負極活物質によっては要望されるエ
ネルギー密度の達成が困難であった。そこで炭素材料に
代えて、ケイ素を負極活物質に用いることが検討されて
いる。2. Description of the Related Art As portable electronic devices have been reduced in size and weight, secondary batteries having higher energy density have been demanded. Non-aqueous secondary batteries, especially lithium secondary batteries, are expected to meet such demands.However, it is difficult to achieve the required energy density depending on conventionally used carbon material-based negative electrode active materials such as graphite. there were. Therefore, use of silicon as a negative electrode active material instead of a carbon material has been studied.
【０００３】例えば、特開平７−２９６０２号公報に
は、ケイ素をリチウムイオン二次電池の負極活物質とし
て用いることが開示されている。また、ＷＯ９８／２４
１３５号には、ケイ素またはその化合物を、有機材料ま
たは炭素材料の存在下で非酸化性雰囲気において焼成
し、得られたケイ素／炭素複合体を負極として用いるこ
とが開示されている。かかる負極は、初期の充放電にお
いて、従来の黒鉛等の炭素系材料を用いた負極の２倍以
上のエネルギー密度を示すことが確認されている。For example, Japanese Patent Application Laid-Open No. Hei 7-29602 discloses that silicon is used as a negative electrode active material of a lithium ion secondary battery. In addition, WO98 / 24
No. 135 discloses that silicon or a compound thereof is calcined in a non-oxidizing atmosphere in the presence of an organic material or a carbon material, and the obtained silicon / carbon composite is used as a negative electrode. It has been confirmed that such a negative electrode exhibits an energy density twice or more that of a conventional negative electrode using a carbon-based material such as graphite in initial charge and discharge.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記従来のケ
イ素を活物質に用いる負極を備えた非水系二次電池にお
いては、充放電の繰り返しに伴い放電可能容量が低下す
る問題、即ちサイクル特性が十分でない問題があった。However, in the above-mentioned conventional non-aqueous secondary battery provided with a negative electrode using silicon as an active material, the problem that the dischargeable capacity decreases with repetition of charging and discharging, that is, the cycle characteristics are reduced. There were not enough problems.
【０００５】ケイ素を活物質に用いた負極において、負
極の充放電はケイ素中へのリチウムイオンの吸蔵・放出
により行われる。かかる負極における放電可能容量の低
下の原因には、電子導電性低下による分極増大、リチウ
ムイオンの吸蔵・放出以外の副反応による充電電流消費
など種々のものがある。In a negative electrode using silicon as an active material, charging and discharging of the negative electrode is performed by inserting and extracting lithium ions into silicon. There are various causes of the decrease in the dischargeable capacity of the negative electrode, such as an increase in polarization due to a decrease in electron conductivity, and a consumption of charging current by a side reaction other than occlusion / release of lithium ions.
【０００６】そこで本発明は、サイクル特性の良好な二
次電池を提供することを目的とする。Accordingly, an object of the present invention is to provide a secondary battery having good cycle characteristics.
【０００７】[0007]
【課題を解決するための手段】ケイ素を活物質とする負
極と、非水系電解液を備えた非水系二次電池において、
非水系電解液が含フッ素リチウム塩を電解質として含む
場合に、非水系電解液中のフッ化水素量を３μｇ／ｇ以
下とすることにより、二次電池のサイクル特性を改善で
きることを見い出した。In a non-aqueous secondary battery provided with a negative electrode containing silicon as an active material and a non-aqueous electrolyte,
It has been found that when the non-aqueous electrolyte contains a fluorine-containing lithium salt as an electrolyte, the cycle characteristics of the secondary battery can be improved by setting the amount of hydrogen fluoride in the non-aqueous electrolyte to 3 μg / g or less.
