JP2001266940A - Non-aqueous electrolytic solution for secondary battery - Google Patents
Non-aqueous electrolytic solution for secondary batteryInfo
- Publication number
- JP2001266940A JP2001266940A JP2000074149A JP2000074149A JP2001266940A JP 2001266940 A JP2001266940 A JP 2001266940A JP 2000074149 A JP2000074149 A JP 2000074149A JP 2000074149 A JP2000074149 A JP 2000074149A JP 2001266940 A JP2001266940 A JP 2001266940A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- electrolyte
- battery
- lithium
- electrolytic solution
- 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.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、二次電池用非水電
解液の改良技術に関する。The present invention relates to a technique for improving a non-aqueous electrolyte for a secondary battery.
【0002】[0002]
【従来の技術】近年、カメラ一体型ビデオテ−プレコ−
ダ(VTR)、携帯電話、ラップトップコンピュータ等
の新しいポータブル電源として、特に、従来のニッケル
ーカドミニウム(Ni−Cd)二次電池や鉛二次電池に
比べ軽量で高容量且つ高エネルギー密度のリチウム二次
電池が注目されている。リチウム二次電池の構成例の一
例は、負極にLiのド−プおよび脱ド−プが可能な炭素
材料を用い、リチウムを負極活物質として用い、正極に
Liのド−プおよび脱ド−プが可能な金属酸化物例えば
LiMn2O4 等のMn含有リチウム酸化物を用い、
電解液に非水溶媒とリチウム化合物を電解質とした電解
液を用いている。2. Description of the Related Art In recent years, camera-integrated video tape recorders have been developed.
As a new portable power source such as a VTR, a mobile phone, a laptop computer, etc., in particular, lithium which is lighter, has a higher capacity and a higher energy density than conventional nickel-cadmium (Ni-Cd) secondary batteries or lead secondary batteries. Secondary batteries are attracting attention. An example of a configuration example of a lithium secondary battery uses a carbon material capable of doping and dedoping Li for a negative electrode, using lithium as a negative electrode active material, and doping and dedoping Li for a positive electrode. Using a metal oxide that can be doped, for example, a Mn-containing lithium oxide such as LiMn 2 O 4 ,
An electrolyte using a non-aqueous solvent and a lithium compound as an electrolyte is used as the electrolyte.
【0003】従来より、リチウム二次電池の非水電解液
の電解質としては、上記のようにリチウム化合物例えば
LiPF6 のようなフッ素含有無機又は有機リチウム
化合物が使用されている。また、非水溶媒としては、炭
酸プロピレン(PC)、炭酸エチレン(EC)、炭酸ジ
メチル(DMC)、炭酸エチルメチル(MEC)、炭酸
ジエチル(DEC)、γーブチロラクトン(GBL)、
酢酸エチル(EA)、プロピオン酸メチル(MPR)、
1,2−ジメトキシエタン(DME)、2−メチルテト
ラヒドロフラン(2−MeTHF)等が用いられてい
る。Conventionally, a lithium compound, for example, a fluorine-containing inorganic or organic lithium compound such as LiPF 6 has been used as an electrolyte of a nonaqueous electrolyte of a lithium secondary battery. Examples of the non-aqueous solvent include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), diethyl carbonate (DEC), γ-butyrolactone (GBL),
Ethyl acetate (EA), methyl propionate (MPR),
1,2-Dimethoxyethane (DME), 2-methyltetrahydrofuran (2-MeTHF) and the like are used.
