JP3203118B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3203118B2 JP3203118B2 JP35046093A JP35046093A JP3203118B2 JP 3203118 B2 JP3203118 B2 JP 3203118B2 JP 35046093 A JP35046093 A JP 35046093A JP 35046093 A JP35046093 A JP 35046093A JP 3203118 B2 JP3203118 B2 JP 3203118B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- aqueous electrolyte
- electrolyte secondary
- present
- 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]
【産業上の利用分野】本発明は、炭素材料を負極材料と
する負極を備える非水電解液二次電池に係わり、詳しく
は放電末期の負極側における電解液の分解を起こりにく
くすることによりサイクル特性及び保存特性に優れた非
水電解液二次電池を得ることを目的とした、負極の改良
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery provided with a negative electrode using a carbon material as a negative electrode material, and more particularly, to a cycle by reducing decomposition of the electrolyte on the negative electrode side at the end of discharge. The present invention relates to improvement of a negative electrode for the purpose of obtaining a non-aqueous electrolyte secondary battery having excellent characteristics and storage characteristics.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
非水電解液二次電池が、エネルギー密度が高く、しかも
水の分解電圧を考慮する必要が無いため高電圧化が可能
であるなどの利点があることから、脚光を浴びつつあ
る。2. Description of the Related Art In recent years,
Non-aqueous electrolyte secondary batteries have been attracting attention because of their advantages such as high energy density and the fact that there is no need to consider the decomposition voltage of water, which enables higher voltages.
【０００３】而して、非水電解液二次電池の負極材料と
して、サイクル寿命の長期化を図るべく、樹枝状の電析
リチウムの成長に因る内部短絡の虞れの無いコークス、
黒鉛、有機物焼成体等のリチウムイオンを吸蔵及び放出
することが可能な炭素材料が提案されている。As a negative electrode material for a non-aqueous electrolyte secondary battery, in order to prolong the cycle life, there is no possibility of internal short circuit due to the growth of dendritic electrodeposited lithium.
Carbon materials capable of occluding and releasing lithium ions, such as graphite and fired organic materials, have been proposed.
【０００４】しかしながら、炭素材料を負極材料として
用いると、負極電位が２Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）以上
に貴となる放電末期に電解液の分解が起こり、特に負極
集電体の材料として銅を用いた場合には、銅の溶出が同
時に起こる。これらの原因により、従来のこの種の非水
電解液二次電池には、サイクル特性及び放電状態での保
存特性が良くないという問題があった。However, when a carbon material is used as a negative electrode material, decomposition of an electrolytic solution occurs at the end of discharge when the negative electrode potential becomes more than 2 V (vs. Li / Li + ), and particularly, copper is used as a material for the negative electrode current collector. In the case of using, copper elution occurs simultaneously. For these reasons, conventional non-aqueous electrolyte secondary batteries of this type have a problem in that cycle characteristics and storage characteristics in a discharged state are poor.
【０００５】本発明は、この問題を解決するべくなされ
たものであって、その目的とするところは、放電末期に
おける負極電位の急上昇を防止することにより、サイク
ル特性及び放電状態での保存特性に優れた非水電解液二
次電池を提供するにある。The present invention has been made to solve this problem, and an object of the present invention is to prevent a sudden increase in the negative electrode potential at the end of discharge to improve cycle characteristics and storage characteristics in a discharged state. An object of the present invention is to provide an excellent non-aqueous electrolyte secondary battery.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水電解液二次電池（以下、「本発明電
池」と称する。）は、リチウムイオンを吸蔵及び放出す
ることが可能な炭素材料を負極に用いてなる非水電解液
二次電池において、前記炭素材料に、ＦｅＯ、Ｆｅ
Ｏ 2 、Ｆｅ 2 Ｏ 3 、ＳｎＯ、ＳｎＯ 2 、Ｖ 2 Ｏ 5 、Ｂｉ
2 Ｓｎ 3 Ｏ 9 、ＷＯ 3 、Ｎｂ 2 Ｏ 5 及びＭｏＯ 3 よりな
る群から選ばれた少なくとも一種の金属酸化物が、当該
金属酸化物と前記炭素材料との総量に対して、１〜１０
重量％添加されてなる。A non-aqueous electrolyte secondary battery according to the present invention for achieving the above object (hereinafter referred to as "battery of the present invention") is capable of occluding and releasing lithium ions. In a non-aqueous electrolyte secondary battery using a possible carbon material for a negative electrode, the carbon material may include FeO, Fe
O 2 , Fe 2 O 3 , SnO, SnO 2 , V 2 O 5 , Bi
I than 2 Sn 3 O 9, WO 3 , Nb 2 O 5 and MoO 3
At least one metal oxide selected from the group consisting of 1 to 10 with respect to the total amount of the metal oxide and the carbon material.
