JPH04237967A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH04237967A JPH04237967A JP3005038A JP503891A JPH04237967A JP H04237967 A JPH04237967 A JP H04237967A JP 3005038 A JP3005038 A JP 3005038A JP 503891 A JP503891 A JP 503891A JP H04237967 A JPH04237967 A JP H04237967A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- battery
- lithium
- active material
- chemical formula
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract 4
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract 4
- 239000000126 substance Substances 0.000 claims description 38
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 11
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract 2
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 239000006182 cathode active material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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
Abstract
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、特に正極活物質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 with an improved positive electrode active material.
【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質二次電池は
高電圧で高エネルギー密度となることが期待され、多く
の研究が行なわれている。[Conventional technology]
Non-aqueous electrolyte secondary batteries using lithium, lithium alloys, or lithium compounds as negative electrodes are expected to have high voltage and high energy density, and many studies are being conducted.
【０００３】特に、これら電池の正極活物質として（化
２）に示す化学式の物質などがよく検討されている。In particular, substances having the chemical formula shown in (Chemical formula 2) have been extensively studied as positive electrode active materials for these batteries.
【０００４】0004
【化２】[Case 2]
【０００５】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（化３）に示す化学式の物質お
よび（化４）に示す化学式の物質が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。These cathode active materials have a potential of about 3 V with respect to Li, but recently a substance with the chemical formula shown in (Chemical formula 3) and a substance with the chemical formula shown in (Chemical formula 4) show a potential of 4 V or more with respect to Li. It is attracting attention as a positive electrode active material.
【０００６】[0006]
【化３】[Chemical formula 3]
【０００７】[0007]
【化４】[C4]
【０００８】すなわち、電池の高エネルギー密度を得る
手段として容量の増加とともに電池電圧を高める努力が
なされている。That is, efforts are being made to increase battery voltage as well as increase capacity as a means of obtaining high energy density of batteries.
【０００９】このうち、（化４）に示す物質は、その放
電容量が大きく、優れた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。Among these, the material shown in (Chemical formula 4) is considered to be promising as a positive electrode active material because it has a large discharge capacity and may have excellent cycle characteristics.
【００１０】さらに、二次電池として重要な必要特性の
１つであるサイクル特性を向上するため、（化４）に示
す化学式の物質を骨格とする（化５）に示す化学式で表
わされる複合酸化物を正極活物質として用いる改良がな
され、充放電サイクル特性の一層の向上が図られている
。Furthermore, in order to improve the cycle characteristics, which is one of the important characteristics required for a secondary battery, a composite oxide represented by the chemical formula shown in (Chemical formula 5) whose skeleton is a substance shown in the chemical formula shown in (Chemical formula 4) Improvements have been made to use these materials as positive electrode active materials, and further improvements in charge/discharge cycle characteristics are being attempted.
【００１１】[0011]
【化５】[C5]
【００１２】0012
【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、放電容量が大きくサイクル特性の優れ
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、充電後の電池の自己放電特性が不充分で
あるという問題があった。非水電解液二次電池の自己放
電については電池内部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。[Problems to be Solved by the Invention] By using the above positive electrode active material, a nonaqueous electrolyte secondary battery with a large discharge capacity and excellent cycle characteristics can be realized, but the charging voltage is 4V.
Therefore, there was a problem that the self-discharge characteristics of the battery after charging were insufficient. Self-discharge of non-aqueous electrolyte secondary batteries is caused by trace amounts of moisture inside the battery and decomposition of the electrolyte solvent, causing problems such as an increase in battery internal resistance and a decrease in charge/discharge capacity. In particular, these phenomena become more pronounced as the battery voltage increases, and become more pronounced during high-temperature storage.
【００１３】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なう
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だけでは良好な自己放電
特性を得ることができない。Regarding moisture brought into the battery,
Efforts are being made to suppress the introduction of moisture into the battery through purification such as distillation of the electrolyte and drying of 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, it is not possible to obtain good self-discharge characteristics only by removing the moisture.