【0004】しかしながら、リチウム二次電池における
負極活物質であるリチウムは、反応性に富み、上記電解
質との間で反応を起こし、その反応生成物が電極表面に
被膜となって付着し、その被膜が電池特性に大きく影響
を与えている。又、非水溶媒における炭酸エステル類
は、リチウムと反応してイオン伝導性を有する炭酸塩の
被膜を生成する為、電池内部抵抗の増加等の電池特性に
及ぼす悪影響は少なく、さらに、この被膜が負極表面の
保護膜となり、電池の保存特性等を良好にしているの
で、従来より炭素材料よりなる負極のリチウム二次電池
用非水電解液の主成分となっているが、当該炭酸エステ
ル類の中には、比較的に融点が高く、また、粘性率が高
いという欠点のあるものも存在し、又、炭酸ジメチル
(DMC)あるいは炭酸ジエチル(DEC)等の直鎖状
の炭酸エステル類は、誘電率が低く、電解液溶媒とした
時の電解液の導電率が小さく、高出力な二次電池として
要求される充分な急速充電特性あるいは低温放電特性が
得られなかったりするという難点がある。さらに、炭酸
エステル類は、電解質のフッ素含有無機又は有機リチウ
ム化合物の分解により遊離するHFにより分解が起こ
り、炭酸ガスやオレフィンガスを生成する為、内圧が上
昇し、電池が膨れやサイクル容量の劣化という問題があ
った。更に又、正極におけるMn含有リチウム酸化物で
は、上記HFによりMnが溶出し電池の膨れ及び放電特
性の低下を来すという問題もある。However, lithium, which is a negative electrode active material in a lithium secondary battery, is highly reactive and reacts with the above-mentioned electrolyte, and the reaction product adheres to the electrode surface as a film, and the film is formed. Greatly affect the battery characteristics. In addition, carbonates in a non-aqueous solvent react with lithium to form a film of a carbonate having ion conductivity, so that adverse effects on battery characteristics, such as an increase in battery internal resistance, are small. Since it becomes a protective film on the surface of the negative electrode and improves the storage characteristics and the like of the battery, it has conventionally been the main component of the nonaqueous electrolyte for a lithium secondary battery of a negative electrode made of a carbon material. Some of them have disadvantages such as relatively high melting point and high viscosity, and linear carbonates such as dimethyl carbonate (DMC) and diethyl carbonate (DEC) are: The dielectric constant is low, the conductivity of the electrolyte when used as an electrolyte solvent is low, and there is a problem that sufficient fast charging characteristics or low-temperature discharging characteristics required for a high-output secondary battery cannot be obtained. Furthermore, carbonates are decomposed by HF released by the decomposition of the fluorine-containing inorganic or organic lithium compound in the electrolyte to generate carbon dioxide gas and olefin gas, so that the internal pressure rises and the battery swells and the cycle capacity deteriorates. There was a problem. Further, in the case of the Mn-containing lithium oxide in the positive electrode, there is a problem that Mn is eluted by the HF, thereby causing swelling of the battery and lowering of discharge characteristics.
【0005】[0005]
【発明が解決しようとする課題】本発明は、かかる従来
技術の有する欠点を解消できる技術を提供することを目
的としたものである。本発明の前記ならびにそのほかの
目的と新規な特徴は、本明細書の記述および添付図面か
らも明らかになるであろう。SUMMARY OF THE INVENTION An object of the present invention is to provide a technique capable of solving the drawbacks of the prior art. The above and other objects and novel features of the present invention will become apparent from the description of this specification and the accompanying drawings.
【0006】[0006]
【課題を解決するための手段】本発明は、 Liのド−
プおよび脱ド−プが可能な炭素材料等よりなる負極とL
iのド−プおよび脱ド−プが可能な金属酸化物材料等よ
りなる正極とを有してなる二次電池に使用でき、非水溶
媒と、電解質としてリチウム化合物を含む二次電池用非
水電解液において、次の式1で表されるヘキサメチレン
テトラミンSUMMARY OF THE INVENTION The present invention relates to a method for producing Li
And a negative electrode made of a carbon material or the like which can be
i can be used for a secondary battery having a positive electrode made of a metal oxide material or the like which can be doped and dedoped, and can be used for a secondary battery containing a non-aqueous solvent and a lithium compound as an electrolyte. In water electrolyte, hexamethylenetetramine represented by the following formula 1
【式1】 を含有してなることを特徴とする二次電池用非水電解液
に係るものである。又、その好ましい実施態様として、
当該二次電池用非水電解液における前記ヘキサメチレン
テトラミンの濃度が0.001〜5重量%であること、
又、電解質のリチウム化合物がフッ素を含有するリチウ
ム化合物であることを特徴とする二次電池用非水電解液
に係るものである。(Equation 1) The present invention relates to a non-aqueous electrolyte for a secondary battery, characterized by comprising: Also, as a preferred embodiment thereof,
The concentration of the hexamethylenetetramine in the nonaqueous electrolyte for a secondary battery is 0.001 to 5% by weight;
The present invention also relates to a non-aqueous electrolyte for a secondary battery, wherein the lithium compound of the electrolyte is a lithium compound containing fluorine.
