JP3439085B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3439085B2 JP3439085B2 JP22512697A JP22512697A JP3439085B2 JP 3439085 B2 JP3439085 B2 JP 3439085B2 JP 22512697 A JP22512697 A JP 22512697A JP 22512697 A JP22512697 A JP 22512697A JP 3439085 B2 JP3439085 B2 JP 3439085B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- 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 - Lifetime
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Classifications
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- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、負極活物質として
リチウムを用いた非水系電解液二次電池、即ちリチウム
電池の保存特性の改良に関するものである。TECHNICAL FIELD The present invention relates to improvement of storage characteristics of a non-aqueous electrolyte secondary battery using lithium as a negative electrode active material, that is, a lithium battery.
【０００２】[0002]
【従来の技術】負極活物質として例えばリチウムを用い
るリチウム電池は、高エネルギー密度電池として注目さ
れており、活発な研究が行われている。2. Description of the Related Art A lithium battery using, for example, lithium as a negative electrode active material has been attracting attention as a high energy density battery and has been actively researched.
【０００３】一般にこの種電池では、非水系電解液を構
成する溶媒として、エチレンカーボネート、プロピレン
カーボネート、ブチレンカーボネート、ジメチルカーボ
ネート、ジエチルカーボネート、スルホラン、1,2-ジメ
トキシエタン、テトラヒドロフラン、1,3-ジオキソラン
等の単独、二成分あるいは三成分混合物が使用されてい
る。そして、この中に溶解される溶質として、LiPF6、L
iBF4、LiClO4、LiCF3SO3、LiASF6、LiN(CF3SO2)2、LiCF
3(CF2)3SO3等を列挙することができる。Generally, in this type of battery, as a solvent constituting the non-aqueous electrolyte, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, sulfolane, 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxolane. Etc. are used alone, binary or ternary mixtures. Then, as solutes dissolved in this, LiPF 6 , L
iBF 4 , LiClO 4 , LiCF 3 SO 3 , LiA S F 6 , LiN (CF 3 SO 2 ) 2 , LiCF
3 (CF 2 ) 3 SO 3 etc. can be enumerated.
【０００４】ところで、この種二次電池において、使用
される有機溶媒を含む電解液によって、その反応性が大
きく異なり、電池特性が変化する。特に、サイクル特性
や、充電後の保存特性が左右される。これは、一般に、
リチウム電池は高電圧であるため、電解液の分解などの
副反応は避けがたい。その結果、サイクル特性や保存特
性の面で問題があった。By the way, in this type of secondary battery, the reactivity is greatly different depending on the electrolytic solution containing the organic solvent used, and the battery characteristics are changed. In particular, cycle characteristics and storage characteristics after charging are affected. This is generally
Since lithium batteries have high voltage, side reactions such as electrolyte decomposition are unavoidable. As a result, there are problems in terms of cycle characteristics and storage characteristics.
【０００５】そこで、特開平6-13107号公報には、電解
液にピリジンを添加することにより、電池の特性を向上
させることが提案されている。ここでは、負極に黒鉛か
らなる炭素材料を用い、ピリジンを添加することによっ
て、電解液の安定性を向上させている。然し乍ら、この
電池を充電状態で長時間保存すると自己放電が大きく、
充電保存特性に問題が生じる。従って、保存時の自己放
電を抑制することは、この種電池の実用化において重要
な課題となっている。Therefore, Japanese Patent Laid-Open No. 6-13107 proposes to improve the characteristics of the battery by adding pyridine to the electrolytic solution. Here, the stability of the electrolytic solution is improved by using a carbon material made of graphite for the negative electrode and adding pyridine. However, if this battery is stored in a charged state for a long time, self-discharge will be large,
There is a problem with charge storage characteristics. Therefore, suppressing self-discharge during storage is an important issue in the practical application of this type of battery.
【０００６】[0006]
【発明が解決しようとする課題】本発明はこの種二次電
池を保存した場合の自己放電を抑制し、充電後の保存特
性を向上させる優れた非水系電解液を提案するものであ
る。DISCLOSURE OF THE INVENTION The present invention proposes an excellent non-aqueous electrolyte solution which suppresses self-discharge when a secondary battery of this kind is stored and improves storage characteristics after charging.