【００１４】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リチウムとの反応が起こ
りやすくなり、電池の性能低下が生じると考えられる。[0014] It is thought that the reaction between the positive electrode active material and the electrolyte solvent and the reaction between the substance produced by this reaction and the negative electrode lithium tend to occur, resulting in a decrease in battery performance.
【００１５】本発明はこのような課題を解決するもので
、自己放電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。[0015] The present invention solves these problems and aims to provide a non-aqueous electrolyte secondary battery with improved self-discharge characteristics.
【００１６】[0016]
【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液二次電池は、リチウム、リチウ
ム合金またはリチウム化合物の負極、（化５）に示す化
学式で表わされる複合酸化物を用いた正極活物質および
非水電解液を有し、前記正極活物質にアルカリ金属水酸
化物を添加したものを用い、またアルカリ金属水酸化物
の添加量を前記正極活物質１００ｇあたり０．０５〜０
．１５モルとするものである。[Means for Solving the Problem] In order to solve this problem, the nonaqueous electrolyte secondary battery of the present invention includes a negative electrode of lithium, a lithium alloy, or a lithium compound, and a composite oxide represented by the chemical formula shown in (Chemical formula 5). The cathode active material has a non-aqueous electrolyte and an alkali metal hydroxide is added to the cathode active material, and the amount of the alkali metal hydroxide added is 0.5 g per 100 g of the cathode active material. 05～0
．． The amount is 15 moles.
【００１７】[0017]
【作用】 この構成により本発明の非水電解液二次電池
は、非水電解液二次電池内部におけるアルカリ金属水酸
化物の働きは明確ではないが、その作用としては、有機
電解液の分解の抑制や分解生成物との反応などを挙げる
ことができる。この結果、溶媒分解生成物が原因と考え
られる電池性能の低下を軽減できるものと思われる。[Function] With this configuration, the non-aqueous electrolyte secondary battery of the present invention can be used to decompose the organic electrolyte, although the function of the alkali metal hydroxide inside the non-aqueous electrolyte secondary battery is not clear. Examples include suppression of oxidation and reaction with decomposition products. As a result, it seems possible to reduce the decrease in battery performance that is thought to be caused by solvent decomposition products.
【００１８】[0018]
【実施例】以下本発明の一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.
【００１９】（実施例１）電池の製造を次のようにして
行なう。正極活物質として（化６）に示す化学式の物質
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、アルカリ金属水酸化物として水酸化リ
チウム１．８ｇを水溶液として添加し、混合した。この
混合物を８０℃で１０時間乾燥し、その後、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。(Example 1) A battery was manufactured as follows. 3.0 g of acetylene black as a conductive agent was mixed with 100 g of a substance having the chemical formula shown in (Chemical formula 6) as a positive electrode active material, and 1.8 g of lithium hydroxide as an alkali metal hydroxide was added as an aqueous solution and mixed. This mixture was dried at 80° C. for 10 hours, and then 4.0 g of polytetrafluoroethylene resin as a binder was mixed to prepare a positive electrode mixture.
【００２０】[0020]
【化６】[C6]
【００２１】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。製造
した電池の断面図を図３に示す。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。負極として直径１７
．５ｍｍ厚さ０．３ｍｍのリチウム板４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。非水
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、これをセパレー
タ３上および負極４上に加えた。その後電池を封口した
。上記のようにして得られた電池をＡとする。[0021] 0.1 gram of positive electrode mixture is 17.5 mm in diameter.
The positive electrode was press-molded at 1 ton/cm2. A cross-sectional view of the manufactured battery is shown in FIG. Place the molded positive electrode 1 in the case 2. A porous polypropylene film as a separator 3 was placed on the positive electrode 1 . Diameter 17 as negative electrode
．． A lithium plate 4 having a thickness of 5 mm and a thickness of 0.3 mm was press-bonded to a sealing plate 5 equipped with a gasket 6 made of polypropylene. A propylene carbonate solution in which 1 mol/l of lithium perchlorate was dissolved was used as the non-aqueous electrolyte, and this was added onto the separator 3 and the negative electrode 4. After that, the battery was sealed. The battery obtained as described above is designated as A.