【0007】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【0008】本発明によれば炭酸エステル類にかかわら
ず各種の非水溶媒を使用することができる。本発明にお
いて使用される非水溶媒としては、例えば、炭酸プロピ
レン(PC)、炭酸エチレン(EC)、炭酸ジメチル
(DMC)、炭酸エチルメチル(MEC)、炭酸ジエチ
ル(DEC)、γーブチロラクトン(GBL)、酢酸エ
チル(EA)、プロピオン酸メチル(MPR)、プロピ
オン酸エチル(EPR)、1,2−ジメトキシエタン
(DME)、1,2−ジエトキシエタン(DEE)、2
−メチルテトラヒドロフラン(2−MeTHF)、テト
ラヒドロフラン(THF)、スルホラン(SL)、メチ
ルスルホラン(MeSL)等従来より二次電池用非水電
解液において用いられているような各種の溶媒を使用す
ることができ、これらは二種以上を混合して用いてもよ
い。According to the present invention, various non-aqueous solvents can be used regardless of carbonates. Examples of the non-aqueous solvent used in the present invention include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), diethyl carbonate (DEC), and γ-butyrolactone (GBL). ), Ethyl acetate (EA), methyl propionate (MPR), ethyl propionate (EPR), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE),
-Various solvents such as methyltetrahydrofuran (2-MeTHF), tetrahydrofuran (THF), sulfolane (SL), and methylsulfolane (MeSL) which have been conventionally used in nonaqueous electrolytes for secondary batteries can be used. These may be used in combination of two or more.
【0009】本発明の二次電池用非水電解液において
は、電解質としてリチウム化合物が使用される。これに
より、本電解質はリチウム二次電池の電解液として特に
有用となる。このようなリチウム化合物としては、フッ
素を含有するリチウム化合物例えばLiAsF6、Li
PF6、LiBF4、LiCF3SO3、LiN(CF
3SO2)2、LiC(CF3SO2)3を使用するこ
とができるが、例えば、LiClO4等の従来からリチ
ウム二次電池において用いられているようなものも使用
することができる。電解質であるリチウム化合物の二次
電池用非水電解液中での濃度は、導電率の点等から0.
1〜3.0mol/リットル、好ましくは0.3〜2.
0mol/リットルとするとよい。In the non-aqueous electrolyte for a secondary battery according to the present invention,
Uses a lithium compound as an electrolyte. to this
Therefore, this electrolyte is particularly useful as an electrolyte for lithium secondary batteries.
Will be useful. As such a lithium compound, fluorine is used.
-Containing lithium compounds such as LiAsF6, Li
PF6, LiBF4, LiCF3SO3, LiN (CF
3SO2)2, LiC (CF3SO2)3Use
For example, LiClO4Etc.
Also used in secondary batteries
can do. Secondary of lithium compound as electrolyte
The concentration in the non-aqueous electrolyte for a battery is set at 0.1 from the viewpoint of conductivity.
1 to 3.0 mol / l, preferably 0.3 to 2.
It is good to be 0 mol / liter.
【0010】上記ヘキサメチレンテトラミンの非水電解
液中での濃度は、0.001〜5重量%好ましくは0.
01〜0.5重量%であることが望ましい。0.001
重量%未満では、充放電特性等の改善効果が充分でな
く、一方、5重量%を超えても、当該効果が飽和し、逆
に電池容量が低下する傾向にある。The concentration of the above hexamethylenetetramine in the non-aqueous electrolyte is 0.001 to 5% by weight, preferably 0.1 to 5% by weight.
The content is desirably from 0.01 to 0.5% by weight. 0.001
When the amount is less than 5% by weight, the effect of improving the charge / discharge characteristics and the like is not sufficient. On the other hand, when the amount exceeds 5% by weight, the effect is saturated and the battery capacity tends to decrease.