【０００７】[0007]
【課題を解決するための手段】本発明は、正極と、リチ
ウムまたはリチウムの吸蔵放出の可能な負極材料からな
る負極と、有機溶媒と溶質とからなる非水系電解液とを
備えた非水系電解液二次電池において、前記有機溶媒
が、モノフルオロ燐酸リチウム(Li2PO3F)、ジフルオロ
燐酸リチウム(LiPO2F2)からなる群から選ばれた少なく
とも１種の添加剤を含有することを特徴とするものであ
る。The present invention provides a non-aqueous electrolysis comprising a positive electrode, a negative electrode composed of lithium or a negative electrode material capable of inserting and extracting lithium, and a non-aqueous electrolytic solution containing an organic solvent and a solute. In the liquid secondary battery, the organic solvent contains at least one additive selected from the group consisting of lithium monofluorophosphate (Li 2 PO 3 F) and lithium difluorophosphate (LiPO 2 F 2 ). It is a feature.
【０００８】この理由は、添加剤としてのモノフルオロ
燐酸リチウム、ジフルオロ燐酸リチウムの内の１種を添
加した非水系電解液を用いると、この添加剤がリチウム
と反応し、良質な被膜が正極及び負極界面に形成され
る。この被膜が、充電状態の活物質と有機溶媒との直接
接触を抑制して、活物質と電解液との接触を因とする非
水系電解液の分解を抑制すると考えられる。この様にし
て、保存後の保存特性を向上させることが可能となる。The reason for this is that when a non-aqueous electrolyte containing one of lithium monofluorophosphate and lithium difluorophosphate as an additive is used, the additive reacts with lithium and a high-quality coating is formed on the positive electrode and the positive electrode. It is formed at the negative electrode interface. It is considered that this film suppresses the direct contact between the active material in the charged state and the organic solvent and suppresses the decomposition of the non-aqueous electrolytic solution due to the contact between the active material and the electrolytic solution. In this way, the storage characteristics after storage can be improved.
【０００９】前記添加剤の中でも、モノフルオロ燐酸リ
チウムが、正、負極上に最適な被膜を形成し易い若しく
は負極上に吸着し易いと考えられ、好ましい。このよう
にして、自己放電率が一層抑制可能となる。Among the above-mentioned additives, lithium monofluorophosphate is preferable because it is considered to be positive, easy to form an optimum coating film on the negative electrode or easy to adsorb on the negative electrode. In this way, the self-discharge rate can be further suppressed.
【００１０】そして、前記添加剤の添加量としては、前
記有機溶媒の重量に対して0.01重量％以上20.0重量％以
下、特に好ましくは0.１重量％から5.0重量％の範囲と
するのが好ましく、この種非水系電解液二次電池の保存
後の放電容量の低下を抑制するという観点から好適であ
る。The amount of the additive added is preferably 0.01% by weight or more and 20.0% by weight or less, more preferably 0.1% by weight to 5.0% by weight, based on the weight of the organic solvent. This is preferable from the viewpoint of suppressing a decrease in discharge capacity after storage of this kind of non-aqueous electrolyte secondary battery.
【００１１】この種電池の負極としては、電気化学的に
リチウムイオンを吸蔵及び放出することが可能な物質、
又は金属リチウムを電極材料とするものが例示される。
電気化学的にリチウムイオンを吸蔵及び放出することが
可能な物質としては、黒鉛、コークス、有機物焼成体等
の炭素材料、及びリチウム−アルミニウム合金、リチウ
ム−マグネシウム合金、リチウム−インジウム合金、リ
チウム−錫合金、リチウム−タリウム合金、リチウム−
鉛合金、リチウム−ビスマス合金等のリチウム合金が例
示される。As the negative electrode of this type of battery, a substance capable of electrochemically absorbing and desorbing lithium ions,
Alternatively, a material using metallic lithium as an electrode material is exemplified.
Examples of the substance capable of electrochemically absorbing and desorbing lithium ions include carbon materials such as graphite, coke, and organic material calcined products, and lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, lithium-tin. Alloy, Lithium-Thallium alloy, Lithium-
Examples are lead alloys and lithium alloys such as lithium-bismuth alloys.
【００１２】この中でも、炭素材料である、黒鉛、コー
クス、有機物焼成体が、好ましい。Among these, carbon materials such as graphite, coke, and an organic material fired body are preferable.
