JP2005259641A - Electrolytic solution and electrode for lithium secondary battery, lithium secondary battery, and manufacturing method of those - Google Patents
Electrolytic solution and electrode for lithium secondary battery, lithium secondary battery, and manufacturing method of those Download PDFInfo
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Abstract
Description
本発明はサイクル安定性に優れ、液洩れの恐れがないリチウム二次電池用の電解液、電極、リチウム二次電池およびこれらの製造方法に関する。 The present invention relates to an electrolytic solution, an electrode, a lithium secondary battery, and a method for producing the same for a lithium secondary battery having excellent cycle stability and no risk of liquid leakage.
現在、市販されているリチウム二次電池は一般に、正極活物質としてコバルト酸リチウム、マンガン酸リチウムなどが、負極活物質として黒鉛などの炭素材料が、また、電解液としてリチウム塩を炭酸エチレンや炭酸プロピレンなどの有機溶媒に溶解したものが採用されており、このリチウム二次電池は他のニッケル水素二次電池、ニッケルカドミウム二次電池、鉛二次電池などに比べて優れたエネルギー密度を有している。 Currently, lithium secondary batteries that are commercially available generally include lithium cobaltate and lithium manganate as a positive electrode active material, carbon materials such as graphite as a negative electrode active material, and lithium salts as ethylene carbonate and carbonic acid as an electrolyte. What is dissolved in an organic solvent such as propylene is used, and this lithium secondary battery has superior energy density compared to other nickel hydrogen secondary batteries, nickel cadmium secondary batteries, lead secondary batteries, etc. ing.
高いエネルギー密度を有するリチウム二次電池は、ビデオカメラ、携帯電話、デジタルカメラ、ノートパソコンなどの携帯機器用の電源として広く採用されている。これらの携帯機器が普及した近年は、その情報処理量の増大に伴う機器の電力消費量の増大と稼動時間延長のニーズから、二次電池の更なる高容量化や長寿命化が強く望まれている。 A lithium secondary battery having a high energy density is widely used as a power source for portable devices such as a video camera, a mobile phone, a digital camera, and a laptop computer. In recent years when these portable devices have become widespread, there is a strong demand for higher secondary battery capacity and longer life due to the need for increased power consumption and extended operating time due to increased information processing. ing.
またリチウム二次電池は電気自動車用の電源、電力貯蔵装置用の電源への応用も検討されており、これらの比較的大容量の二次電池には長寿命化と同時に高い安全性も要求されている。 Lithium secondary batteries are also being considered for use in power sources for electric vehicles and power storage devices. These relatively large-capacity secondary batteries are required to have long life and high safety. ing.
このようなリチウム二次電池の更なる高エネルギー密度化、長寿命化、安全性向上に対する要請から個々の構成材料の改良や新規な高性能物質の探索について精力的に研究開発が続けられている。 Due to the demand for higher energy density, longer life, and improved safety of such lithium secondary batteries, research and development has continued energetically to improve individual constituent materials and search for new high-performance materials. .
本発明が改良しようとするリチウム二次電池の電解液としては一般にＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＣＦ3ＳＯ3Ｌｉなどのリチウム塩を炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチル、γ―ブチルラクトンなどの有機溶媒に溶解したものが用いられる。電解液は正極や負極の種類によって様々な電解質と電解液の組み合わせの中から適正な電解液が選ばれる。 As an electrolyte for a lithium secondary battery to be improved by the present invention, lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , CF 3 SO 3 Li are generally used as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ- Those dissolved in an organic solvent such as butyl lactone are used. As the electrolytic solution, an appropriate electrolytic solution is selected from a combination of various electrolytes and electrolytic solutions depending on the type of the positive electrode or the negative electrode.
例えば炭酸エチレンや炭酸プロピレンなどの有機電解液を黒鉛負極と電気化学的に反応させてその表面にＳＥＩ（Ｓｏｌｉｄ Ｅｌｅｃｔｒｏｌｙｔｅ Ｉｎｔｅｒｆａｃｅ：固体電解質界面）と呼ばれる皮膜を形成することにより、サイクル安定性が増すことが知られている。 For example, an organic electrolyte such as ethylene carbonate or propylene carbonate is electrochemically reacted with a graphite negative electrode to form a film called SEI (Solid Electrolyte Interface) on the surface, thereby increasing cycle stability. It has been known.
また、電解液に少量の添加剤を添加することによりリチウム二次電池の性能を改善する方法が知られている。 A method for improving the performance of a lithium secondary battery by adding a small amount of an additive to an electrolytic solution is also known.