% By weight.
【０００７】[0007]
【０００８】金属酸化物の添加量は、当該金属酸化物と
前記炭素材料との総量（１００重量％）に対して、１〜
１０重量％の範囲である。金属酸化物の添加量が１重量
％未満の場合は過少のため負極電位の急上昇が充分に防
止されず、一方同添加量が１０重量％を越えた場合は、
炭素材料の量が少なくなり電池容量が低下するととも
に、添加せる金属酸化物の導電性が低いことに起因して
負極の抵抗が大きくなり、その結果負極での充電反応が
不均一となり電解液が分解する電位部分が部分的に存在
するようになるため充電状態での保存特性が低下する。The addition amount of the metal oxide is 1 to 100% by weight based on the total amount of the metal oxide and the carbon material (100% by weight).
It is in the range of 10% by weight. When the addition amount of the metal oxide is less than 1% by weight, a sharp increase in the negative electrode potential is not sufficiently prevented because the amount is too small. On the other hand, when the addition amount exceeds 10% by weight,
As the amount of carbon material decreases and the battery capacity decreases, the resistance of the negative electrode increases due to the low conductivity of the metal oxide to be added. Since the potential portion to be decomposed partially exists, storage characteristics in a charged state are deteriorated.
【０００９】本発明における炭素材料としては、リチウ
ムイオンを吸蔵及び放出することが可能なものであれば
特に制限されないが、格子面（００２）面のｄ値（ｄ
002 ）が３．３５〜３．４０Åで、ｃ軸方向の結晶子の
大きさ（Ｌｃ）が５００Å以上である、黒鉛化度が高
く、しかも結晶性の高い炭素材料を用いた場合に、特に
放電末期に負極の表面で電解液の分解が顕著に起こる。
それゆえ、リチウムイオンを吸蔵及び放出することが可
能な金属酸化物を炭素材料に添加する本発明の効果も、
上記範囲のｄ002 及びＬｃを有する炭素材料を用いた場
合に特に顕著に発現される。The carbon material in the present invention is not particularly limited as long as it can occlude and release lithium ions, but the d value (d
002 ) is 3.35 to 3.40 °, the crystallite size in the c-axis direction (Lc) is 500 ° or more, and a highly graphitized carbon material with high crystallinity is used. At the end of discharge, the decomposition of the electrolytic solution occurs remarkably on the surface of the negative electrode.
Therefore, the effect of the present invention in which a metal oxide capable of inserting and extracting lithium ions is added to the carbon material,
This is particularly noticeable when a carbon material having d 002 and Lc in the above ranges is used.
