JP3245886B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3245886B2 JP3245886B2 JP12732091A JP12732091A JP3245886B2 JP 3245886 B2 JP3245886 B2 JP 3245886B2 JP 12732091 A JP12732091 A JP 12732091A JP 12732091 A JP12732091 A JP 12732091A JP 3245886 B2 JP3245886 B2 JP 3245886B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- aqueous electrolyte
- secondary battery
- electrolyte 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]
【産業上の利用分野】本発明は、非水電解液二次電池に
関し、特に正極を改良した非水電解液二次電池に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery having an improved positive electrode.
【０００２】[0002]
【従来の技術】リチウム，リチウム合金またはリチウム
化合物を負極とする非水電解液二次電池は高電圧で高エ
ネルギー密度となることが期待され、多くの研究が行わ
れている。2. Description of the Related Art A non-aqueous electrolyte secondary battery using lithium, a lithium alloy or a lithium compound as a negative electrode is expected to have a high voltage and a high energy density, and much research has been conducted.
【０００３】特に、これら電池の正極活物質としてＭｎ
Ｏ2やＴｉＳ2がよく検討されている。これらの正極活物
質はＬｉに対する電位が３Ｖ程度であるが、最近、Ｌｉ
Ｍｎ 2Ｏ4およびＬｉＣｏＯ2がＬｉに対して４Ｖ以上の
電位を示す正極活物質として注目されている。In particular, Mn is used as a positive electrode active material of these batteries.
OTwoAnd TiSTwoHas been well studied. These positive electrode active materials
The potential of Li is about 3 V with respect to Li.
Mn TwoOFourAnd LiCoOTwoIs more than 4V with respect to Li
It is attracting attention as a positive electrode active material showing a potential.
【０００４】すなわち、電池の高エネルギー密度を得る
手段として容量の拡大とともに電池電圧を高める努力が
なされている。That is, efforts have been made to increase the battery voltage as well as the capacity as a means for obtaining a high energy density of the battery.
【０００５】このうち、ＬｉＣｏＯ2は、その放電容量
が大きく、優れた充放電サイクル特性を有する可能性が
あることから正極活物質として有望と考えられている。[0005] Among them, LiCoO 2 is considered to be promising as a positive electrode active material because it has a large discharge capacity and may have excellent charge / discharge cycle characteristics.
【０００６】さらに、二次電池として重要な必要特性の
１つである充放電サイクル特性を向上するため、ＬｉＣ
ｏＯ2へのＭｎ，Ｎｉ，Ｃｒ，Ｆｅなどの添加も試みら
れ、充放電サイクル特性の一層の向上が図られている。Further, in order to improve the charge / discharge cycle characteristics, which is one of the important necessary characteristics as a secondary battery, LiC
Attempts have been made to add Mn, Ni, Cr, Fe, and the like to oO 2, and further improvement of charge / discharge cycle characteristics has been achieved.
【０００７】[0007]
【発明が解決しようとする課題】上記の正極活物質を用
いることにより放電容量が大きく充放電サイクル特性に
優れた非水電解液二次電池を実現できるが、充電電圧が
４Ｖを越えるため、充電後の電池の高温保存特性が不充
分であるという問題があった。非水電解液二次電池の高
温保存については電池内部の正極活物質ＬｉＣｏＯ2に
混在する可能性のあるＬｉＯＨなどのアルカリ、電解液
中の微量水分や電解液溶媒の分解が原因となり、電池内
部抵抗の増大や充放電容量の低下という問題を引き起こ
す。特に電池電圧が高くなるほどこれらの現象は顕著に
なり、また、高温保存時においてより著しいものとな
る。A non-aqueous electrolyte secondary battery having a large discharge capacity and excellent charge-discharge cycle characteristics can be realized by using the above-mentioned positive electrode active material. There was a problem that the high-temperature storage characteristics of the later battery were insufficient. High temperature storage of non-aqueous electrolyte secondary batteries is caused by the decomposition of alkalis such as LiOH, which may be mixed in the positive electrode active material LiCoO 2 inside the batteries, trace moisture in the electrolyte, and electrolyte solvents. This causes problems such as an increase in resistance and a decrease in charge / discharge capacity. In particular, these phenomena become more remarkable as the battery voltage becomes higher, and become more remarkable during high-temperature storage.