【0011】本発明の二次電池用非水電解液は、例え
ば、非水溶媒を撹拌しながら、その中に電解質としてリ
チウム化合物を添加して溶解させ、上記ヘキサメチレン
テトラミンを添加して溶解させることにより製造するこ
とができる。The non-aqueous electrolyte for a secondary battery of the present invention is dissolved by adding a lithium compound as an electrolyte into the non-aqueous solvent while stirring the non-aqueous solvent, and adding and dissolving the above hexamethylenetetramine. It can be manufactured by the following.
【0012】本発明の二次電池用非水電解液は、リチウ
ム化合物を電解質とする種々の二次電池に適用できる。
特に、フッ素含有無機又は有機リチウム化合物を電解質
とする種々の二次電池に有効である。Liのド−プおよ
び脱ド−プが可能な炭素材料よりなる負極を有してなる
二次電池に好ましく適用することができる。即ち、充電
時にLiを吸蔵させ、放電時に放出させる炭素材料より
なる負極を有してなる二次電池に有効である。上記Li
のド−プおよび脱ド−プは、例えば、リチウム金属、リ
チウム合金またはリチウムイオンにより行なうことがで
きる。ここで、リチウム合金としては、リチウムーアル
ミニウム合金を例示することができる。負極を構成する
炭素材料には、例えば、熱分解炭素類、コークス類(ピ
ッチコークス、ニードルコークス、石油コークス等)、
グラファイト類、有機高分子化合物焼成体(フェノール
樹脂、フラン樹脂等を適当な温度で焼成し炭素化したも
の)、炭素繊維、活性炭等が挙げられる。当該炭素材料
は、黒鉛化したものでもよい。The non-aqueous electrolyte for a secondary battery of the present invention can be applied to various secondary batteries using a lithium compound as an electrolyte.
In particular, it is effective for various secondary batteries using a fluorine-containing inorganic or organic lithium compound as an electrolyte. The present invention can be preferably applied to a secondary battery having a negative electrode made of a carbon material capable of doping and dedoping Li. That is, the present invention is effective for a secondary battery having a negative electrode made of a carbon material that causes Li to be inserted during charging and released during discharging. Li above
Can be carried out, for example, with lithium metal, lithium alloy or lithium ion. Here, as the lithium alloy, a lithium-aluminum alloy can be exemplified. Examples of the carbon material constituting the negative electrode include pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke, etc.),
Graphites, organic polymer compound fired bodies (phenol resins, furan resins, etc. fired at an appropriate temperature and carbonized), carbon fibers, activated carbon and the like can be mentioned. The carbon material may be graphitized.
【0013】一方、正極は、充放電が可能な種々の材料
から形成することができ、例えば、LiCoO2、Li
NiO2、LiMn2O4、LiMnO2などのLix
MO 2(ここで、Mは一種以上の遷移金属であり、xは
電池の充放電状態によって異なり、通常0.05≦x≦
1.20である)で表される、リチウムと一種以上の遷
移金属との複合酸化物や、FeS2、TiS2、V2O
5、MoO3、MoS 2などの遷移元素のカルコゲナイ
トあるいはポリアセチレン、ポリピロール等のポリマー
等を使用することができるが、就中、前記目的からは、
本発明は、Liのド−プおよび脱ド−プが可能な金属酸
化物材料等より形成する場合に有効で、特に、LiMn
2O4、LiMnO2などのフッ素を含有するリチウム
化合物の場合に有効である。On the other hand, the positive electrode is made of various chargeable / dischargeable materials.
For example, LiCoO2, Li
NiO2, LiMn2O4, LiMnO2Li such asx
MO 2(Where M is one or more transition metals and x is
Normally 0.05 ≦ x ≦
1.20), lithium and one or more transitions
Complex oxide with metal transfer, FeS2, TiS2, V2O
5, MoO3, MoS 2Chalcogenai of transition elements such as
Or polymers such as polyacetylene and polypyrrole
Etc. can be used, but above all, from the above purpose,
The present invention relates to a metal acid capable of doping and dedoping Li.