【００１０】[0010]
【作用】炭素材料に所定量の金属酸化物が添加されてい
るので、放電末期においても負極電位が急上昇しにく
い。すなわち、放電末期における電池電圧の低下が緩や
かになる。それゆえ、電解液の分解や集電体材料（銅な
ど）の溶出が起こりにくい卑な負極電位領域で各サイク
ルにおける放電を終止することが容易になる。なお、金
属酸化物の添加により負極電位が急上昇しにくくなる理
由は定かでないが、充電時に炭素材料に吸蔵されたリチ
ウムイオンの殆どが、放電末期に電解質中へ放出されて
も、充電時に金属酸化物に吸蔵されたリチウムイオンが
放出されるまでは、この金属酸化物中のリチウムイオン
が負極電位の急上昇を抑止するためと推察される。Since a predetermined amount of metal oxide is added to the carbon material, the potential of the negative electrode is unlikely to increase rapidly even at the end of discharge. That is, the decrease in the battery voltage at the end of discharge becomes gentle. Therefore, it becomes easy to terminate the discharge in each cycle in a low negative electrode potential region where decomposition of the electrolytic solution and elution of the current collector material (such as copper) do not easily occur. It is not clear why the addition of the metal oxide makes it difficult for the negative electrode potential to rapidly rise. However, even if most of the lithium ions occluded in the carbon material at the time of charging are released into the electrolyte at the end of discharging, the metal oxide is not charged during charging. Until the lithium ions occluded by the object are released, it is presumed that the lithium ions in the metal oxide suppress a rapid rise in the negative electrode potential.
【００１１】[0011]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples, and may be carried out by appropriately changing the scope of the present invention. Is possible.
【００１２】（実施例１） 〔正極の作製〕正極活物質としてのＬｉＣｏＯ2 ９０重
量部と、導電剤としての人造黒鉛５重量部と、結着剤と
してのポリフッ化ビニリデン５重量部のＮ−メチルピロ
リドン溶液とを混練してスラリーを調製し、このスラリ
ーを正極集電体としてのアルミニウム箔の両面に、ドク
ターブレード法により塗布し、１５０°Ｃで２時間真空
乾燥して正極を作製した。(Example 1) [Preparation of positive electrode] N-containing 90 parts by weight of LiCoO 2 as a positive electrode active material, 5 parts by weight of artificial graphite as a conductive agent, and 5 parts by weight of polyvinylidene fluoride as a binder A slurry was prepared by kneading the mixture with a methylpyrrolidone solution, and this slurry was applied to both sides of an aluminum foil as a positive electrode current collector by a doctor blade method, and vacuum-dried at 150 ° C. for 2 hours to produce a positive electrode.
【００１３】〔負極の作製〕黒鉛粉末（ｄ002 ＝３．３
５７Å；Ｌｃ＝５００Å）９５重量部と、添加剤として
のＦｅＯ粉末５重量部と、結着剤としてのポリフッ化ビ
ニリデン５重量部のＮ−メチルピロリドン溶液とを混練
してスラリーを調製し、このスラリーを負極集電体とし
ての銅箔の両面に、ドクターブレード法により塗布し、
１５０°Ｃで２時間真空乾燥して負極を作製した。[Preparation of Negative Electrode] Graphite powder (d 002 = 3.3)
57 °; Lc = 500 °) 95 parts by weight, 5 parts by weight of FeO powder as an additive, and an N-methylpyrrolidone solution of 5 parts by weight of polyvinylidene fluoride as a binder were kneaded to prepare a slurry. The slurry is applied to both sides of a copper foil as a negative electrode current collector by a doctor blade method,
Vacuum drying was performed at 150 ° C. for 2 hours to produce a negative electrode.
【００１４】〔電解液の調製〕エチレンカーボネートと
ジエチルカーボネートとの等体積混合溶媒に、ＬｉＰＦ
6 を１モル／リットル溶かして電解液を調製した。[Preparation of Electrolyte Solution] LiPF was added to an equal volume mixed solvent of ethylene carbonate and diethyl carbonate.
6 was dissolved at 1 mol / liter to prepare an electrolytic solution.
【００１５】〔電池の組立〕以上の正負両極及び電解液
を用いてＡＡサイズ（単３型）の本発明電池ＢＡ１を組
み立てた。なお、セパレータとしてイオン透過性のポリ
プロピレン製の微多孔膜を用いた。[Assembly of Battery] An AA (AA) type battery BA1 of the present invention was assembled using the above positive and negative electrodes and the electrolytic solution. Note that an ion-permeable polypropylene microporous membrane was used as a separator.