【０００８】電池内部へ持ち込まれる水分については、
電解液の蒸留処理を始めとする精製および正極活物質の
乾燥処理などにより電池内部への水分の持込みを抑える
努力がなされている。しかし、充放電を繰り返し行う必
要のある二次電池の場合、特に、充電電圧が４Ｖを越え
る場合にはこれら水分の除去などの前処理だけでは良好
な高温保存特性を得ることができない。[0008] Regarding moisture brought into the battery,
Efforts have been made to suppress the incorporation of water into the battery by purifying the electrolyte solution, including the distillation process, and drying the positive electrode active material. However, in the case of a secondary battery that needs to be repeatedly charged and discharged, particularly when the charging voltage exceeds 4 V, good high-temperature storage characteristics cannot be obtained only by pretreatment such as removal of water.
【０００９】正極活物質と電解液溶媒との反応やこの反
応により生成した物質と負極活物質との反応が起こりや
すくなり、電池の性能低下が生じると考えられる。It is considered that the reaction between the positive electrode active material and the electrolytic solution solvent and the reaction between the substance produced by this reaction and the negative electrode active material are likely to occur, and the performance of the battery will be reduced.
【００１０】本発明はこのような課題を解決するもの
で、高温保存特性を向上した非水電解液二次電池を提供
することを目的とする。An object of the present invention is to solve such a problem and to provide a non-aqueous electrolyte secondary battery having improved high-temperature storage characteristics.
【００１１】[0011]
【課題を解決するための手段】この課題を解決するため
本発明の非水電解質二次電池は、ＬｉＣｏＯ２で表わさ
れる複合酸化物を活物質とする正極と、リチウムを吸蔵
放出することができる負極および非水電解液を有し、前
記正極中に無水ＳｉＯ２、Ａｌ２Ｏ３、Ｖ２Ｏ５、Ｉｒ
Ｏ２から選ばれる少なくとも１つの固体酸を１モルのＬ
ｉＣｏＯ２に対して０．００２モルから０．２モル添加
したものを用いる。To solve this problem, a nonaqueous electrolyte secondary battery according to the present invention comprises a positive electrode using a composite oxide represented by LiCoO2 as an active material, and a negative electrode capable of inserting and extracting lithium. And a non-aqueous electrolyte, wherein the positive electrode contains anhydrous SiO2, Al2O3 , V2O5, Ir
At least one solid acid selected from O2 is
What added 0.002 mol-0.2 mol with respect to iCoO2 is used.
【００１２】[0012]
【００１３】[0013]
【００１４】[0014]
【作用】この構成により、本発明の非水電解質二次電池
の内部における無水ＳｉＯ２、Ａｌ２Ｏ３、Ｖ２Ｏ５、
ＩｒＯ２から選ばれる少なくとも１つの固体酸の働きと
して、残留アルカリとの高い反応性を挙げることができ
る。According to this structure, anhydrous SiO2, Al2O3 , V2O5,
The function of at least one solid acid selected from IrO2 includes high reactivity with residual alkali.
【００１５】本発明における正極活物質ＬｉＣｏＯ２に
混在する可能性のあるＬｉＯＨなどのアルカリへの作用
を考えることができる。正極中に無水ＳｉＯ２、Ａｌ２
Ｏ３、Ｖ２Ｏ５、ＩｒＯ２から選ばれる少なくとも１つ
の固体酸を添加することにより、残留アルカリを減少さ
せることが可能で、残留アルカリが原因と考えられる高
温保存による電池性能の低下を軽減できる。The effect of the present invention on alkali such as LiOH, which may be present in the positive electrode active material LiCoO 2, can be considered. Anhydrous SiO2, Al2 in positive electrode
By adding at least one solid acid selected from O 3 , V 2 O 5 , and IrO 2, residual alkali can be reduced, and a decrease in battery performance due to high-temperature storage, which is considered to be caused by the residual alkali, can be reduced.
【００１６】[0016]
【実施例】以下、本発明の実施例の非水電解液二次電池
について図面を基にして説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS A non-aqueous electrolyte secondary battery according to an embodiment of the present invention will be described below with reference to the drawings.