【０００８】電解質に含フッ素リチウム塩を用いた場
合、含フッ素リチウム塩の製造時に不純物としてフッ化
水素が残留しており、さらに電解液中に不可避的に混入
する水分と含フッ化リチウム塩が反応してフッ化水素が
生じる。かかるフッ化水素は、電池の放電可能容量を低
下させる。[0008] When a fluorine-containing lithium salt is used for the electrolyte, hydrogen fluoride remains as an impurity during the production of the fluorine-containing lithium salt. Reacts to produce hydrogen fluoride. Such hydrogen fluoride reduces the dischargeable capacity of the battery.
【０００９】したがって、電解液中のフッ化水素濃度を
一定の値以下に抑制することにより、電池のサイクル特
性を改善することができる。Therefore, the cycle characteristics of the battery can be improved by suppressing the concentration of hydrogen fluoride in the electrolyte below a certain value.
【００１０】[0010]
【発明の実施の形態】本発明の非水系二次電池における
負極は、ケイ素を負極活物質材料とするものであり、ケ
イ素単体を用いても良いし、焼成によりケイ素に変化し
得るケイ素化合物を用いて焼成しても良い。焼成により
ケイ素に変化し得るケイ素化合物には、酸化ケイ素など
の無機ケイ素化合物や、シリコーン樹脂、有機ケイ素化
合物等がある。尚、好ましいのはケイ素単体での使用で
ある。BEST MODE FOR CARRYING OUT THE INVENTION The negative electrode in the non-aqueous secondary battery of the present invention uses silicon as a negative electrode active material, and may use simple silicon or a silicon compound which can be converted to silicon by firing. It may be used and fired. Silicon compounds that can be converted to silicon by firing include inorganic silicon compounds such as silicon oxide, silicone resins, and organic silicon compounds. Preferably, silicon is used alone.
【００１１】かかる負極活物質は、例えば、炭素質導電
剤及び結着剤と共に電極形状に成型し、非酸化性雰囲気
において焼成して負極としても良い。Such a negative electrode active material may be formed into an electrode shape together with, for example, a carbonaceous conductive agent and a binder, and fired in a non-oxidizing atmosphere to form a negative electrode.
【００１２】炭素質導電剤には、黒鉛、コークス、ピッ
チ炭化物等の炭素材料、又はナフタレン、アセナフチレ
ン等の縮合系多環炭化水素化合物等の炭化する有機材料
を使用することができる。また、結着剤には、焼成後に
電気化学的に安定な樹脂であれば使用可能であり、ポリ
エチレン、ポリプロピレン、ポリフッ化ビニリデン等の
熱可塑性樹脂、ウレタン樹脂、フェノール樹脂等の熱硬
化性樹脂が使用できる。As the carbonaceous conductive agent, a carbon material such as graphite, coke and pitch carbide, or a carbonizable organic material such as a condensed polycyclic hydrocarbon compound such as naphthalene and acenaphthylene can be used. As the binder, any resin that is electrochemically stable after firing can be used. Thermoplastic resins such as polyethylene, polypropylene, and polyvinylidene fluoride, and urethane resins and thermosetting resins such as phenolic resins can be used. Can be used.
【００１３】電極形状に成型するには、例えば、負極活
物質を炭素質導電剤及び結着剤と共にｎ−メチル−２−
ピロリドン等の溶媒に分散してスラリー化し、これを集
電体となる金属シートまたは焼成により消失する高分子
シートに塗布し、溶媒揮発させる。次に、電極形状に成
型後、非酸化性雰囲気において焼成することにより、炭
素質導電剤及び結着剤が炭化すると共に負極活物質と燒
結し、負極が得られる。尚、非酸化性雰囲気とは、窒素
雰囲気、アルゴン雰囲気等である。In order to form the electrode into an electrode shape, for example, the negative electrode active material is mixed with a carbonaceous conductive agent and a binder in n-methyl-2-
The slurry is dispersed in a solvent such as pyrrolidone to form a slurry. The slurry is applied to a metal sheet serving as a current collector or a polymer sheet which disappears by firing, and the solvent is volatilized. Next, after being formed into an electrode shape, by firing in a non-oxidizing atmosphere, the carbonaceous conductive agent and the binder are carbonized and sintered with the negative electrode active material to obtain a negative electrode. Note that the non-oxidizing atmosphere is a nitrogen atmosphere, an argon atmosphere, or the like.