【００２２】同様の方法により水酸化カリウムを添加し
た正極を用いた電池をＢ、水酸化ナトリウムを添加した
正極を用いた電池をＣ、水酸化カリウムと水酸化ナトリ
ウムをそれぞれ０．９ｇ添加した正極を用いた電池をＤ
、水酸化リチウム、水酸化カリウム、水酸化ナトリウム
をそれぞれ０．６ｇ添加した正極を用いた電池をＥとす
る。A battery using a positive electrode to which potassium hydroxide was added using the same method was B, a battery using a positive electrode to which sodium hydroxide was added was C, a positive electrode to which 0.9 g each of potassium hydroxide and sodium hydroxide were added. A battery using D
, a battery using a positive electrode to which 0.6 g of each of lithium hydroxide, potassium hydroxide, and sodium hydroxide was added is designated as E.
【００２３】比較例として、アルカリ金属水酸化物を添
加しない電池として、（化６）に示す化学式の物質１０
０ｇ、アセチレンブラック３．０ｇ、ポリ４弗化エチレ
ン樹脂４．０ｇを混合して正極合剤として使用し、以下
、同様に電池を構成した。この電池をＦとする。As a comparative example, as a battery to which no alkali metal hydroxide was added, substance 10 having the chemical formula shown in (Chemical formula 6) was used.
0 g, acetylene black 3.0 g, and polytetrafluoroethylene resin 4.0 g were mixed and used as a positive electrode mixture, and a battery was constructed in the same manner. This battery is designated as F.
【００２４】電池の自己放電試験を次の方法で行なう。
すなわち上記の方法で得られた電池について、１ｍＡの
定電流で４．２ボルトまで充電し、３ボルトまで放電し
、この充電放電を１０サイクル行なった後、１１サイク
ル目の充電が終わった後、６０℃で３週間貯蔵した。
貯蔵後同じ条件で放電した。ここで、自己放電率は次の
ように定義した。A self-discharge test of the battery was conducted in the following manner. That is, the battery obtained by the above method was charged to 4.2 volts with a constant current of 1 mA, discharged to 3 volts, and after 10 cycles of charging and discharging, after the 11th cycle of charging was completed, Stored at 60°C for 3 weeks. After storage, it was discharged under the same conditions. Here, the self-discharge rate was defined as follows.
【００２５】自己放電率＝（１０サイクル目の放電電気
量−１１サイクル目の放電電気量）／１０サイクル目の
放電電気量上記各電池の６０℃保存にともなう電池内部
抵抗の変化を図１に示す。従来構成の電池Ｆ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、本実施例の電池Ａ〜Ｅに
おいては、電池内部抵抗の増加は小さいものであり、電
池Ｆの１／４程度である。Self-discharge rate = (Amount of discharged electricity in the 10th cycle - Amount of electricity discharged in the 11th cycle) / Amount of discharged electricity in the 10th cycle Figure 1 shows the change in battery internal resistance of each of the above batteries as they are stored at 60°C. show. In battery F with the conventional configuration, a rapid increase in battery internal resistance was observed immediately after storage, and it reached 30Ω or more after 4 weeks. On the other hand, in batteries A to E of this example, the increase in battery internal resistance is small, about 1/4 of that in battery F.
【００２６】また、（表１）には、各電池の３週間後の
自己放電率を示す。Table 1 also shows the self-discharge rate of each battery after 3 weeks.
【００２７】[0027]
【表１】[Table 1]
【００２８】電池Ｆは非常に大きな自己放電率であるが
、本実施例の電池Ａ〜Ｅでは１０％以内に抑えられてい
る。このように正極へアルカリ金属水酸化物を添加する
ことは高温保存にともなう自己放電を抑制する効果があ
り、水酸化カリウム、水酸化、水酸化リチウムのいずれ
を添加した場合にも効果がある。Battery F has a very high self-discharge rate, but batteries A to E of this example have a self-discharge rate that is suppressed to within 10%. Adding an alkali metal hydroxide to the positive electrode in this way has the effect of suppressing self-discharge associated with high-temperature storage, and the addition of potassium hydroxide, hydroxide, or lithium hydroxide is also effective.