【００１７】（実施例１）電池の製造は次のようにして
行う。正極活物質としてＬｉＣｏＯ2 １００ｇに導電
剤としてアセチレンブラック ３．０ｇを混合し、さら
に、無水ＳｉＯ2３．０８ｇ（ＬｉＣｏＯ2 １モルに対
して０．０５モル）を添加、混合し、さらに、結着剤と
してのポリ４弗化エチレン樹脂４．０ｇを混合して正極
合剤とした。正極合剤０．１グラムを直径１７．５mmに
１トン／cm2でプレス成型して、正極とした。図１にお
いて、成型した正極１をケース２に置く。正極１の上に
セパレータ３としての多孔性ポリプロピレンフィルムを
置いた。負極４として直径１７．５mm厚さ０．３mmのリ
チウム板を、ポリプロピレン製ガスケット６を付けた封
口板５に圧着した。(Example 1) A battery is manufactured as follows. 100 g of LiCoO 2 as a positive electrode active material was mixed with 3.0 g of acetylene black as a conductive agent, and 3.08 g of anhydrous SiO 2 (0.05 mol per 1 mol of LiCoO 2 ) was added and mixed. A positive electrode mixture was prepared by mixing 4.0 g of polytetrafluoroethylene resin as a binder. 0.1 grams of the positive electrode mixture was press-formed at a diameter of 17.5 mm at 1 ton / cm 2 to obtain a positive electrode. In FIG. 1, a molded positive electrode 1 is placed in a case 2. A porous polypropylene film as a separator 3 was placed on the positive electrode 1. A lithium plate having a diameter of 17.5 mm and a thickness of 0.3 mm as the negative electrode 4 was pressure-bonded to the sealing plate 5 to which a polypropylene gasket 6 was attached.
【００１８】非水電解液として、プロピレンカーボネー
ト溶液に１モル／ｌの過塩素酸リチウムを溶解したもの
を用いた。このようにして得た非水電解液をセパレータ
３上および負極４上に加えた。その後ケース２の上縁部
をかしめて電池を封口した。As the non-aqueous electrolyte, a solution prepared by dissolving 1 mol / l of lithium perchlorate in a propylene carbonate solution was used. The non-aqueous electrolyte thus obtained was added onto the separator 3 and the negative electrode 4. Thereafter, the upper edge of the case 2 was swaged to seal the battery.
【００１９】さらに、無水ＳｉＯ2の正極活物質に対す
る添加濃度（正極活物質に対するモル比）についても検
討を行い、その添加濃度範囲は（表１）に示した。Further, the addition concentration of anhydrous SiO 2 to the positive electrode active material (molar ratio to the positive electrode active material) was also examined, and the addition concentration range is shown in Table 1.
【００２０】比較のため、無水ＳｉＯ2を添加しない正
極について上記と同様な方法で電池を製造した。For comparison, a battery was manufactured in the same manner as described above for the positive electrode to which no anhydrous SiO 2 was added.
【００２１】電池の高温保存試験を次の方法で行う。す
なわち、上記の方法で得られた電池について、２０℃に
おいて１mAの定電流で４．２ボルトまで充電し、次いで
これを３ボルトまで放電した。この充電放電を１０サイ
クル行った後、１１サイクル目の充電が終わった後、６
０℃で４週間保存した。保存後２０℃に戻し、同じ条件
で放電した。ここで、容量維持率は次のように定義し
た。A high-temperature storage test of the battery is performed by the following method. That is, the battery obtained by the above method was charged at 20 ° C. at a constant current of 1 mA to 4.2 volts, and then discharged to 3 volts. After performing this charge and discharge for 10 cycles, after completing the charge for the eleventh cycle, 6
Stored at 0 ° C. for 4 weeks. After storage, the temperature was returned to 20 ° C., and the battery was discharged under the same conditions. Here, the capacity retention rate was defined as follows.
【００２２】 容量維持率＝１００×１１サイクル目の放電電気量／１
０サイクル目の放電電気量 また、保存終了後に充電を行い、その後の放電容量を評
価した。Capacity retention rate = 100 × discharged electricity amount at 11th cycle / 1
Discharged electricity at the 0th cycle Further, after the storage, the battery was charged, and the discharge capacity after that was evaluated.
【００２３】ここで、容量回復率を次のように定義し
た。 容量回復率＝１００×１２サイクル目の放電電気量／１
０サイクル目の放電電気量 上記各電池の６０℃４週間保存にともなう電池内部抵抗
の変化を示す図２において、内部抵抗は電池電圧をバイ
アス電圧とし、１．０kHzにおいて振幅１００mVの条件
で２０℃において測定した。Here, the capacity recovery rate was defined as follows. Capacity recovery rate = 100 × discharged electricity amount at 12th cycle / 1
Electricity Discharge at Cycle 0 FIG. 2 shows the change in internal resistance of the above-mentioned batteries during storage at 60 ° C. for 4 weeks. In FIG. 2, the internal resistance was 20 ° C. under the condition of a battery voltage as a bias voltage and an amplitude of 100 mV at 1.0 kHz. Was measured.