【００１４】本発明の非水系二次電池には、含フッ素リ
チウム塩から成る電解質を非水系溶媒に適当な濃度で溶
解させた電解液を用いる。含フッ素リチウム塩とは、六
フッ化リン酸リチウム、六フッ化ヒ酸リチウム、過塩素
酸リチウム、トリフルオロメタンスルホン酸リチウム、
四フッ化ホウ酸リチウム等である。中でも、過放電時の
安定性、環境保全の観点から、六フッ化リン酸リチウム
の使用が好ましい。The non-aqueous secondary battery of the present invention uses an electrolytic solution obtained by dissolving an electrolyte comprising a fluorine-containing lithium salt in a non-aqueous solvent at an appropriate concentration. Fluorinated lithium salts include lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate,
And lithium tetrafluoroborate. Among them, use of lithium hexafluorophosphate is preferred from the viewpoints of stability during overdischarge and environmental protection.
【００１５】非水系溶媒には、一般的に非水系二次電池
に使用される極性溶媒であればいずれも使用可能であ
り、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等が使用
できる。また、これらを２種以上混合して用いても良
い。中でも、環状カーボネートであるエチレンカーボネ
ートと、鎖状カーボネートであるジメチルカーボネート
の混合溶媒が好ましい。As the non-aqueous solvent, any polar solvent generally used for non-aqueous secondary batteries can be used, and propylene carbonate, ethylene carbonate,
Dimethyl carbonate, diethyl carbonate and the like can be used. These may be used in combination of two or more. Among them, a mixed solvent of ethylene carbonate as a cyclic carbonate and dimethyl carbonate as a chain carbonate is preferable.
【００１６】かかる非水系電解液には、少量のフッ化水
素が不可避的に含まれる。フッ化水素は、電解質である
含フッ素リチウム塩の製造時に不純物として残留してお
り、さらに、含フッ素リチウム塩が溶媒中に含まれる水
分と反応することによっても生成する。例えば、含フッ
素リチウム塩である六フッ化リン酸リチウムは、水分と
反応して次式によりフッ化水素を生成する。 ＬｉＰＦ6 ＋ Ｈ2Ｏ → ＬｉＦ ＋ ＰＯＦ3 ＋ ２ＨＦ Such a non-aqueous electrolytic solution inevitably contains a small amount of hydrogen fluoride. Hydrogen fluoride remains as an impurity during the production of a fluorinated lithium salt as an electrolyte, and is also generated by the reaction of the fluorinated lithium salt with water contained in a solvent. For example, lithium hexafluorophosphate, which is a fluorine-containing lithium salt, reacts with moisture to generate hydrogen fluoride according to the following formula. LiPF 6 + H 2 O → LiF + POF 3 + 2HF
【００１７】フッ化水素は、電池の放電可能容量を低下
させる。そこで、本発明は電解液中に含まれるフッ化水
素の量を５００μｇ／ｇ以下、好ましくは２５０μｇ／
ｇ以下、さらに好ましくは１５０μｇ／ｇ以下に抑制す
ることにより、サイクル特性の良好な非水系二次電池を
得ることができる。[0017] Hydrogen fluoride reduces the dischargeable capacity of the battery. Therefore, the present invention reduces the amount of hydrogen fluoride contained in the electrolytic solution to 500 μg / g or less, preferably 250 μg / g.
g, more preferably 150 μg / g or less, a non-aqueous secondary battery with good cycle characteristics can be obtained.