これらの添加剤としては例えばメチルフラン、ベンゼン、塩化エチルトリメチルアンモニウム、ポリエチレングリコールジメチルエーテル、ＡｌＩ3、ＳｎＩ2、ＣＯ2などが挙げられる。これらの添加剤は負極表面上に良好なＳＥＩを形成し、電解液の分解などの副反応やデンドライトの生成を抑制する効果があると言われている。 Examples of these additives include methyl furan, benzene, ethyl trimethyl ammonium chloride, polyethylene glycol dimethyl ether, AlI 3 , SnI 2 , CO 2 and the like. These additives are said to form good SEI on the negative electrode surface and to suppress side reactions such as decomposition of the electrolytic solution and generation of dendrite.
また、液洩れの恐れがある電解液を固体化あるいはゲル状に半固体化する試みがなされており、ポリエチレンオキサイドやポリアクリロニトリルなどの高分子成分に電解液を含浸してゲル状にした電解質を用いた軽量で薄型のリチウム二次電池が開発されている。 In addition, attempts have been made to solidify or semi-solidize electrolytes that may leak, and to make electrolytes impregnated with electrolytes into polymer components such as polyethylene oxide and polyacrylonitrile. A lightweight and thin lithium secondary battery used has been developed.
本発明は、サイクル安定性に優れて長寿命であるとともに安全性の高いリチウム二次電池に使用して好適な電解液、電極、リチウム二次電池、およびそれらの製造方法を提供することを課題としている。 An object of the present invention is to provide an electrolytic solution, an electrode, a lithium secondary battery, and a method for producing them suitable for use in a lithium secondary battery having excellent cycle stability and a long life and high safety. It is said.
リチウム二次電池のサイクル安定性に関しては充放電で活物質にリチウムイオンが出入りする反応を円滑に進めることが重要であり、この反応を円滑に進めるには活物質表面に形成される界面反応層を電池の充放電反応に対して安定であり、電解液と活物質との間のリチウムイオンの通過に対して抵抗が低いようにする必要がある。 Regarding the cycle stability of a lithium secondary battery, it is important to smoothly advance a reaction in which lithium ions enter and exit the active material by charging and discharging, and an interfacial reaction layer formed on the active material surface in order to facilitate this reaction Must be stable to the charge / discharge reaction of the battery and have low resistance to the passage of lithium ions between the electrolyte and the active material.
本発明者らは活物質表面に形成される界面反応層について、電解液に活物質と反応して安定なＳＥＩを形成すると考えられる種々の反応物質を添加して、電気化学的に反応させて界面反応層を形成する実験を行い、充放電性能を評価して適正な反応物質について鋭意検討した結果、イソシアネート基を有する低分子化合物が優れた界面反応層を形成し、優れたサイクル安定性を有することを見い出した。 For the interfacial reaction layer formed on the active material surface, the present inventors added various reactants that are considered to react with the active material to form a stable SEI in the electrolytic solution, and reacted electrochemically. As a result of conducting experiments to form an interfacial reaction layer, evaluating charge / discharge performance, and diligently examining appropriate reactants, low molecular weight compounds having an isocyanate group formed an excellent interfacial reaction layer, resulting in excellent cycle stability. Found to have.
更に電解液中でイソシアネート基とポリオールを反応させて形成されるゲル電解質は従来の電解液と同等の充放電特性を示し、洩液の恐れのないリチウム二次電池を得ることができ、本発明に至った。 Furthermore, the gel electrolyte formed by reacting an isocyanate group and a polyol in the electrolytic solution exhibits charge / discharge characteristics equivalent to those of the conventional electrolytic solution, and a lithium secondary battery free from the risk of leakage can be obtained. It came to.
すなわち、本発明は、イソシアネート基を有する低分子化合物を溶解したリチウム二次電池用の非水電解液を提供する。 That is, the present invention provides a nonaqueous electrolytic solution for a lithium secondary battery in which a low molecular compound having an isocyanate group is dissolved.
また、本発明は、前記電解液と化学的に若しくは電気化学的に反応させることによって、リチウムイオンを可逆に挿入および脱離可能な電極を提供する。 In addition, the present invention provides an electrode capable of reversibly inserting and desorbing lithium ions by chemically or electrochemically reacting with the electrolytic solution.