【００１６】図１は作製した本発明電池ＢＡ１の断面図
であり、同図に示す本発明電池ＢＡ１は、正極１及び負
極２、これら両電極を離間するセパレータ３、正極リー
ド４、負極リード５、正極外部端子６、負極缶７などか
らなる。正極１及び負極２は非水電解液が注入されたセ
パレータ３を介して渦巻き状に巻き取られた状態で負極
缶７内に収容されており、正極１は正極リード４を介し
て正極外部端子６に、また負極２は負極リード５を介し
て負極缶７に接続され、電池ＢＡ１内部で生じた化学エ
ネルギーを電気エネルギーとして外部へ取り出し得るよ
うになっている。FIG. 1 is a cross-sectional view of the battery BA1 of the present invention produced. The battery BA1 of the present invention shown in FIG. 1 has a positive electrode 1 and a negative electrode 2, a separator 3 separating these electrodes, a positive electrode lead 4, and a negative electrode lead 5. , A positive electrode external terminal 6, a negative electrode can 7, and the like. The positive electrode 1 and the negative electrode 2 are housed in a negative electrode can 7 while being spirally wound through a separator 3 into which a non-aqueous electrolyte is injected, and the positive electrode 1 is connected to a positive electrode terminal via a positive electrode lead 4. 6, and the negative electrode 2 is connected to a negative electrode can 7 via a negative electrode lead 5, so that chemical energy generated inside the battery BA1 can be extracted to the outside as electric energy.
【００１７】（実施例２〜１０） 負極の作製において、ＦｅＯ粉末５重量部に代えて、Ｆ
ｅＯ2 、Ｆｅ2 Ｏ3 、ＳｎＯ、ＳｎＯ2 、Ｖ2 Ｏ5 、Ｂ
ｉ2 Ｓｎ3 Ｏ9 、ＷＯ3 、Ｎｂ2 Ｏ5 、ＭｏＯ3 を５重
量部用いたこと以外は実施例１と同様にして、順に本発
明電池ＢＡ２〜ＢＡ１０を組み立てた。(Examples 2 to 10 ) In the preparation of the negative electrode, instead of 5 parts by weight of FeO powder, F
eO 2 , Fe 2 O 3 , SnO, SnO 2 , V 2 O 5 , B
Batteries BA2 to BA10 of the present invention were assembled in the same manner as in Example 1 except that 5 parts by weight of i 2 Sn 3 O 9 , WO 3 , Nb 2 O 5 , and MoO 3 were used.
【００１８】（比較例１）負極の作製において、ＦｅＯ
等の添加剤を添加しなかったこと以外は実施例１と同様
にして、比較電池ＢＣ１を組み立てた。Comparative Example 1 In the production of the negative electrode, FeO
A comparative battery BC1 was assembled in the same manner as in Example 1 except that no additives such as were added.
【００１９】〔各電池の放電状態での保存特性〕 本発明電池ＢＡ１〜ＢＡ１０及び比較電池ＢＣ１につい
て、２００ｍＡで４．２Ｖまで充電した後、２００ｍＡ
で２．７５Ｖまで放電したときの、放電直後の開回路電
圧、６０°Ｃで５日間保存した後の開回路電圧及び６０
°Ｃで１０日間保存した後の開回路電圧をそれぞれ求め
た。次いで、６０°Ｃで１０日間保存した後の各電池
を、２００ｍＡで４．２Ｖまで充電した後、２００ｍＡ
で２．７５Ｖまで放電して、放電容量を求めた。結果を
表１に示す。[Storage Characteristics in Discharged State of Each Battery] The batteries BA1 to BA10 of the present invention and the comparative battery BC1 were charged at 200 mA to 4.2 V and then charged at 200 mA.