【００１８】電解液中のフッ化水素量を抑制するには、
含フッ素リチウム塩中の不純物としてのフッ化水素の混
入量を減少すると同時に、溶媒中の水分量を減少させれ
ば良い。尚、溶媒中の水分は、リチウム金属を負極活物
質に用いる場合と異なり、負極活物質であるケイ素自身
と反応するものではない。したがって、溶媒中の水分量
は、電解液中のフッ化水素の濃度が必要範囲に収まるよ
うに抑制すれば足りる。To suppress the amount of hydrogen fluoride in the electrolyte,
It suffices to reduce the amount of hydrogen fluoride as an impurity in the fluorinated lithium salt and, at the same time, reduce the amount of water in the solvent. Note that, unlike the case where lithium metal is used as the negative electrode active material, the water in the solvent does not react with silicon itself, which is the negative electrode active material. Therefore, it is sufficient to suppress the amount of water in the solvent so that the concentration of hydrogen fluoride in the electrolytic solution falls within a required range.
【００１９】本発明のリチウム二次電池に用いる正極に
は、ＬｉxＣｏＯ2、ＬｉxＮｉＯ2、スピネル構造のＬｉ
xＭｎ2Ｏ4及びＭｇをドープしたＬｉxＣｏＯ2等のリチ
ウム遷移金属酸化物を用いることが好ましい。The positive electrode used in the lithium secondary battery of the present invention includes Li x CoO 2 , Li x NiO 2 and Li having a spinel structure.
It is preferable to use a lithium transition metal oxide such as Li x CoO 2 doped with x Mn 2 O 4 and Mg.
【００２０】[0020]
【実施例】（負極の製造）負極活物質としての純度９
９．９％、平均粒径１μｍのケイ素粉末（高純度化学
（株））８０重量部と、炭素質導電剤としてのグラファ
イト／ピッチ混合物（グラファイト９０重量部とピッチ
１０重量部の混合物、商品名グラフィトン、大阪化成
（株））２０重量部とをスパーテルにより混合し、窒素
雰囲気下１１００℃３時間焼成した後、振動ミルを用い
て５分間粉砕して、原料粉末を得た。原料粉末３０重量
部に、ポリフッ化ビニリデン（商品名ＫＦ−１１００、
呉羽化学（株））のｎ−メチル−２−ピロリドン溶液
（１０重量％）７０重量部を加え、振動ミルにより１０
分間混合してスラリー状とした。アプリケータ（ギャッ
プ５００μｍ）を用いてこのスラリーを銅箔（厚さ３０
μｍ）に塗布し、８０℃３０分間乾燥後、直径２０ｍｍ
の円形に裁断し、平板プレス機により１．５×１０8Ｐ
ａの圧力をかけて圧着し、塗膜を得た。塗膜を窒素雰囲
気下７５０℃３時間焼成し、負極を得た。EXAMPLES (Production of negative electrode) Purity 9 as negative electrode active material
9.9%, 80 parts by weight of silicon powder having an average particle diameter of 1 μm (Kojundo Chemical Co., Ltd.), and a graphite / pitch mixture (a mixture of 90 parts by weight of graphite and 10 parts by weight of pitch) as a carbonaceous conductive agent Grafton and 20 parts by weight of Osaka Kasei Co., Ltd. were mixed with a spatula, baked at 1100 ° C. for 3 hours in a nitrogen atmosphere, and pulverized for 5 minutes using a vibration mill to obtain raw material powder. To 30 parts by weight of the raw material powder, polyvinylidene fluoride (trade name KF-1100,
70 parts by weight of an n-methyl-2-pyrrolidone solution (10% by weight) of Kureha Chemical Co., Ltd. were added, and 10 parts by a vibration mill.
Mix for a minute to make a slurry. Using an applicator (gap 500 μm), this slurry was coated with copper foil (thickness 30).
μm), dried at 80 ° C. for 30 minutes,
And cut into 1.5 × 10 8 P
A pressure was applied under pressure to obtain a coating film. The coating film was fired at 750 ° C. for 3 hours under a nitrogen atmosphere to obtain a negative electrode.