Effective when formed from a nitride material, etc.
2O4, LiMnO2Lithium containing fluorine such as
It is effective for compounds.
【0014】本発明の二次電池用非水電解液を使用した
二次電池の形状については特に限定されることはなく、
ボタン型、円筒型、角型、コイン型等の種々の形状にす
ることができる。The shape of the secondary battery using the non-aqueous electrolyte for a secondary battery of the present invention is not particularly limited.
Various shapes such as a button type, a cylindrical type, a square type, and a coin type can be used.
【0015】[0015]
【実施例】以下、本発明を実施例に基づいて更に説明す
る。The present invention will be further described below with reference to examples.
【0016】実施例1.炭酸エチレン(EC)、炭酸プ
ロピレン(PC)、γーブチロラクトン(GBL)、炭
酸ジメチル(DMC)、炭酸ジエチル(DEC)、炭酸
エチルメチル(MEC)の各溶媒に、LiPF6 を1
mol/リットルの濃度に溶解したものに、更にそれぞ
れにヘキサメチレンテトラミン0.5重量%を溶解した
電解液を50mlステンレス耐圧容器に密閉して、85
℃、100時間保持した後のHF濃度をアルカリ滴定に
より測定した。Embodiment 1 FIG. LiPF 6 was added to each solvent of ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (MEC).
mol / l of a solution dissolved in a concentration of 0.5% by weight of hexamethylenetetramine and sealed in a 50 ml stainless steel pressure vessel.
The HF concentration after keeping at 100C for 100 hours was measured by alkali titration.
【0017】比較例1.実施例1においてヘキサメチレ
ンテトラミンを添加しなかった以外は同様の電解液を上
述と同様の条件で試験した。Comparative Example 1 The same electrolytic solution was tested under the same conditions as described above except that hexamethylenetetramine was not added in Example 1.
【0018】実施例2.当該実施例で用いた非水電解液
二次電池は、正極と負極とセパレータと非水電解液とボ
タン型電池容器と正極側集電体と負極側集電体とガスケ
ットとを有してなるもので、上記正極として、LiMn
2O4を正極活物質とする合剤をペレット状に加圧成形
した成形品を使用し、また、負極として、黒鉛系MCM
Bを負極活物質担体とした合剤をペレット状に加圧成形
した成形品を使用した。また、非水電解液には、炭酸エ
チレン(EC)と炭酸ジエチル(DEC)との混合溶媒
(容量比2:3)に、LiPF6からなる電解質を濃度
1mol/リットルにて含有させ、さらに、ヘキサメチ
レンテトラミン0.5重量%を含有してなる溶液を使用
した。更に、上記セパレータにはポリプロピレン製の不
織布よりなるセパレータを用い、正極側集電体はステン
レス鋼により構成し、一方、負極側集電体はニッケルエ
キスパンドメタルにより構成し、さらに、上記電池容器
はステンレス鋼より構成し、その正極缶と負極缶をポリ
プロピレンのガスケットにより固定した。以上のように
して作製した電池について、充放電サイクル特性を調べ
た。尚、充電は定電流法とし、上限電圧を4.2V、定
電流での電流密度を0.5Cに設定し、放電は、電流密
度を0.5Cに設定し、終止電圧は、2.7Vとした。
通常充放電は25℃で100サイクル実施した。100
サイクルでの電池容量の比較から評価した。Embodiment 2 FIG. The non-aqueous electrolyte secondary battery used in this example has a positive electrode, a negative electrode, a separator, a non-aqueous electrolyte, a button-type battery container, a positive electrode current collector, a negative electrode current collector, and a gasket. Wherein the positive electrode is LiMn
A molded product obtained by press-molding a mixture containing 2 O 4 as a positive electrode active material into a pellet is used, and a graphite-based MCM is used as a negative electrode.