The open circuit voltage immediately after the discharge when discharged to 2.75 V at 60 ° C., the open circuit voltage after storage at 60 ° C. for 5 days, and 60 ° C.
The open circuit voltage after storage at 10 ° C. for 10 days was determined. Next, each battery after being stored at 60 ° C. for 10 days was charged at 200 mA to 4.2 V, and then charged at 200 mA.
Was discharged to 2.75 V to determine the discharge capacity. Table 1 shows the results.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表１に示すように、本発明電池ＢＡ１〜Ｂ
Ａ１０は、比較電池ＢＣ１に比し、保存に因る電圧降下
が極めて小さい。これは、本発明電池ＢＡ１〜ＢＡ１０
では自己放電による負極電位の上昇が緩やかであったの
に対して、比較電池ＢＣ１では自己放電により負極電位
が急上昇したことを示している。また、本発明電池ＢＡ
１〜ＢＡ１０では６０°Ｃで１０日間保存した後の放電
容量が大きいのに対して、比較電池ＢＣ１では同放電容
量が小さい。これは、比較電池ＢＣ１では、保存中に電
解液の分解が激しく起こったためである。As shown in Table 1, the batteries BA1 to B of the present invention
A10 has a significantly smaller voltage drop due to storage than the comparative battery BC1. This is because the batteries BA1 to BA10 of the present invention
Shows that the rise in the negative electrode potential due to self-discharge was gradual, whereas the comparative battery BC1 showed a rapid rise in the negative electrode potential due to self-discharge. In addition, the battery BA of the present invention
1 to BA10 have a large discharge capacity after being stored at 60 ° C. for 10 days, while the comparative battery BC1 has a small discharge capacity. This is because in the comparative battery BC1, the decomposition of the electrolytic solution occurred vigorously during storage.
【００２２】〔添加剤の添加量と１サイクル目の放電容
量及びサイクル寿命との関係〕負極の作製において、Ｆ
ｅＯ粉末５重量部に代えて、Ｂｉ2 Ｓｎ3 Ｏ9 粉末を種
々の割合で黒鉛粉末に添加したこと以外は実施例１と同
様にして、非水電解液二次電池を組み立て、各電池の１
サイクル目の放電容量及びサイクル寿命を調べた。サイ
クル寿命は、放電容量が１サイクル目の放電容量の７５
％以下となった時点のサイクル数で評価した。結果を、
図２に示す。[Relationship between the amount of additive and the discharge capacity and cycle life in the first cycle]
A non-aqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that Bi 2 Sn 3 O 9 powder was added to the graphite powder at various ratios instead of 5 parts by weight of the eO powder. 1
The discharge capacity and cycle life at the cycle were examined. The cycle life is 75% of the discharge capacity in the first cycle.
% Was evaluated based on the number of cycles. The result
As shown in FIG.
【００２３】図２は、Ｂｉ2 Ｓｎ3 Ｏ9 粉末の添加量と
１サイクル目の放電容量及びサイクル寿命との関係を、
左縦軸にサイクル数（回）を、右縦軸に１サイクル目の
放電容量（ｍＡｈ）を、また横軸にＢｉ2 Ｓｎ3 Ｏ9 粉
末の添加量（重量％；黒鉛粉末とＢｉ2 Ｓｎ3 Ｏ9 粉末
の総量に占めるＢｉ2 Ｓｎ3 Ｏ9 粉末の重量％）をとっ
て示したグラフであり、同図に示すように、Ｂｉ2 Ｓｎ
3 Ｏ9 粉末の添加量が１重量％未満であると、サイクル
寿命が短くなり、また同添加量が１０重量％を越える
と、１サイクル目の放電容量（電池容量）が低下する。
このことから、電池容量が大きく、しかもサイクル寿命
の長い電池を得るためには、Ｂｉ2 Ｓｎ3Ｏ9 粉末の添
加量を１〜１０重量％に規制する必要があることが分か
る。なお、他の添加剤についても、それらの添加量を上
記範囲に規制する必要があることを確認した。FIG. 2 shows the relationship between the amount of Bi 2 Sn 3 O 9 powder added and the discharge capacity and cycle life in the first cycle.