【００２１】（電解液の調製）エチレンカーボネートと
ジメチルカーボネートの等体積混合溶媒に、六フッ化リ
ン酸リチウムを１ｍｏｌ／Ｌ溶解させ、電解液中のフッ
化水素濃度が１０００、７５０、５００、２５０、１０
０、３０及び３μｇ／ｇの７種類の電解液を調製した。(Preparation of Electrolyte Solution) Lithium hexafluorophosphate (1 mol / L) is dissolved in an equal volume mixed solvent of ethylene carbonate and dimethyl carbonate, and the concentration of hydrogen fluoride in the electrolyte solution is 1000, 750, 500, 250 , 10
Seven types of electrolyte solutions of 0, 30, and 3 μg / g were prepared.
【００２２】（正極の製造）Ｌｉ2ＣＯ3とＣｏＣＯ3を
モル比Ｌｉ／Ｃｏ＝１／１で秤量し、イソピルアルコー
ルを用いてボールミルで湿式混合した後、イソプロピル
アルコールを蒸発させ、８００℃１時間仮焼成を行っ
た。仮焼成した粉末を振動ミルにて再粉砕した後、成型
型に入れ、１．３×１０8Ｐａの圧力により直径２０ｍ
ｍ、厚さ０．５ｍｍのペレットに成型した。得られたペ
レットを８００℃１０時間焼成して正極を得た。(Production of Positive Electrode) Li 2 CO 3 and CoCO 3 were weighed at a molar ratio of Li / Co = 1/1 and wet-mixed with isopropyl alcohol in a ball mill. Preliminary firing was performed for one hour. The calcined powder is re-ground by a vibrating mill, then put into a mold, and has a diameter of 20 m under a pressure of 1.3 × 10 8 Pa.
m and molded into a pellet having a thickness of 0.5 mm. The obtained pellet was fired at 800 ° C. for 10 hours to obtain a positive electrode.
【００２３】（コイン型電池の作製）得られた負極、７
種類の電解液及び正極を用いてコイン型電池を作製し
た。セパレーターとして２５μｍ厚の多孔性ポリエチレ
ンフィルム（旭化成（株））を用いた。(Preparation of coin type battery)
A coin-type battery was manufactured using the different types of electrolytes and the positive electrode. A 25 μm-thick porous polyethylene film (Asahi Kasei Corporation) was used as a separator.
【００２４】（コイン型電池の評価）得られたコイン型
電池について、定電流一定電圧充放電試験を行い、表１
の結果を得た。(Evaluation of Coin-Type Battery) The obtained coin-type battery was subjected to a constant current constant voltage charge / discharge test.
Was obtained.
【００２５】表１ Table 1
【００２６】[0026]
【発明の効果】本発明は、ケイ素を活物質とする負極
と、非水系電解液を備えた非水系二次電池であって、非
水系電解液が含フッ素リチウム塩を電解質として含む場
合に、非水系電解液中のフッ化水素量を２５０μｇ／ｇ
以下とすることにより、良好なサイクル特性の非水系二
次電池を提供することができる。According to the present invention, there is provided a non-aqueous secondary battery including a negative electrode containing silicon as an active material and a non-aqueous electrolyte, wherein the non-aqueous electrolyte contains a fluorine-containing lithium salt as an electrolyte. 250 μg / g of hydrogen fluoride in non-aqueous electrolyte
By performing the following, a non-aqueous secondary battery having good cycle characteristics can be provided.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/02 - 4/04 H01M 4/38 H01M 10/40 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) H01M 4/02-4/04 H01M 4/38 H01M 10/40
Claims (1)
有機材料と共に焼成してなる負極と、非水系電解液を備
えた非水系二次電池であって、 非水系電解液が含フッ素リチウム塩を含み、該非水系電
解液中のフッ化水素量が３μｇ／ｇ以下である非水系二
次電池。1. A non-aqueous secondary battery comprising a negative electrode obtained by firing silicon or a compound thereof together with a carbon material or an organic material, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte contains a fluorine-containing lithium salt. A non-aqueous secondary battery in which the amount of hydrogen fluoride in the non-aqueous electrolyte is 3 μg / g or less.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05064499A JP3179434B2 (en) | 1999-02-26 | 1999-02-26 | Non-aqueous secondary battery |
| EP99973178A EP1054462A4 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
| US09/600,176 US6413672B1 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
| PCT/JP1999/006776 WO2000033404A1 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
| KR1020007008486A KR100609862B1 (en) | 1998-12-03 | 1999-12-02 | Lithium secondary cell and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05064499A JP3179434B2 (en) | 1999-02-26 | 1999-02-26 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000251933A JP2000251933A (en) | 2000-09-14 |
| JP3179434B2 true JP3179434B2 (en) | 2001-06-25 |
Family