【００２４】無水ＳｉＯ2を添加しない電池では、保存
直後から急激な電池内部抵抗の増加が認められ、４週間
後には３０Ω以上になる。一方、実施例の電池において
は、電池内部抵抗の増加は小さいものである。In the battery to which no anhydrous SiO 2 was added, a sharp increase in the battery internal resistance was observed immediately after storage, and it became 30Ω or more after 4 weeks. On the other hand, in the battery of the example, the increase in the battery internal resistance is small.
【００２５】また、（表１）には、各電池の正極合剤１
ｇ当りの初期放電容量および４週間後の容量維持率，容
量回復率を示す。Table 1 shows the positive electrode mixture 1 of each battery.
The initial discharge capacity per g and the capacity retention rate and capacity recovery rate after 4 weeks are shown.
【００２６】[0026]
【表１】 [Table 1]
【００２７】無水ＳｉＯ2を添加しない電池では、６０
℃４週間保存にともない非常に大きな容量低下を示す。
一方、無水ＳｉＯ2を添加した電池では容量維持率およ
び容量回復率が高い。しかし、電池の初期容量は無水Ｓ
ｉＯ2の添加量が０．２モルを越えると急激に減少して
いる。したがって、特に容量維持率が８０％以上で、容
量回復率が８５％以上であった無水ＳｉＯ2の添加濃度
０．００２〜０．２モルの範囲が望ましいことがわかっ
た。このように正極への無水ＳｉＯ2の添加は高温保存
にともなう容量低下を抑制する効果がある。In the case of a battery without addition of anhydrous SiO 2 , 60
It shows a very large capacity decrease with storage at 4 ° C for 4 weeks.
On the other hand, a battery to which anhydrous SiO 2 is added has a high capacity retention rate and a capacity recovery rate. However, the initial capacity of the battery is anhydrous S
When the added amount of iO 2 exceeds 0.2 mol, the amount rapidly decreases. Therefore, it was found that the addition concentration of anhydrous SiO 2 in which the capacity retention rate was 80% or more and the capacity recovery rate was 85% or more was particularly desirable in the range of 0.002 to 0.2 mol. As described above, the addition of anhydrous SiO 2 to the positive electrode has an effect of suppressing a decrease in capacity due to high-temperature storage.
【００２８】（実施例２）つぎに、Ａｌ2Ｏ3についての
検討を行った。(Example 2) Next, Al 2 O 3 was examined.
【００２９】電池の製造および高温保存試験は実施例１
と同様に行った。上記各電池の６０℃４週間保存にとも
なう電池内部抵抗の変化を示す図３において、Ａｌ2Ｏ3
を添加しない電池では、保存直後から急激な電池内部抵
抗の増加が認められ、４週間後には３０Ω以上になる。
一方、実施例の電池においては、電池内部抵抗の増加は
小さいものである。The battery production and high-temperature storage test were conducted in Example 1.
The same was done. In FIG. 3, which shows the change in the battery internal resistance following storage of each of the above batteries at 60 ° C. for 4 weeks, Al 2 O 3
In the battery without addition of, a sudden increase in the battery internal resistance was observed immediately after storage, and it became 30Ω or more after 4 weeks.
On the other hand, in the battery of the example, the increase in the battery internal resistance is small.
【００３０】また、（表２）には、各電池の正極合剤１
ｇ当りの初期放電容量および４週間後の容量維持率，容
量回復率を示す。Table 2 shows the positive electrode mixture 1 of each battery.
The initial discharge capacity per g and the capacity retention rate and capacity recovery rate after 4 weeks are shown.
【００３１】[0031]
【表２】 [Table 2]
【００３２】Ａｌ2Ｏ3を添加しない電池では、６０℃４
週間保存にともない非常に大きな容量低下を示すが、Ａ
ｌ2Ｏ3を添加した電池では容量維持率および容量回復率
が高い。しかし、電池の初期容量はＡｌ2Ｏ3の添加量が
０．２モルを越えると急激に減少している。したがっ
て、特に容量維持率が７５％以上で、容量回復率が８０
％以上であったＡｌ2Ｏ3の添加濃度０．００２〜０．２
モルの範囲が望ましいことがわかった。このように正極
へのＡｌ2Ｏ3の添加は高温保存にともなう容量低下を抑
制する効果がある。In the case of a battery to which Al 2 O 3 is not added, a temperature of 60 ° C.