この場合、前記電解液に、前記電極を浸漬して、化学的に反応させることができ、また、前記電解液に前記電極を浸漬して電圧をかけ、電気化学的に反応させることができる。 In this case, the electrode can be immersed and chemically reacted in the electrolytic solution, and the electrode can be immersed and electrochemically reacted in the electrolytic solution.
更に、本発明は、イソシアネート基を有する低分子化合物を溶解した電解液に、ポリオールとウレタン化触媒を配合し、加熱してゲル化させて得たゲル電解質を提供する。 Furthermore, this invention provides the gel electrolyte obtained by mix | blending a polyol and a urethanization catalyst with the electrolyte solution which melt | dissolved the low molecular compound which has an isocyanate group, and making it gelatinize by heating.
このゲル電解質を用いて液洩れの恐れがないリチウム二次電池を提供できる。 By using this gel electrolyte, it is possible to provide a lithium secondary battery that is free from the risk of liquid leakage.
以上説明した本発明によれば、長寿命化が可能で、サイクル安定性の優れた非水電解液、ゲル電解質、電極、リチウム二次電池およびそれらの製造方法が提供される。 According to the present invention described above, a nonaqueous electrolytic solution, a gel electrolyte, an electrode, a lithium secondary battery, and a method for producing them can be provided that can extend the life and have excellent cycle stability.
本発明で開示された方法により製造されるリチウム電池は優れたサイクル安定性を示し、ゲル電解質を用いたものは漏液の恐れがなく、産業的に価値が高い。 The lithium battery produced by the method disclosed in the present invention exhibits excellent cycle stability, and those using a gel electrolyte have no fear of leakage and are industrially valuable.
低分子量のイソシアネート化合物は、ヘキサメチレンジイソシアネート、ジフェニルメタンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ターシャルブチルイソシアネート、イソプロピルイソシアネート、ブチルイソシアネート、シクロヘキシルイソシアネート、オクタデシルイソシアネート、フェニルイソシアネート、プロピルイソシアネート、フロロフェニルイソシアネート、ヘキシルイソシアネート、トルエンジイソシアネート、キシレンジイソシアネート、トリレンジイソシアネートなどが挙げられる。イソシアネート化合物の分子量は５００以下が好ましい。 The low molecular weight isocyanate compounds are hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, tertiary butyl isocyanate, isopropyl isocyanate, butyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, propyl isocyanate, fluorophenyl isocyanate, hexyl isocyanate, toluene diisocyanate. , Xylene diisocyanate, tolylene diisocyanate and the like. The molecular weight of the isocyanate compound is preferably 500 or less.
電解液への低分子量のイソシアネート化合物の配合量は０．０１重量％から５重量％の範囲が好ましい。 The blending amount of the low molecular weight isocyanate compound in the electrolytic solution is preferably in the range of 0.01 wt% to 5 wt%.
イソシアネート化合物の配合量が０．０１重量％より少ないと活物質表面に十分な反応層が形成できず、サイクル安定性の面で顕著な添加効果が得られない。 When the blending amount of the isocyanate compound is less than 0.01% by weight, a sufficient reaction layer cannot be formed on the active material surface, and a remarkable addition effect cannot be obtained in terms of cycle stability.
イソシアネート化合物の配合量が５重量％より多いと、活物質表面に必要以上に反応層が形成され、サイクル安定性は優れるものの活物質の容量が十分に引き出せないなどの問題を生じる。 When the compounding amount of the isocyanate compound is more than 5% by weight, a reaction layer is formed more than necessary on the surface of the active material, and the cycle stability is excellent, but the capacity of the active material cannot be sufficiently extracted.
電解液に溶解した低分子量のイソシアネートと電極活物質とを反応させて活物質表面に低分子量イソシアネートの反応層を形成させる方法としては、化学的方法と電気化学的方法がある。 There are a chemical method and an electrochemical method as a method for forming a reaction layer of low molecular weight isocyanate on the surface of the active material by reacting the low molecular weight isocyanate dissolved in the electrolytic solution with the electrode active material.
低分子量のイソシアネートと活物質とを化学的に反応させる方法は、低分子量のイソシアネートを溶解した電解液中に活物質をコーティングした電極を浸漬して行われる。室温ではこの反応は数日を要するが、４０℃から６０℃に加熱することにより、数時間でこの反応を完結させることができる。 A method of chemically reacting a low molecular weight isocyanate and an active material is performed by immersing an electrode coated with the active material in an electrolytic solution in which a low molecular weight isocyanate is dissolved. Although this reaction takes several days at room temperature, the reaction can be completed in several hours by heating from 40 ° C to 60 ° C.