【００１３】また、この種電池の溶質としては、LiP
F6、LiAsF6、LiSbF6、LiBF4、LiClO4、LiCF3SO3が適す
るが、特に放電容量、保存特性の面からLiPF6が最適で
ある。The solute of this type of battery is LiP.
F 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiClO 4 , and LiCF 3 SO 3 are suitable, but LiPF 6 is particularly suitable in terms of discharge capacity and storage characteristics.
【００１４】尚、この種電池の有機溶媒としては、ジオ
キソラン、エチレンカーボネート、プロピレンカーボネ
ート、ブチレンカーボネート、ビニレンカーボネート、
ジメチルカーボネート、ジエチルカーボネート、エチル
メチルカーボネート、スルホラン、テトラヒドロフラン
の単体、もしくはこれらの混合物を使用することが可能
である。As the organic solvent for this type of battery, dioxolane, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate,
It is possible to use dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, sulfolane, tetrahydrofuran alone or a mixture thereof.
【００１５】この種電池の正極としては、マンガン、コ
バルト、ニッケル、バナジウム、ニオブを少なくとも一
種含む金属酸化物を使用することができるが、これに限
定されるものではない。As the positive electrode of this type of battery, a metal oxide containing at least one of manganese, cobalt, nickel, vanadium and niobium can be used, but the present invention is not limited thereto.
【００１６】[0016]
【発明の実施の形態】以下に、本発明の実施例につき詳
述する。
（実験１）この実験１では、添加剤としてのモノフルオ
ロ燐酸リチウム、ジフルオロ燐酸リチウムの添加効果を
調べるため、その添加の有無、ピリジン添加の電池と比
較した。
［実施例１］（モノフルオロ燐酸リチウム添加）
図１に、本発明の一実施例としての円筒型非水系電解液
二次電池の断面図を示す。金属酸化物からなる正極１は
正極集電体に塗着され、この正極１と天然黒鉛からなる
負極２とはセパレータ３を介して渦巻き電極体を構成し
ている。前記正極１の正極集電体には、正極リード４が
接続され、前記負極２の負極集電体には、負極リード５
が接続されている。前記渦巻き電極体は負極缶６に収納
され、負極リード５と接続されている。一方、負極缶６
の上部周端の開口部には、ポリプロピレン製の絶縁パッ
キング７が配置され、封口蓋８を兼ねる正極外部端子に
より密閉されている。尚、正極リード４は正極外部端子
部と接続されている。そして、上記セパレータ３には、
本発明の要点である添加剤を含んだ非水系電解液が含浸
されている。Embodiments of the present invention will be described in detail below. (Experiment 1) In this experiment 1, in order to examine the effect of adding lithium monofluorophosphate and lithium difluorophosphate as additives, the presence or absence of addition of the additives and the comparison with batteries containing pyridine were compared. [Example 1] (Addition of lithium monofluorophosphate) Fig. 1 shows a cross-sectional view of a cylindrical non-aqueous electrolyte secondary battery as an example of the present invention. The positive electrode 1 made of a metal oxide is applied to a positive electrode current collector, and the positive electrode 1 and the negative electrode 2 made of natural graphite form a spiral electrode body via a separator 3. The positive electrode lead 4 is connected to the positive electrode current collector of the positive electrode 1, and the negative electrode lead 5 is connected to the negative electrode current collector of the negative electrode 2.
Are connected. The spiral electrode body is housed in a negative electrode can 6 and connected to the negative electrode lead 5. On the other hand, negative electrode can 6
An insulating packing 7 made of polypropylene is placed in the opening at the upper peripheral end of the, and is sealed by a positive electrode external terminal which also serves as a sealing lid 8. The positive electrode lead 4 is connected to the positive electrode external terminal portion. And, in the separator 3,
It is impregnated with a non-aqueous electrolytic solution containing an additive which is the main point of the present invention.