【００２９】さらに、これらのアルカリ金属水酸化物を
混合して添加した場合にも同様の効果が認められる。Furthermore, similar effects are observed when a mixture of these alkali metal hydroxides is added.
【００３０】（実施例２）さらに、正極への水酸化リチ
ウムの添加量について検討した。正極活物質としては、
（化７）に示す化学式の物質１００ｇを用いた。図２に
水酸化リチウムの添加量（活物質１００ｇに対するモル
数）とこれらの正極を用いた電池の６０℃、３週間保存
後の電池内部抵抗との関係を示す。(Example 2) Furthermore, the amount of lithium hydroxide added to the positive electrode was investigated. As a positive electrode active material,
100 g of a substance having the chemical formula shown in (Chemical formula 7) was used. FIG. 2 shows the relationship between the amount of lithium hydroxide added (number of moles per 100 g of active material) and the internal resistance of batteries using these positive electrodes after storage at 60° C. for 3 weeks.
【００３１】[0031]
【化７】[C7]
【００３２】結果から正極への水酸化リチウムの添加量
が０．０５モル〜０．１５モルの範囲で電池内部抵抗の
増加を抑える効果が認められる。したがって、正極への
水酸化リチウムの添加量は活物質１００ｇに対して、０
．０５モル〜０．１５モルの範囲が望ましい。[0032] The results show that the addition amount of lithium hydroxide to the positive electrode in the range of 0.05 mol to 0.15 mol has the effect of suppressing the increase in battery internal resistance. Therefore, the amount of lithium hydroxide added to the positive electrode is 0 per 100 g of active material.
．． A range of 0.05 mol to 0.15 mol is desirable.
【００３３】また、水酸化カリウム、水酸化ナトリウム
の場合にも、同様の結果が得られ、正極活物質として（
化８）に示す化学式の物質を用いた場合にも同じ効果が
認められた。Similar results were also obtained in the case of potassium hydroxide and sodium hydroxide, and (
The same effect was observed when a substance having the chemical formula shown in Chemical Formula 8) was used.
【００３４】[0034]
【化８】[Chemical formula 8]
【００３５】以上のように、（化５）に示す化学式で表
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、正極中にアルカリ金属水酸化物を添加するこ
とにより、自己放電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 non-aqueous electrolyte battery using a composite oxide represented by the chemical formula (5) as a positive electrode active material, the self-discharge characteristics can be improved by adding an alkali metal hydroxide to the positive electrode. A non-aqueous electrolyte secondary battery with excellent properties can be obtained.
【００３６】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、溶質として過塩素酸リチウム、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、自己放電特性は悪く、正極中にアルカリ金属水
酸化物を添加することによる自己放電特性の向上は認め
られず、実施例で示したプロピレンカーボネートを用い
た場合の約２倍の自己放電率であった。本実施例では正
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。[0036] In the above examples, the electrolyte was 1 mol/
These are the results when using a propylene carbonate solution in which 1 liter of lithium perchlorate was dissolved, but in addition to this as an electrolyte, lithium perchlorate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, and borofluoride were used as solutes. Lithium chloride, propylene carbonate as solvent,
Electrolytes using carbonates such as ethylene carbonate, and esters such as gamma butyrolactone and methyl acetate were good. However, when ethers such as dimethoxyethane and tetrahydrofuran are used, the self-discharge characteristics are poor, and no improvement in self-discharge characteristics was observed by adding an alkali metal hydroxide to the positive electrode. The self-discharge rate was approximately twice that when using propylene carbonate. In this example, since the positive electrode has a voltage of 4 V or more, it is thought that the ethers are oxidized.