It shows a very large capacity decrease with weekly storage.
A battery to which l 2 O 3 is added has a high capacity retention rate and a capacity recovery rate. However, the initial capacity of the battery sharply decreases when the amount of Al 2 O 3 added exceeds 0.2 mol. Therefore, especially when the capacity retention rate is 75% or more, the capacity recovery rate is 80%.
% Or more of the additive concentration of Al 2 O 3 of 0.002 to 0.2
A molar range has been found to be desirable. Thus, the addition of Al 2 O 3 to the positive electrode has the effect of suppressing a decrease in capacity due to high-temperature storage.
【００３３】また、固体酸として、Ｖ2Ｏ5，ＩｒＯ2を
用いた場合にも同様の効果が認められた。Similar effects were observed when V 2 O 5 and IrO 2 were used as solid acids.
【００３４】検討した固体酸の中では高温保存特性への
効果は無水ＳｉＯ2の場合に最も顕著であった。Among the solid acids studied, the effect on high-temperature storage characteristics was most pronounced in the case of anhydrous SiO 2 .
【００３５】以上のように、ＬｉＣｏＯ２で表わされる
複合酸化物を正極活物質とする非水電解質電池におい
て、正極中に無水ＳｉＯ２、Ａｌ２Ｏ３、Ｖ２Ｏ５、Ｉ
ｒＯ２から選ばれる少なくとも１つの固体酸を添加する
ことにより、高温保存特性に優れた非水電解質二次電池
を得ることができる。As described above, in a nonaqueous electrolyte battery using a composite oxide represented by LiCoO2 as a positive electrode active material, anhydrous SiO2, Al2O3 , V2O5, I2
By adding at least one solid acid selected from rO2, a non-aqueous electrolyte secondary battery having excellent high-temperature storage characteristics can be obtained.
【００３６】さらに、これらの固体酸を混合して添加し
た場合にも同様の効果が認められた。Further, similar effects were observed when these solid acids were mixed and added.
【００３７】以上の実施例では、電解液として１モル／
ｌの過塩素酸リチウムを溶解したプロピレンカーボネー
ト溶液を用いた場合の結果であるが、電解液としてこれ
以外に、溶質として６フッ化燐酸リチウムやトリフロロ
メタンスルフォン酸リチウム，ホウフッ化リチウム、溶
媒としてプロピレンカーボネート，エチレンカーボネー
トなどのカーボネート類、ガンマーブチロラクトン，酢
酸メチルなどのエステル類を用いた電解液が良好であっ
た。しかしながら、ジメトキシエタンやテトラヒドロフ
ランなどのエーテル類を使用した場合には、高温保存特
性は悪く、電解液中にルイス酸を添加することにより高
温保存特性の向上は認められなかった。実施例では正極
は４Ｖ以上の電圧となるため、エーテル類は酸化される
ためと考えている。In the above embodiment, 1 mol / mol of the electrolytic solution was used.
1 is a result of using a propylene carbonate solution in which 1 part of lithium perchlorate is dissolved. In addition to this as an electrolyte, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium borofluoride as a solute, and a solvent as a solvent are used. Electrolyte solutions using carbonates such as propylene carbonate and ethylene carbonate and esters such as gamma-butyrolactone and methyl acetate were good. However, when ethers such as dimethoxyethane and tetrahydrofuran were used, the high-temperature storage characteristics were poor, and no improvement in the high-temperature storage characteristics was observed by adding a Lewis acid to the electrolytic solution. In the embodiment, it is considered that since the voltage of the positive electrode becomes 4 V or more, ethers are oxidized.
【００３８】[0038]
【発明の効果】以上の実施例の説明で明らかなように、
本発明の非水電解液二次電池によれば、リチウムを吸蔵
放出できる負極、ＬｉＣｏＯ２で表わされる複合酸化物
を活物質とする正極および非水電解液を有し、正極中に
無水ＳｉＯ２、Ａｌ２Ｏ３、Ｖ２Ｏ５、ＩｒＯ２から選
ばれる少なくとも１つの固体酸を添加したものを用いる
ことにより、高温保存特性が良好な非水電解質二次電池
を得ることができ、産業上の意義は大きい。As is clear from the above description of the embodiment,
ADVANTAGE OF THE INVENTION According to the non-aqueous electrolyte secondary battery of this invention, it has the negative electrode which can occlude and release lithium, the positive electrode which uses the composite oxide represented by LiCoO2 as an active material, and a non-aqueous electrolyte, and contains anhydrous SiO2, Al2O3 in a positive electrode. By using a material to which at least one solid acid selected from V2O5 and IrO2 is added, a non-aqueous electrolyte secondary battery having good high-temperature storage characteristics can be obtained, which has great industrial significance.