低分子量のイソシアネートと活物質とを電気化学的に反応させる方法は、低分子量のイソシアネートを溶解した電解液中に活物質をコーティングした電極を浸漬し、該電極に電位を印加して行われる。界面反応層の形成は正極と負極とを夫々単独で低分子量のイソシアネートと反応させることにより達成されるが、両極を同時に低分子量のイソシアネートの溶解した電解液に浸漬し、両極に３Ｖ以上の電位差をかけることによっても達成される。 A method of electrochemically reacting a low molecular weight isocyanate and an active material is performed by immersing an electrode coated with the active material in an electrolytic solution in which a low molecular weight isocyanate is dissolved, and applying a potential to the electrode. The formation of the interfacial reaction layer is achieved by reacting the positive electrode and the negative electrode independently with low molecular weight isocyanate, but both electrodes are immersed in an electrolyte solution in which low molecular weight isocyanate is dissolved at the same time, and a potential difference of 3 V or more is applied to both electrodes. It is also achieved by applying.
すなわち、より簡単には通常の電解液を用いたリチウム二次電池を組み立てる方法において、低分子量のイソシアネート化合物が溶解した電解液を用いて該電池を組み立て、正極と負極とに３Ｖ以上の電位差をかけて初期の充電反応により活物質と低分子量のイソシアネート化合物を反応させることができる。 More specifically, in a method of assembling a lithium secondary battery using a normal electrolyte solution, the battery is assembled using an electrolyte solution in which a low molecular weight isocyanate compound is dissolved, and a potential difference of 3 V or more is generated between the positive electrode and the negative electrode. The active material and the low molecular weight isocyanate compound can be reacted by the initial charging reaction.
また、本発明では活物質表面に低分子量のイソシアネートを反応させた層を形成した後に、あるいは反応層を形成すると同時に、ポリオールとウレタン化触媒とを配合してゲル電解質を形成する。 In the present invention, a gel electrolyte is formed by blending a polyol and a urethanization catalyst after forming a layer obtained by reacting a low molecular weight isocyanate on the active material surface or simultaneously with forming a reaction layer.
ポリオールとしては分子量１０００から５０００の２官能あるいは３官能のポリオールが望ましい。 As the polyol, a bifunctional or trifunctional polyol having a molecular weight of 1000 to 5000 is desirable.
ウレタン化触媒としては代表的にはスズ化合物が用いられる。 As the urethanization catalyst, a tin compound is typically used.
電解液中に低分子量のイソシアネートとポリオールと微量のスズ化合物とを溶解し、４０℃から８０℃の温度で数時間から数十時間加熱することによりゲル電解質を得ることができる。 A gel electrolyte can be obtained by dissolving a low molecular weight isocyanate, a polyol and a trace amount of a tin compound in an electrolytic solution and heating at a temperature of 40 ° C. to 80 ° C. for several hours to several tens of hours.
電解液中のゲル化剤の配合量としては５重量％から２０重量％が好ましい。 The blending amount of the gelling agent in the electrolytic solution is preferably 5 to 20% by weight.
電解液中のゲル化剤の配合量が５重量％よりも少ない場合は、ゲルが形成し難しくなる。 When the blending amount of the gelling agent in the electrolytic solution is less than 5% by weight, a gel is difficult to form.
電解液中のゲル化剤の配合量が２０重量％よりも多い場合は、ゲル電解質のイオン伝導度が低下し、活物質の容量が十分に引き出せなくなる。 When the blending amount of the gelling agent in the electrolytic solution is more than 20% by weight, the ionic conductivity of the gel electrolyte is lowered and the capacity of the active material cannot be sufficiently extracted.
低分子量のイソシアネートとポリオールとの配合割合はイソシアネート基のモル数とポリオールのＯＨ基のモル数が当量となるように配合することが好ましい。 The blending ratio of the low molecular weight isocyanate and the polyol is preferably blended so that the number of moles of isocyanate groups and the number of moles of OH groups of the polyol are equivalent.
ウレタン化触媒の配合量は０．０１重量％から０．１重量％の範囲が好ましい。
ウレタン化触媒の配合量が０．０１重量％よりも少ないと、ゲル化反応が進み難くなる問題があり、逆に、ウレタン化触媒の配合量が０．１重量％よりも多いと、触媒を不必要に多く加えることになり、多量の触媒が電池の充放電反応に悪影響を及ぼす恐れがある。
The blending amount of the urethanization catalyst is preferably in the range of 0.01% by weight to 0.1% by weight.