The left vertical axis indicates the number of cycles (times), the right vertical axis indicates the discharge capacity (mAh) of the first cycle, and the horizontal axis indicates the amount of Bi 2 Sn 3 O 9 powder added (% by weight; graphite powder and Bi 2 Sn). 3 O 9% by weight of Bi 2 Sn 3 O 9 powder relative to the total amount of powder) is a graph showing taking, as shown in the figure, Bi 2 Sn
If the amount of the 3 O 9 powder is less than 1% by weight, the cycle life becomes short, and if the amount exceeds 3% by weight, the discharge capacity (battery capacity) in the first cycle decreases.
From this, it is understood that in order to obtain a battery having a large battery capacity and a long cycle life, it is necessary to regulate the addition amount of Bi 2 Sn 3 O 9 powder to 1 to 10% by weight. In addition, it was confirmed that the amount of other additives needed to be regulated in the above range.
【００２４】叙上の実施例では本発明を円筒型電池に適
用する場合の具体例について説明したが、電池の形状に
特に制限はなく、本発明は扁平型、角型等、種々の形状
の非水系電池に適用し得るものである。In the above embodiment, a specific example in which the present invention is applied to a cylindrical battery has been described. However, the shape of the battery is not particularly limited, and the present invention is applicable to various shapes such as a flat type and a square type. It can be applied to non-aqueous batteries.
【００２５】[0025]
【発明の効果】炭素材料に所定量のリチウムを吸蔵及び
放出することが可能な特定の金属酸化物が添加されてい
るので、放電末期においても負極電位が急上昇しにく
い。それゆえ、充放電サイクル時又は放電状態で保存し
た時に電解液の分解や集電体材料（銅など）の溶出が起
こりにくくなり、充放電サイクル特性及び放電状態での
保存特性に優れる。According to the present invention, since a specific metal oxide capable of occluding and releasing a predetermined amount of lithium is added to the carbon material, the negative electrode potential hardly rises rapidly even at the end of discharge. Therefore, decomposition of the electrolytic solution and elution of the current collector material (such as copper) during a charge / discharge cycle or when stored in a discharged state are less likely to occur, and the charge / discharge cycle characteristics and the storage characteristics in a discharged state are excellent.
【図１】実施例で作製した本発明電池の断面図である。FIG. 1 is a cross-sectional view of a battery of the present invention produced in an example.
【図２】Ｂｉ2 Ｓｎ3 Ｏ9 粉末の添加量と１サイクル目
の放電容量及びサイクル寿命との関係を示すグラフであ
る。FIG. 2 is a graph showing the relationship between the amount of Bi 2 Sn 3 O 9 powder added and the discharge capacity and cycle life in the first cycle.
ＢＡ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータ BA1 Battery of the present invention 1 Positive electrode 2 Negative electrode 3 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (56)参考文献 特開 平５−174872（ＪＰ，Ａ) 特開 平６−349524（ＪＰ，Ａ) 特開 平５−258773（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/02 - 4/04 H01M 10/40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Nishio, Inventor 2-5-5, Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshihiko Saito 2-5-2, Keihanhondori, Moriguchi-shi, Osaka No. 5 Inside Sanyo Electric Co., Ltd. (56) References JP-A-5-174872 (JP, A) JP-A-6-349524 (JP, A) JP-A-5-258773 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01M 4/02-4/04 H01M 10/40
Claims (1)
可能な炭素材料を負極に用いてなる非水電解液二次電池
において、前記炭素材料に、ＦｅＯ、ＦｅＯ 2 、Ｆｅ 2
Ｏ 3 、ＳｎＯ、ＳｎＯ 2 、Ｖ 2 Ｏ 5 、Ｂｉ 2 Ｓｎ
3 Ｏ 9 、ＷＯ 3 、Ｎｂ 2 Ｏ 5 及びＭｏＯ 3 よりなる群か
ら選ばれた少なくとも一種の金属酸化物が、当該金属酸
化物と前記炭素材料との総量に対して、１〜１０重量％
添加されていることを特徴とする非水電解液二次電池。1. The method according to claim 1, wherein lithium ions are inserted and released.