【図１】本発明の実施例の非水電解液二次電池の縦断面
図FIG. 1 is a longitudinal sectional view of a nonaqueous electrolyte secondary battery according to an embodiment of the present invention.
【図２】同実施例１の電池の６０℃保存にともなう電池
内部抵抗の変化を示したグラフFIG. 2 is a graph showing a change in internal resistance of the battery of Example 1 during storage at 60 ° C.
【図３】同実施例２の電池の６０℃保存にともなう電池
内部抵抗の変化を示したグラフFIG. 3 is a graph showing a change in internal resistance of the battery of Example 2 during storage at 60 ° C.
１ 正極 ２ ケース ３ セパレータ ４ 負極 ５ 封口板 ６ ガスケット DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Case 3 Separator 4 Negative electrode 5 Sealing plate 6 Gasket
───────────────────────────────────────────────────── フロントページの続き (72)発明者 長谷川 正樹 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 豊口 ▲吉▼徳 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭63−121259（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/58 H01M 4/62 H01M 10/40 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaki Hasegawa 1006 Kazuma Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-63-121259 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/58 H01M 4/62 H01M 10/40
Claims (1)
活物質とする正極と、リチウムを吸蔵放出することがで
きる負極および非水電解液を有し、前記正極中に無水Ｓ
ｉＯ２、Ａｌ２Ｏ３、Ｖ２Ｏ５、ＩｒＯ２から選ばれる
少なくとも１つの固体酸を１モルのＬｉＣｏＯ２に対し
て０．００２モルから０．２モル添加した非水電解液二
次電池。1. A positive electrode comprising a composite oxide represented by LiCoO2 as an active material, a negative electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte, wherein anhydrous S is contained in the positive electrode.
A non-aqueous electrolyte secondary battery in which at least one solid acid selected from iO2, Al2O3 , V2O5 and IrO2 is added in an amount of 0.002 to 0.2 mol per 1 mol of LiCoO2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12732091A JP3245886B2 (en) | 1991-05-30 | 1991-05-30 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12732091A JP3245886B2 (en) | 1991-05-30 | 1991-05-30 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04355056A JPH04355056A (en) | 1992-12-09 |
| JP3245886B2 true JP3245886B2 (en) | 2002-01-15 |
Family
ID=14957019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12732091A Expired - Fee Related JP3245886B2 (en) | 1991-05-30 | 1991-05-30 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3245886B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049872A1 (en) * | 2005-10-26 | 2007-05-03 | Lg Chem, Ltd. | Mixture for anode of improved adhesive strength and lithium secondary battery containing the same |
| JP7471765B2 (en) | 2017-11-20 | 2024-04-22 | 王子ホールディングス株式会社 | Animal bedding and method for disposing of animal bedding |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6753112B2 (en) | 2000-12-27 | 2004-06-22 | Kabushiki Kaisha Toshiba | Positive electrode active material and non-aqueous secondary battery using the same |
| JP4503964B2 (en) * | 2003-09-19 | 2010-07-14 | 株式会社東芝 | Nonaqueous electrolyte secondary battery |
| JP4736943B2 (en) * | 2006-05-17 | 2011-07-27 | 日亜化学工業株式会社 | Positive electrode active material for lithium secondary battery and method for producing the same |
| JP5332338B2 (en) * | 2008-06-23 | 2013-11-06 | Ｔｄｋ株式会社 | Electrode and lithium ion secondary battery |
| JP6016029B2 (en) * | 2013-03-22 | 2016-10-26 | 株式会社豊田自動織機 | Positive electrode for lithium ion secondary battery and lithium ion secondary battery |
| JP6964280B2 (en) * | 2016-12-28 | 2021-11-10 | パナソニックＩｐマネジメント株式会社 | Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
-
1991
- 1991-05-30 JP JP12732091A patent/JP3245886B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049872A1 (en) * | 2005-10-26 | 2007-05-03 | Lg Chem, Ltd. | Mixture for anode of improved adhesive strength and lithium secondary battery containing the same |
| JP7471765B2 (en) | 2017-11-20 | 2024-04-22 | 王子ホールディングス株式会社 | Animal bedding and method for disposing of animal bedding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04355056A (en) | 1992-12-09 |
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