If the blending amount of the urethanization catalyst is less than 0.01% by weight, there is a problem that the gelation reaction is difficult to proceed. Conversely, if the blending amount of the urethanization catalyst is more than 0.1% by weight, the catalyst An unnecessarily large amount is added, and a large amount of catalyst may adversely affect the charge / discharge reaction of the battery.
電解液を用いたリチウム二次電池を組み立てる通常の方法で、低分子量のイソシアネート化合物とポリオールとウレタン化触媒とが溶解した電解液を用いて電池を組み立て、４０℃から８０℃の温度で数時間から数十時間加熱することにより、漏液の恐れのないリチウム電池を製造することができる。 A battery is assembled using an electrolytic solution in which a low molecular weight isocyanate compound, a polyol, and a urethanization catalyst are dissolved in a usual method for assembling a lithium secondary battery using an electrolytic solution, and is heated at a temperature of 40 ° C. to 80 ° C. for several hours. By heating for several tens of hours, it is possible to manufacture a lithium battery with no risk of leakage.
電解質としてのＬｉＰＦ6を１モル／Ｌ（以下、１Ｍと記載）の濃度でプロピレンカーボネート（ＰＣ）とエチレンカーボネート（ＥＣ）の１：１（体積比）混合溶媒に溶解したものを電解液として用い、これにヘキサメチレンジイソシアネートを１重量％となるように添加した。 A solution obtained by dissolving LiPF 6 as an electrolyte in a 1: 1 (volume ratio) mixed solvent of propylene carbonate (PC) and ethylene carbonate (EC) at a concentration of 1 mol / L (hereinafter referred to as 1M) is used as an electrolytic solution. To this, hexamethylene diisocyanate was added to 1% by weight.
この溶液に黒鉛負極を浸漬し、４０℃で６時間加熱して反応させた。 A graphite negative electrode was immersed in this solution and reacted by heating at 40 ° C. for 6 hours.
黒鉛負極を取り出し、マンガン酸リチウム正極とセパレータを挟んで電池を組み立て、１Ｍ−ＬｉＰＦ6／ＰＣ：ＥＣ電解液を注入した。 A graphite negative electrode was taken out, a battery was assembled with a lithium manganate positive electrode and a separator in between, and 1M-LiPF 6 / PC: EC electrolyte was injected.
ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にマンガン酸リチウム正極を浸漬して、４０℃で６時間加熱して反応させた。 1M-LiPF6 / PC containing 1% by weight of hexamethylene diisocyanate: A lithium manganate positive electrode was immersed in an EC electrolyte, and reacted by heating at 40 ° C. for 6 hours.
マンガン酸リチウム正極を取り出し、黒鉛負極とセパレータを挟んで電池を組み立て、１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液を注入した。 A lithium manganate positive electrode was taken out, a battery was assembled with a graphite negative electrode and a separator in between, and 1M-LiPF6 / PC: EC electrolyte was injected.
マンガン酸リチウム正極と黒鉛負極との間にセパレータを挟んで電池を組み立て、ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液を注入した。 A battery was assembled with a separator sandwiched between a lithium manganate positive electrode and a graphite negative electrode, and 1M-LiPF6 / PC: EC electrolyte containing 1% by weight of hexamethylene diisocyanate was injected.
この電池を４０℃で６時間加熱した。 The battery was heated at 40 ° C. for 6 hours.
マンガン酸リチウム正極と黒鉛負極との間にセパレータを挟んで電池を組み立て、ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液を注入した。 A battery was assembled with a separator sandwiched between a lithium manganate positive electrode and a graphite negative electrode, and 1M-LiPF6 / PC: EC electrolyte containing 1% by weight of hexamethylene diisocyanate was injected.
この電池を時間率０．１Ｃ（Ｃは定格容量を電流値で除して求まる時間の逆数）の一定電流で上限電位４Ｖまで充電し、上限電位に到達した後は４Ｖ一定電位で、電流値が時間率１Ｃの０．１％に低下するまで充電した。 This battery is charged to a maximum potential of 4V with a constant current at a time rate of 0.1C (C is the reciprocal of the time obtained by dividing the rated capacity by the current value). After reaching the upper limit potential, the current value is constant at 4V. The battery was charged until the time rate dropped to 0.1% of 1C.
１Ｍ−ＬｉＰＦ6／ＰＣ：ＥＣ電解液にヘキサメチレンジイソシアネートを１重量％となるように添加した。 1M-LiPF 6 / PC: Hexamethylene diisocyanate was added to the EC electrolyte so as to be 1% by weight.