【００１７】ところで、前記正極１は、コバルト酸リチ
ウム(LiCoO2)を主材料として用いている。このために、
コバルト酸リチウムと、導電剤としての人造黒鉛粉末
と、結着剤としてのポリフッ化ビニリデン粉末とを、そ
れぞれ90：５：５の重量比で混合して、ペーストを準備
している。そして、このペーストをアルミニウム箔から
なる正極集電体に塗着成形した後、150℃で乾燥処理し
て、正極１を作製した。By the way, the positive electrode 1 uses lithium cobalt oxide (LiCoO 2 ) as a main material. For this,
Lithium cobalt oxide, artificial graphite powder as a conductive agent, and polyvinylidene fluoride powder as a binder were mixed in a weight ratio of 90: 5: 5 to prepare a paste. Then, this paste was applied and molded on a positive electrode current collector made of aluminum foil, and then dried at 150 ° C. to prepare a positive electrode 1.
【００１８】一方、前記負極２は、負極材料としての天
然黒鉛と結着剤としてのポリフッ化ビニリデンとを95：
５の重量比で混合してペーストを得、銅箔からなる集電
体に塗着形成した後、150℃で乾燥処理することにより
作製した。On the other hand, the negative electrode 2 is composed of natural graphite as a negative electrode material and polyvinylidene fluoride as a binder of 95:
The mixture was mixed at a weight ratio of 5 to obtain a paste, which was applied to a collector made of copper foil to form a paste, and then dried at 150 ° C. to prepare a paste.
【００１９】そして、電解液としてのエチレンカーボネ
ート(EC)とジエチルカーボネート(DEC)の混合有機溶媒
に、溶質としてヘキサフルオロ燐酸リチウムを1モル／l
の割合で溶解したものに、添加剤としてのモノフルオロ
燐酸リチウム(Li2PO3F)を混合有機溶媒の重量に対して
1.0重量％の割合で添加して、非水系電解液を得る。尚、
セパレータ3には、イオン透過性のポリプロピレン製の
微多孔膜を使用している。Then, 1 mol / l of lithium hexafluorophosphate is used as a solute in a mixed organic solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) as an electrolytic solution.
Lithium monofluorophosphate (Li 2 PO 3 F) as an additive to the solution dissolved in the ratio of
1.0 wt% is added to obtain a non-aqueous electrolytic solution. still,
For the separator 3, an ion-permeable polypropylene microporous membrane is used.
【００２０】このようにして、直径14.0mm、高さ50.0mm
(AAサイズ)の本発明電池Ａを作製した。
［実施例２］（ジフルオロ燐酸リチウム添加）
前記実施例１において使用したモノフルオロ燐酸リチウ
ムに代えて、添加剤としてジフルオロ燐酸リチウム(LiP
O2F2)を使用したこと以外は同様にして、本発明電池Ｂ
を作製した。
［実施例３］（モノフルオロ燐酸リチウム＋ジフルオロ
燐酸リチウム添加）
前記実施例１において使用したモノフルオロ燐酸リチウ
ムに代えて、添加剤としてモノフルオロ燐酸リチウム(L
i2PO3F)とジフルオロ燐酸リチウム(LiPO2F2)との混合物
を使用したこと以外は同様にして、本発明電池Ｃを作製
した。
［実施例４］（モノフルオロ燐酸リチウム添加、溶媒の
変更）
前記実施例１において使用したエチレンカーボネート(E
C)とジエチルカーボネート(DEC)とからなる混合有機溶
媒に代えて、プロピレンカーボネート(PC)とジエチルカ
ーボネート(DEC)とからなる混合有機溶媒を使用したこ
と以外は同様にして、本発明電池Ｄを作製した。
［比較例１］前記実施例１においてモノフルオロ燐酸リ
チウムを添加しない電解液を使用して同様の電池を作製
し、これを比較電池Ｘとした。
［比較例２］前記実施例１においてモノフルオロ燐酸リ
チウムに代えて、添加剤としてピリジンを添加した電解
液を使用して同様の電池を作製し、これを比較電池Ｙと
した。この電池は、特開平6-13107号公報に開示された
ピリジン添加の技術思想に近いものである。In this way, the diameter is 14.0 mm and the height is 50.0 mm.
A battery A of the present invention of (AA size) was produced. [Example 2] (Addition of lithium difluorophosphate) Instead of the lithium monofluorophosphate used in Example 1, lithium difluorophosphate (LiP) was used as an additive.
O 2 F 2 ) was used in the same manner as in the present invention battery B.