【００３７】[0037]
【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、リ
チウム合金またはリチウム化合物の負極、（化５）に示
す化学式で表わされる複合酸化物を用いた正極活物質、
および非水電解液を有し、前記正極活物質にアルカリ金
属水酸化物を添加したものを用いることにより自己放電
特性が良好な非水電解液二次電池を得ることができ、産
業上の意義は大きい。[Effects of the Invention] As is clear from the description of the above embodiments, according to the nonaqueous electrolyte secondary battery of the present invention, a negative electrode of lithium, lithium alloy, or lithium compound, represented by the chemical formula shown in (Chemical formula 5) Cathode active material using composite oxide,
By using a positive electrode active material containing a non-aqueous electrolyte and an alkali metal hydroxide added to the positive electrode active material, a non-aqueous electrolyte secondary battery with good self-discharge characteristics can be obtained, which has industrial significance. is big.
【図１】本発明の実施例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. 1 is a graph showing the change in internal resistance of the battery according to Example 1 of the present invention as it is stored at 60°C.
【図２】本発明の実施例２の水酸化リチウムの添加量（
活物質１００ｇに対するモル数）とこれらの正極を用い
た電池の６０℃保存後の電池内部抵抗との関係を示した
グラフFIG. 2: Addition amount of lithium hydroxide in Example 2 of the present invention (
Graph showing the relationship between the number of moles per 100 g of active material) and the battery internal resistance after storage at 60°C of batteries using these positive electrodes
【図３】本発明の実施例に用いたコイン型の電池の縦断
面図[Fig. 3] Vertical cross-sectional view of a coin-shaped battery used in an example of the present invention
Claims (2)
合物の負極、（化１）に示す化学式で表わされる複合酸
化物を用いた正極活物質、および非水電解液を有し、前
記正極活物質にアルカリ金属水酸化物を添加した非水電
解液二次電池。 【化１】1. A negative electrode made of lithium, a lithium alloy, or a lithium compound, a positive electrode active material using a composite oxide represented by the chemical formula shown in (Chemical formula 1), and a non-aqueous electrolyte, wherein the positive electrode active material contains an alkali. A non-aqueous electrolyte secondary battery containing metal hydroxide. [Chemical formula 1]
質１００ｇあたり０．０５〜０．１５モルである請求項
１記載の非水電解液二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the amount of the alkali metal hydroxide added is 0.05 to 0.15 mol per 100 g of positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3005038A JP2558957B2 (en) | 1991-01-21 | 1991-01-21 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3005038A JP2558957B2 (en) | 1991-01-21 | 1991-01-21 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04237967A true JPH04237967A (en) | 1992-08-26 |
| JP2558957B2 JP2558957B2 (en) | 1996-11-27 |
Family
ID=11600279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3005038A Expired - Fee Related JP2558957B2 (en) | 1991-01-21 | 1991-01-21 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2558957B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100378012B1 (en) * | 2000-11-09 | 2003-03-29 | 삼성에스디아이 주식회사 | Positive active material composition for lithium secondary battery and lithium secondary battery using same |
| US20100237277A1 (en) * | 2004-12-20 | 2010-09-23 | Haruchika Ishii | Nonaqueous electrolyte battery, battery pack and positive electrode active material |
| JP2013131392A (en) * | 2011-12-21 | 2013-07-04 | Toyota Motor Corp | Method of manufacturing lithium ion secondary battery |
-
1991
- 1991-01-21 JP JP3005038A patent/JP2558957B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100378012B1 (en) * | 2000-11-09 | 2003-03-29 | 삼성에스디아이 주식회사 | Positive active material composition for lithium secondary battery and lithium secondary battery using same |
| US20100237277A1 (en) * | 2004-12-20 | 2010-09-23 | Haruchika Ishii | Nonaqueous electrolyte battery, battery pack and positive electrode active material |
| JP2013131392A (en) * | 2011-12-21 | 2013-07-04 | Toyota Motor Corp | Method of manufacturing lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2558957B2 (en) | 1996-11-27 |
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