Non-aqueous electrolyte secondary battery using a carbon material as a negative electrode
In the carbon material,FeO, FeO Two , Fe Two
O Three , SnO, SnO Two , V Two O Five , Bi Two Sn
Three O 9 , WO Three , Nb Two O Five And MoO Three Group consisting of
At least one ofThe metal oxide is the metal acid
1 to 10% by weight based on the total amount of the compound and the carbon material
A non-aqueous electrolyte secondary battery characterized by being added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35046093A JP3203118B2 (en) | 1993-12-27 | 1993-12-27 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35046093A JP3203118B2 (en) | 1993-12-27 | 1993-12-27 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07192723A JPH07192723A (en) | 1995-07-28 |
| JP3203118B2 true JP3203118B2 (en) | 2001-08-27 |
Family
ID=18410650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35046093A Expired - Fee Related JP3203118B2 (en) | 1993-12-27 | 1993-12-27 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3203118B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6727535B1 (en) | 1998-11-09 | 2004-04-27 | Paratek Microwave, Inc. | Ferroelectric varactor with built-in DC blocks |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ID20483A (en) * | 1997-04-24 | 1998-12-31 | Matsushita Electric Ind Co Ltd | SECONDARY BATTERIES WITH ELECTROLITE NOT LIQUID |
| US6451482B1 (en) | 1997-04-24 | 2002-09-17 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary batteries |
| EP0886332B1 (en) * | 1997-06-19 | 2000-10-11 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous secondary lithium battery with a negative electrode comprising (CF)n |
| JP3882285B2 (en) * | 1997-09-22 | 2007-02-14 | トヨタ自動車株式会社 | Negative electrode for lithium ion secondary battery |
| JP4114247B2 (en) * | 1998-09-30 | 2008-07-09 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| WO2001022520A1 (en) * | 1999-09-24 | 2001-03-29 | Matsushita Electric Industrial Co., Ltd. | Lithium cell |
| JP3103357B1 (en) | 1999-09-28 | 2000-10-30 | 株式会社サムスン横浜研究所 | Method for producing negative electrode material for lithium secondary battery |
| JP3645463B2 (en) | 2000-01-21 | 2005-05-11 | 株式会社日立製作所 | Semiconductor integrated circuit device |
| JP4560877B2 (en) * | 2000-04-05 | 2010-10-13 | パナソニック株式会社 | Lithium secondary battery |
| JP4815660B2 (en) * | 2000-06-16 | 2011-11-16 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| JP4503807B2 (en) * | 2000-10-11 | 2010-07-14 | 東洋炭素株式会社 | Negative electrode for lithium ion secondary battery and method for producing negative electrode for lithium ion secondary battery |
| JP5487598B2 (en) * | 2008-11-17 | 2014-05-07 | 株式会社豊田中央研究所 | Lithium secondary battery and method of using the same |
| US10193183B2 (en) | 2014-02-28 | 2019-01-29 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary batteries |
| JP6246682B2 (en) * | 2014-09-01 | 2017-12-13 | 日立オートモティブシステムズ株式会社 | Lithium ion secondary battery |
| JP2016081691A (en) * | 2014-10-16 | 2016-05-16 | 日立化成株式会社 | Lithium ion secondary battery, negative electrode and battery system using these |
-
1993
- 1993-12-27 JP JP35046093A patent/JP3203118B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6727535B1 (en) | 1998-11-09 | 2004-04-27 | Paratek Microwave, Inc. | Ferroelectric varactor with built-in DC blocks |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07192723A (en) | 1995-07-28 |
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