Was produced. [Example 3] (Lithium monofluorophosphate + lithium difluorophosphate added) Instead of the lithium monofluorophosphate used in Example 1, lithium monofluorophosphate (L
Battery C of the present invention was produced in the same manner except that a mixture of i 2 PO 3 F) and lithium difluorophosphate (LiPO 2 F 2 ) was used. [Example 4] (Addition of lithium monofluorophosphate and change of solvent) The ethylene carbonate (E
C) and diethyl carbonate (DEC) in place of the mixed organic solvent, propylene carbonate (PC) and diethyl carbonate (DEC) in the same manner except that a mixed organic solvent was used, the present invention battery D It was made. [Comparative Example 1] The same battery as in Example 1 was prepared using an electrolytic solution containing no lithium monofluorophosphate, and this was designated as Comparative Battery X. [Comparative Example 2] A similar battery was prepared by using an electrolytic solution in which pyridine was added as an additive instead of lithium monofluorophosphate in Example 1, and was used as Comparative Battery Y. This battery is similar to the technical idea of pyridine addition disclosed in JP-A-6-13107.
【００２１】これらの本発明電池Ａ、Ｂ、Ｃ、Ｄ及び比
較電池Ｘ、Ｙを用い、各電池の保存特性を比較した。こ
の実験条件は、各電池を作製し一定期間保存した後、実
際に電池を放電させ保存前の容量と比較して、その差を
保存前の容量に対する百分率として容量残存率(％)を定
めた。Using these batteries A, B, C and D of the present invention and comparative batteries X and Y, the storage characteristics of each battery were compared. In this experimental condition, after each battery was prepared and stored for a certain period of time, the battery was actually discharged and compared with the capacity before storage, and the difference in capacity was defined as a percentage of the capacity before storage, and the capacity remaining rate (%) was determined. .
【００２２】この結果を、表１に示す。表１は、添加剤
の種類と添加量(重量％)、保存前の電池の放電容量(mA
h)、保存後の電池の放電容量(mAh)及び容量残存率
（％）の関係を示したものである。The results are shown in Table 1. Table 1 shows the types of additives, the amount added (% by weight), and the discharge capacity (mA) of the battery before storage.
h), the discharge capacity (mAh) of the battery after storage and the remaining capacity ratio (%) are shown.
【００２３】尚、保存前、後の電池の放電容量の測定
は、次のようにして行った。まず、作製直後の各電池を
200mAの定電流で充電終止電圧4.2Ｖまで充電し、放電電
流200mAの定電流で放電終止電圧2.75Ｖまで放電させそ
の容量を実測し、保存前の放電容量とした。次に、保存
前の放電容量を測定した各電池を、200mAの定電流で充
電終止電圧4.2Ｖまで充電し、60℃にて20日間保存した
後、放電電流200mAの定電流で放電終止電圧2.75Ｖまで
放電させてその容量を実測し、保存後の放電容量とし
た。また、容量残存率は、保存前の放電容量に対する保
存後の放電容量をパーセントで表したものである。The discharge capacity of the battery before and after storage was measured as follows. First of all, just after making each battery
It was charged to a final charge voltage of 4.2 V with a constant current of 200 mA, discharged to a final discharge voltage of 2.75 V with a constant current of 200 mA, and its capacity was measured and used as the discharge capacity before storage. Next, each battery whose discharge capacity before storage was measured was charged with a constant current of 200mA to a charge end voltage of 4.2V, and stored at 60 ° C for 20 days, and then a discharge end voltage of 2.75 at a constant current of 200mA. It was discharged to V and its capacity was measured to obtain the discharge capacity after storage. The capacity remaining rate is the discharge capacity after storage expressed in percent with respect to the discharge capacity before storage.
【００２４】[0024]
【表１】 [Table 1]
【００２５】この表１より、本発明電池Ａ、Ｂ、Ｃ及び
Ｄは、比較電池Ｘ、Ｙに比して、容量残存率が大きく、
即ち自己放電が小さくなっており、保存時の電池容量の
低下が抑えられ、自己放電が抑制されていることがわか
る。
（実験２）次にここでは、前記実験１で準備した各電池
のサイクル特性を比較した。この時の実験条件は、作製
直後の各電池を200mAの定電流で充電終止電圧4.2Ｖまで
充電し、放電電流200mAの定電流で放電終止電圧2.75Ｖ
まで放電させるという充放電サイクルを繰り返し行うと
いうものである。From Table 1, the batteries A, B, C and D of the present invention have a large remaining capacity ratio as compared with the comparative batteries X and Y.