A molded product obtained by pressure-forming a mixture containing B as a negative electrode active material carrier into a pellet was used. The non-aqueous electrolyte contains an electrolyte composed of LiPF 6 at a concentration of 1 mol / liter in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 2: 3). A solution containing 0.5% by weight of hexamethylenetetramine was used. Further, a separator made of a nonwoven fabric made of polypropylene is used for the separator, the positive electrode-side current collector is made of stainless steel, while the negative electrode-side current collector is made of nickel expanded metal, and the battery container is made of stainless steel. The positive electrode can and the negative electrode can were made of steel, and were fixed with a polypropylene gasket. The charge / discharge cycle characteristics of the battery fabricated as described above were examined. The charging was performed by the constant current method, the upper limit voltage was set to 4.2 V, the current density at constant current was set to 0.5 C, and the discharge was set to 0.5 C at the current density, and the final voltage was 2.7 V. And
Normal charging and discharging were performed at 25 ° C. for 100 cycles. 100
Evaluation was made based on a comparison of battery capacity in each cycle.
【0019】実施例3.実施例2における非水電解液の
溶媒を炭酸エチレン(EC)と炭酸ジメチル(DMC)
との混合溶媒(容量比1:1)とし、また、正極にLi
CoO2 を使用し、ヘキサメチレンテトラミンの添加
量を0.1重量%とした以外は、上記実施例2と同様に
してボタン型電池を作製し、実施例2と同様の条件下
で、充放電サイクル特性を調べた。Embodiment 3 FIG. The solvent of the non-aqueous electrolyte in Example 2 was ethylene carbonate (EC) and dimethyl carbonate (DMC)
And a mixed solvent (volume ratio 1: 1).
A button-type battery was manufactured in the same manner as in Example 2 except that CoO 2 was used and the addition amount of hexamethylenetetramine was 0.1% by weight, and charge and discharge were performed under the same conditions as in Example 2. The cycle characteristics were examined.
【0020】比較例2.実施例2においてヘキサメチレ
ンテトラミンを添加しなかった以外は、上記実施例2と
同様にしてボタン型電池を作製し、実施例2と同様の条
件下で、充放電サイクル特性を調べた。Comparative Example 2 A button-type battery was prepared in the same manner as in Example 2 except that hexamethylenetetramine was not added in Example 2, and the charge / discharge cycle characteristics were examined under the same conditions as in Example 2.
【0021】比較例3.実施例3においてヘキサメチレ
ンテトラミンを添加しなかった以外は、実施例3と同様
にしてボタン型電池を作製し、実施例2と同様の条件下
で、充放電サイクル特性を調べた。Comparative Example 3 A button-type battery was produced in the same manner as in Example 3 except that hexamethylenetetramine was not added in Example 3, and the charge / discharge cycle characteristics were examined under the same conditions as in Example 2.
【0022】以上の結果を、表1及び図1に示す。The above results are shown in Table 1 and FIG.
【0023】[0023]
【表1】 [Table 1]
【0024】表1に示すように、本発明のヘキサメチレ
ンテトラミンを添加した電解液(実施例1)は、85
℃、100時間後において、当該ヘキサメチレンテトラ
ミンを添加しなかった電解液(比較例1)に比較して、
HFの増加抑制効果があることが判る。As shown in Table 1, the electrolyte solution (Example 1) to which hexamethylenetetramine of the present invention was added was 85%.
100 ° C., after 100 hours, compared with the electrolyte solution (Comparative Example 1) to which the hexamethylenetetramine was not added,
It can be seen that there is an effect of suppressing an increase in HF.
【0025】図1に示すように、本発明のヘキサメチレ
ンテトラミンを添加した電解液(実施例2、3)は、1
00サイクルの放電容量において、当該ヘキサメチレン
テトラミンを加えなかった電解液(比較例2、3)に比
較して、電池容量サイクル劣化が見られず、効果がある
ことが判る。As shown in FIG. 1, the electrolyte solution (Examples 2 and 3) to which hexamethylenetetramine of the present invention was added was 1
At a discharge capacity of 00 cycles, the battery capacity cycle deterioration was not observed as compared with the electrolyte solution to which hexamethylenetetramine was not added (Comparative Examples 2 and 3), indicating that the battery was effective.