ID=12864669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05064499A Expired - Fee Related JP3179434B2 (en) | 1998-12-03 | 1999-02-26 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3179434B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100680650B1 (en) | 2002-11-29 | 2007-02-08 | 미츠이 마이닝 & 스멜팅 콤파니 리미티드 | Negative electrode for non-aqueous electrolyte secondary cell and method for manufacture thereof, and non-aqueous electrolyte secondary cell |
| KR101850950B1 (en) * | 2010-10-20 | 2018-04-20 | 신토고교 가부시키가이샤 | Method and device for manufacturing layered structure constituting all-solid battery, and all-solid battery provided with layered structure |
-
1999
- 1999-02-26 JP JP05064499A patent/JP3179434B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000251933A (en) | 2000-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4186507B2 (en) | Carbon-containing lithium iron composite oxide for positive electrode active material of lithium secondary battery and method for producing the same | |
| JP5099168B2 (en) | Lithium ion secondary battery | |
| JP4046601B2 (en) | Negative electrode material for lithium secondary battery and lithium secondary battery using the same | |
| JP3826746B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2004319129A (en) | Anode active material and nonaqueous electrolyte secondary battery using it | |
| KR101972187B1 (en) | Structurally stable active material for battery electrodes | |
| WO2011052533A1 (en) | Lithium secondary battery | |
| WO2002039523A1 (en) | Positive electrode material and cell comprising the same | |
| CN115799601A (en) | Lithium ion battery | |
| JP2012178327A (en) | Electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for manufacturing electrode for nonaqueous electrolyte secondary battery | |
| CN110104677B (en) | Composite lithium titanate material and preparation method and application thereof | |
| JP3196226B2 (en) | Non-aqueous electrolyte secondary battery | |
| KR20160085089A (en) | Secondary Battery | |
| JP2001126733A (en) | Nonaqueous electrolytic material | |
| JP2005005117A (en) | Battery | |
| JP2013110105A (en) | Negative electrode for lithium ion secondary battery, and lithium ion secondary battery including the negative electrode | |
| JP2016004708A (en) | Cathode active material for lithium ion secondary battery and manufacturing method for the same, and lithium ion secondary battery using the same | |
| KR101375326B1 (en) | Composite anode active material, method of preparing the same, anode and lithium battery containing the material | |
| JP2002117836A (en) | Negative electrode for nonaqueous electrolyte secondary battery and battery using it | |
| US10177370B2 (en) | Positive electrode for lithium ion secondary battery and lithium ion secondary battery using the same | |
| Feng et al. | Electrochemical property of LiMn2O4 in over-discharged conditions | |
| KR101142533B1 (en) | Metal based Zn Negative Active Material and Lithium Secondary Battery Comprising thereof | |
| JP2000156224A (en) | Nonaqueous electrolyte battery | |
| EP3553852B1 (en) | Power battery and positive electrode plate thereof | |
| KR20240017067A (en) | Battery cathode material, manufacturing method thereof, and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090413 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090413 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100413 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110413 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120413 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130413 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130413 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140413 Year of fee payment: 13 |
|
| LAPS | Cancellation because of no payment of annual fees |