That is, it is understood that the self-discharge is small, the decrease in the battery capacity during storage is suppressed, and the self-discharge is suppressed. (Experiment 2) Next, here, the cycle characteristics of the batteries prepared in Experiment 1 were compared. The experimental conditions at this time were to charge each battery immediately after fabrication with a constant current of 200 mA to a charge end voltage of 4.2 V, and with a constant current of discharge current of 200 mA to a discharge end voltage of 2.75 V.
The charging / discharging cycle of discharging up to is repeated.
【００２６】この結果を、図２に示す。図２は、各電池
のサイクル数と放電容量との関係を表している。この結
果より、本発明電池の中でも、有機溶媒としてエチレン
カーボネート(EC)とジエチルカーボネート(DEC)との混
合溶媒を用いた本発明電池Ａ、本発明電池Ｂ及び本発明
電池Ｃの秀逸性が伺える。
（実験３）前記実験１の本発明電池Ａと同様の構成を有
する電池を作製し、非水系電解液に添加するモノフルオ
ロ燐酸リチウム(Li2PO3F)の添加量を変化させ、保存後
の電池の放電容量を比較した。この実験条件は各電池を
作製後、60℃で20日間保存し、電池の放電容量(mAh)を
実測した。The results are shown in FIG. FIG. 2 shows the relationship between the number of cycles of each battery and the discharge capacity. From these results, among the batteries of the present invention, the superiority of the present invention battery A, the present invention battery B and the present invention battery C using the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) as the organic solvent can be seen. . (Experiment 3) A battery having the same configuration as the battery A of the present invention in Experiment 1 was prepared, and the amount of lithium monofluorophosphate (Li 2 PO 3 F) added to the non-aqueous electrolyte solution was changed, and after storage The discharge capacities of the batteries were compared. Under this experimental condition, each battery was manufactured and then stored at 60 ° C. for 20 days, and the discharge capacity (mAh) of the battery was measured.
【００２７】この結果を、表２に示す。表２は、非水系
電解液重量に対するモノフルオロ燐酸リチウムの添加量
と、保存前の電池の放電容量、保存後の電池の放電容量
及び容量残存率（％）の関係を示したものである。尚、
この容量残存率の算出は、前記実験１と同じである。The results are shown in Table 2. Table 2 shows the relationship between the amount of lithium monofluorophosphate added to the weight of the non-aqueous electrolyte solution, the discharge capacity of the battery before storage, the discharge capacity of the battery after storage, and the capacity remaining rate (%). still,
The calculation of the capacity remaining rate is the same as in Experiment 1 above.
【００２８】[0028]
【表２】 [Table 2]
【００２９】この結果より、添加剤であるモノフルオロ
燐酸リチウム(Li2PO3F)の添加量として、有機溶媒の重
量に対して、0.01重量％(電池Ａ１)から20.0重量％(電
池Ａ５)の範囲で添加効果が認められ、保存後の電池容
量の低下を抑制している。この添加量として、添加量0.
1重量％(電池Ａ２)から5.0重量％(電池Ａ３)の範囲が、
保存後の電池の放電容量を低下させないという観点か
ら、特に好ましい。From these results, as an additive amount of lithium monofluorophosphate (Li 2 PO 3 F) as an additive, 0.01% by weight (battery A1) to 20.0% by weight (battery A5) with respect to the weight of the organic solvent. In this range, the effect of addition is recognized, and the decrease in battery capacity after storage is suppressed. As this added amount, the added amount is 0.
The range of 1 wt% (Battery A2) to 5.0 wt% (Battery A3) is
It is particularly preferable from the viewpoint of not reducing the discharge capacity of the battery after storage.
【００３０】尚、実験３ではモノフルオロ燐酸リチウム
の添加量を変化させているが、ジフルオロ燐酸リチウム
(LiPO2F2)を用いた電池であっても、同様の傾向が観察
される。
（実験４）この実験４では、電解液を構成する溶質の種
類を代えて、保存特性を比較した。ここで組み立てた各
電池は、上記実施例１の本発明電池Ａと、溶質以外は、
全て同一条件である。In Experiment 3, the amount of lithium monofluorophosphate added was changed.