【0026】以上本発明者によってなされた発明を実施
例にもとずき具体的に説明したが、本発明は上記実施例
に限定されるものではなく、その要旨を逸脱しない範囲
で種々変更可能であることはいうまでもない。例えば、
上記実施例では、電池の形状はボタン型で説明を行なっ
たが、これに限定されるものではなく、他の角型、円筒
型、コイン型等であっても同様の効果を得ることが出来
る。Although the invention made by the inventor has been specifically described based on the embodiments, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the invention. Needless to say, For example,
In the above embodiment, the shape of the battery is described as a button type, but the shape is not limited to this, and similar effects can be obtained even with other square, cylindrical, coin type, etc. .
【0027】[0027]
【発明の効果】本願において開示される発明のうち代表
的なものによって得られる効果を簡単に説明すれば、下
記のとおりである。すなわち、本発明によれば、二次電
池用非水電解液において、ヘキサメチレンテトラミンを
添加することにより、フッ素含有リチウム塩の分解によ
るHFの発生を抑制し、その電解液を用いた二次電池の
充放電サイクル特性を改善することができる。又、正極
におけるMn含有リチウム酸化物が、上記HFによりM
nが溶出し電池の膨れ及び放電特性の低下を来すという
問題点を解消できる。更には、電解液の分解を抑制し
て、炭酸ガスやオレフィンガスの生成による電池の内圧
の上昇による電池の膨れを防止し、又、非水溶媒を含む
リチウム二次電池における電解液の充放電特性を向上さ
せ、その充放電サイクル特性を改善することができ、更
には、炭素材料よりなる負極の二次電池では、分解が起
こり、使用し難いとされているような非水溶媒を使用で
きるようにすることができる。The effects obtained by the representative ones of the inventions disclosed in the present application will be briefly described as follows. That is, according to the present invention, in a non-aqueous electrolyte for a secondary battery, by adding hexamethylenetetramine, generation of HF due to decomposition of a fluorine-containing lithium salt is suppressed, and a secondary battery using the electrolyte is used. Can be improved in charge-discharge cycle characteristics. Further, the Mn-containing lithium oxide in the positive electrode was changed to M
It is possible to solve the problem that n is eluted to cause swelling of the battery and deterioration of discharge characteristics. Further, the decomposition of the electrolyte is suppressed to prevent the battery from swelling due to an increase in the internal pressure of the battery due to the generation of carbon dioxide gas and olefin gas, and to charge and discharge the electrolyte in a lithium secondary battery containing a non-aqueous solvent. The characteristics can be improved, the charge / discharge cycle characteristics can be improved, and further, in a secondary battery of a negative electrode made of a carbon material, a non-aqueous solvent that is decomposed and is considered difficult to use can be used. You can do so.
【図1】図1は、本発明の作用効果を説明するグラフで
ある。FIG. 1 is a graph illustrating the operation and effect of the present invention.
1…実施例2 2…実施例3 3…比較例2 4…比較例4 1 ... Example 2 2 ... Example 3 3 ... Comparative Example 2 4 ... Comparative Example 4
───────────────────────────────────────────────────── フロントページの続き (72)発明者 六角 隆広 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 (72)発明者 小島 哲雄 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 (72)発明者 上田 定夫 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 (72)発明者 中野 稔 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 Fターム(参考) 5H029 AJ02 AJ05 AJ07 AK03 AK05 AK16 AK18 AL06 AL07 AL08 AL12 AM01 AM02 AM03 AM04 AM05 AM07 DJ09 EJ07 EJ12 HJ10 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takahiro Hexagon 3-11-1 Mizutani Higashi, Fujimi-shi, Saitama Toyama Pharmaceutical Co., Ltd. Shiki Plant (72) Inventor Tetsuo Kojima 3-11 Mizutani-Higashi, Fujimi-shi, Saitama -1 Inside the Shiki Plant of Toyama Pharmaceutical Co., Ltd. (72) Inventor Sadao Ueda 3-1-1-1 Mizutani Higashi, Fujimi City, Saitama Prefecture Inside the Shiki Plant of Toyama Pharmaceutical Co., Ltd. (72) Inventor Minoru Nakano Mizutani, Fujimi City, Saitama Prefecture 3-11-1 Higashi F-term (reference) in the Shiki Plant of Toyama Pharmaceutical Co., Ltd. 5H029 AJ02 AJ05 AJ07 AK03 AK05 AK16 AK18 AL06 AL07 AL08 AL12 AM01 AM02 AM03 AM04 AM05 AM07 DJ09 EJ07 EJ12 HJ10