A similar tendency is observed even in the battery using (LiPO 2 F 2 ). (Experiment 4) In Experiment 4, the types of solutes constituting the electrolytic solution were changed and the storage characteristics were compared. Each of the batteries assembled here was the same as the battery A of the present invention of Example 1 except for the solute.
All have the same conditions.
【００３１】この結果を、表３に示す。表３は、非水系
電解液を構成する溶質の種類と、保存前の電池の放電容
量、保存後の電池の放電容量及び容量残存率（％）の関
係を示したものである。尚、この容量残存率の算出は、
前記実験１と同じである。The results are shown in Table 3. Table 3 shows the relationship between the type of solute constituting the non-aqueous electrolyte solution, the discharge capacity of the battery before storage, the discharge capacity of the battery after storage, and the remaining capacity rate (%). The calculation of the capacity remaining rate is
This is the same as Experiment 1 above.
【００３２】[0032]
【表３】 [Table 3]
【００３３】この結果より、本発明電池の溶質としてLi
PF6、LiAsF6、LiSbF6、LiBF4、LiClO4、LiCF3SO3が使用
できるが、容量残存率の点から云えば、LiPF6、LiAs
F6、LiSbF6、LiBF4、LiClO4が適する。そして、特に容
量残存率の顕著性から云えばLiPF 6が最適である。
（実験５）この実験５では、負極を構成する負極材料の
種類を代えて、保存特性を比較した。ここで組み立てた
各電池は、上記実施例１の本発明電池Ａと、負極材料以
外は、全て同一である。From these results, Li as the solute of the battery of the present invention was obtained.
PF6, LiAsF6, LiSbF6, LiBFFour, LiClOFour, LiCF3SO3Used by
However, from the viewpoint of capacity remaining rate, LiPF6, LiAs
F6, LiSbF6, LiBFFour, LiClOFourIs suitable. And especially Yong
Speaking of the outstanding residual amount, LiPF 6Is the best.
(Experiment 5) In Experiment 5, the negative electrode material constituting the negative electrode
The storage characteristics were compared by changing the type. Assembled here
Each battery was composed of the battery A of the present invention of Example 1 and the negative electrode material
Everything else is the same outside.
【００３４】この結果を、表４に示す。表４は、負極を
構成する負極材料の種類と、保存前の電池の放電容量、
保存後の電池の放電容量及び容量残存率（％）の関係を
示したものである。尚、この容量残存率の算出は、前記
実験１と同じである。The results are shown in Table 4. Table 4 shows the types of negative electrode materials constituting the negative electrode, the discharge capacity of the battery before storage,
It shows the relationship between the discharge capacity and the remaining capacity rate (%) of the battery after storage. The calculation of the capacity remaining rate is the same as in Experiment 1.
【００３５】[0035]
【表４】 [Table 4]
【００３６】この結果より、本発明電池の負極材料とし
ては、金属リチウム(本発明電池Ｆ３)と比較して、炭素
材料が適する。そして、天然黒鉛(本発明電池Ａ)、人造
黒鉛(本発明電池Ｆ１)、石油コークス(本発明電池Ｆ２)
等の炭素材料の中でも、特に容量残存率の顕著性から云
えば天然黒鉛(本発明電池Ａ)が最適である。From these results, as the negative electrode material of the battery of the present invention, the carbon material is more suitable than the lithium metal (the battery of the present invention F3). And natural graphite (invention battery A), artificial graphite (invention battery F1), petroleum coke (invention battery F2)
Among the above carbon materials, natural graphite (the battery A of the present invention) is most suitable from the standpoint of the remarkable residual capacity.
【００３７】尚、上記各実施例では、有機溶媒としてエ
チレンカーボネートとジエチルカーボネートの混合溶
媒、プロピレンカーボネートとジエチルカーボネートの
混合溶媒体を例示したが、ジオキソラン、ブチレンカー
ボネート、ビニレンカーボネート、ジメチルカーボネー
ト、エチルメチルカーボネート、テトラヒドロフランを
添加した混合物を使用することが可能である。In each of the above examples, the mixed solvent of ethylene carbonate and diethyl carbonate and the mixed solvent of propylene carbonate and diethyl carbonate were exemplified as the organic solvent. It is possible to use a mixture with the addition of carbonate, tetrahydrofuran.
【００３８】[0038]
【発明の効果】上述した如く、非水系電解液に、添加剤
であるモノフルオロ燐酸リチウム、ジフルオロ燐酸リチ
ウムの内の少なくとも１種を添加することにより、充電
後の容量残存率を大きくすることができ、この種電池の
保存特性を向上させることができる。そして、特に、前
記添加剤としては、モノフルオロ燐酸リチウムが適して
いる。更に、添加剤の添加量について言えば、前記有機
溶媒の重量に対して0.0１重量％から20.0重量％の範囲
が適し、特に0.1重量％から5.0重量％の範囲とすれば、
電池の保存特性を顕著に向上でき、その工業的価値は極
めて大きい。As described above, by adding at least one of lithium monofluorophosphate and lithium difluorophosphate, which are additives, to the non-aqueous electrolyte, the capacity remaining rate after charging can be increased. Therefore, the storage characteristics of this type of battery can be improved. And, in particular, lithium monofluorophosphate is suitable as the additive. Further, regarding the amount of the additive to be added, the range of 0.01% to 20.0% by weight relative to the weight of the organic solvent is suitable, and particularly the range of 0.1% to 5.0% by weight,
The storage characteristics of the battery can be remarkably improved, and its industrial value is extremely large.
【図１】本発明電池の断面図である。FIG. 1 is a sectional view of a battery of the present invention.
【図２】電池のサイクル特性比較図である。FIG. 2 is a comparative diagram of battery cycle characteristics.
１ 正極 ２ 負極 ３ セパレータ ４ 正極リード ５ 負極リード ６ 負極缶 ７ パッキング ８ 封口体 1 positive electrode 2 Negative electrode 3 separator 4 Positive lead 5 Negative electrode lead 6 Negative electrode can 7 packing 8 Sealing body
───────────────────────────────────────────────────── 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 (56)参考文献 特開 平９−7635（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 ＪＩＣＳＴファイル（ＪＯＩＳ)─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. ) Fields surveyed (Int.Cl. 7 , DB name) H01M 10/40 JISST file (JOIS)
Claims (7)
放出の可能な負極材料からなる負極と、有機溶媒と溶質
とからなる非水系電解液とを備えた非水系電解液二次電
池において、 前記有機溶媒が、モノフルオロ燐酸リチウム、ジフルオ
ロ燐酸リチウムからなる群から選ばれた少なくとも１種
の添加剤を含有することを特徴とする非水系電解液二次
電池。1. A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode made of lithium or a negative electrode material capable of inserting and extracting lithium, and a non-aqueous electrolyte solution made of an organic solvent and a solute. A non-aqueous electrolyte secondary battery, wherein the solvent contains at least one additive selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate.
対して0.01重量％から20.0重量％の範囲であることを特
徴とする請求項１記載の非水系電解液二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the amount of the additive added is in the range of 0.01% by weight to 20.0% by weight with respect to the organic solvent.
対して0.1重量％から5.0重量％の範囲であることを特徴
とする請求項２記載の非水系電解液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 2, wherein the amount of the additive added is in the range of 0.1 wt% to 5.0 wt% with respect to the organic solvent.
特徴とする請求項１記載の非水系電解液二次電池。4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode material is a carbon material.
コークスからなる群から選ばれた少なくとも１種である
ことを特徴とする請求項４記載の非水系電解液二次電
池。5. The carbon material is natural graphite, artificial graphite,
The non-aqueous electrolyte secondary battery according to claim 4, which is at least one selected from the group consisting of coke.
iBF4、LiClO4、LiCF 3SO3からなる群から選ばれた少なく
とも１種であることを特徴とする請求項１記載の非水系
電解液二次電池。6. The solute is LiPF 4.6, LiAsF6, LiSbF6, L
iBFFour, LiClOFour, LiCF 3SO3Less selected from the group consisting of
The non-aqueous system according to claim 1, characterized in that both are one kind.
Electrolyte secondary battery.
する請求項６記載の非水系電解液二次電池。7. The non-aqueous electrolyte secondary battery according to claim 6 , wherein the solute is LiPF 6 .
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