Claims (3)
素材料等よりなる負極とLiのド−プおよび脱ド−プが
可能な金属酸化物材料等よりなる正極とを有してなる二
次電池に使用でき、非水溶媒と、電解質としてリチウム
化合物を含む二次電池用非水電解液において、次の式1
で表されるヘキサメチレンテトラミン 【式1】 を含有してなることを特徴とする二次電池用非水電解
液。1. A negative electrode comprising a carbon material or the like capable of doping and undoping Li and a positive electrode comprising a metal oxide material or the like capable of doping and undoping Li. In a non-aqueous electrolyte for a secondary battery containing a non-aqueous solvent and a lithium compound as an electrolyte, the following formula 1
Hexamethylenetetramine represented by Formula 1 A non-aqueous electrolyte for a secondary battery, comprising:
ンテトラミンの濃度が0.001〜5重量%であること
を特徴とする、請求項1に記載の二次電池用非水電解
液。2. The non-aqueous electrolyte for a secondary battery according to claim 1, wherein the concentration of hexamethylenetetramine in the non-aqueous electrolyte for a secondary battery is 0.001 to 5% by weight. .
有するリチウム化合物であることを特徴とする、請求項
1または2に記載の二次電池用非水電解液。3. The non-aqueous electrolyte for a secondary battery according to claim 1, wherein the lithium compound of the electrolyte is a lithium compound containing fluorine.
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JP2000074149A JP2001266940A (en) | 2000-03-16 | 2000-03-16 | Non-aqueous electrolytic solution for secondary battery |
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JP2000074149A JP2001266940A (en) | 2000-03-16 | 2000-03-16 | Non-aqueous electrolytic solution for secondary battery |
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Family
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100454017B1 (en) * | 2002-05-16 | 2004-10-26 | 주식회사 이앤지텍 | Method for manufacturing organic electrolytic solution and anode of lithium secondary battery and lithium secondary battery having organic electrolytic solution and anode manufactured by the same |
WO2006088002A1 (en) * | 2005-02-18 | 2006-08-24 | Sony Corporation | Electrolyte solution and battery |
WO2007148888A1 (en) | 2006-06-20 | 2007-12-27 | Lg Chem, Ltd. | Electrolyte for improving life characteristics at high temperature and lithium secondary battery comprising the same |
JP2013137873A (en) * | 2011-12-28 | 2013-07-11 | Toyota Industries Corp | Lithium ion secondary battery |
-
2000
- 2000-03-16 JP JP2000074149A patent/JP2001266940A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100454017B1 (en) * | 2002-05-16 | 2004-10-26 | 주식회사 이앤지텍 | Method for manufacturing organic electrolytic solution and anode of lithium secondary battery and lithium secondary battery having organic electrolytic solution and anode manufactured by the same |
WO2006088002A1 (en) * | 2005-02-18 | 2006-08-24 | Sony Corporation | Electrolyte solution and battery |
US8916291B2 (en) | 2005-02-18 | 2014-12-23 | Sony Corporation | Electrolytic solution and battery |
WO2007148888A1 (en) | 2006-06-20 | 2007-12-27 | Lg Chem, Ltd. | Electrolyte for improving life characteristics at high temperature and lithium secondary battery comprising the same |
EP2038959A1 (en) * | 2006-06-20 | 2009-03-25 | LG Chem, Ltd. | Electrolyte for improving life characteristics at high temperature and lithium secondary battery comprising the same |
EP2038959A4 (en) * | 2006-06-20 | 2010-04-07 | Lg Chemical Ltd | Electrolyte for improving life characteristics at high temperature and lithium secondary battery comprising the same |
JP2013137873A (en) * | 2011-12-28 | 2013-07-11 | Toyota Industries Corp | Lithium ion secondary battery |
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