この溶液に黒鉛負極とリチウム金属を浸漬し、短絡させて反応させた。 A graphite negative electrode and lithium metal were immersed in this solution and reacted by short-circuiting.
黒鉛負極を取り出し、マンガン酸リチウム正極とセパレータを挟んで電池を組み立て、電解質として１Ｍ−ＬｉＰＦ6／ＰＣ：ＥＣを注入した。 The graphite negative electrode was taken out, a battery was assembled with the lithium manganate positive electrode and the separator interposed therebetween, and 1M-LiPF 6 / PC: EC was injected as an electrolyte.
１Ｍ−ＬｉＰＦ6／ＰＣ：ＥＣ電解液にヘキサメチレンジイソシアネートを１重量％となるように添加した。 1M-LiPF 6 / PC: Hexamethylene diisocyanate was added to the EC electrolyte so as to be 1% by weight.
この溶液にマンガン酸リチウム正極とリチウム金属を浸漬し、時間率０．１Ｃの一定電流で上限電位４Ｖまで充電し、上限電位に到達した後は４Ｖ一定電位で、電流値が時間率１Ｃの０．１％に低下するまで充電した。 A lithium manganate positive electrode and lithium metal are immersed in this solution, charged to a maximum potential of 4 V at a constant current of 0.1 C time, and after reaching the maximum potential, the current value is 0 at a constant potential of 4 V and a current value of 0 C of 1 C. The battery was charged until it dropped to 1%.
マンガン酸リチウム正極を取り出し、黒鉛負極とセパレータを挟んで電池を組み立て、電解質として１Ｍ−ＬｉＰＦ6／ＰＣ：ＥＣを注入した。 A lithium manganate positive electrode was taken out, a battery was assembled with a graphite negative electrode and a separator interposed therebetween, and 1M-LiPF 6 / PC: EC was injected as an electrolyte.
ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液に黒鉛負極を浸漬して、４０℃で６時間加熱して反応させ、黒鉛負極を取り出した。 A graphite negative electrode was immersed in 1M-LiPF6 / PC: EC electrolyte containing 1% by weight of hexamethylene diisocyanate and heated at 40 ° C. for 6 hours to take out the graphite negative electrode.
ヘキサメチレンジイソシアネート７重量％、分子量２４００の２官能ポリオールを４３重量％、分子量２８００の３官能ポリオールを５０重量％、ウレタン化触媒を０．１重量％の割合で１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にゲル化剤が１０重量％となるように配合した。 1M-LiPF6 / PC: EC electrolyte solution in a ratio of 7% by weight of hexamethylene diisocyanate, 43% by weight of a bifunctional polyol having a molecular weight of 2400, 50% by weight of a trifunctional polyol having a molecular weight of 2800, and 0.1% by weight of a urethanization catalyst The gelling agent was blended so as to be 10% by weight.
黒鉛負極とマンガン酸リチウム正極の間にセパレータを挟んで電池を組み立て、ゲル化剤を１０重量％含む電解質を注入した。 A battery was assembled with a separator sandwiched between a graphite negative electrode and a lithium manganate positive electrode, and an electrolyte containing 10% by weight of a gelling agent was injected.
電池を６０℃で２４時間加熱して、電池内部の電解液をゲル化させた。 The battery was heated at 60 ° C. for 24 hours to gel the electrolyte inside the battery.
ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にマンガン酸リチウム正極を浸漬して、４０℃で６時間加熱して反応させ、正極を取り出した。 1M-LiPF6 / PC containing 1% by weight of hexamethylene diisocyanate: A lithium manganate positive electrode was immersed in an EC electrolytic solution, heated at 40 ° C. for 6 hours to react, and the positive electrode was taken out.
ヘキサメチレンジイソシアネート７重量％、分子量２４００の２官能ポリオールを４３重量％、分子量２８００の３官能ポリオールを５０重量％、ウレタン化触媒を０．１重量％の割合で１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にゲル化剤が１０重量％となるように配合した。 1M-LiPF6 / PC: EC electrolyte solution in a ratio of 7% by weight of hexamethylene diisocyanate, 43% by weight of a bifunctional polyol having a molecular weight of 2400, 50% by weight of a trifunctional polyol having a molecular weight of 2800, and 0.1% by weight of a urethanization catalyst The gelling agent was blended so as to be 10% by weight.
黒鉛負極とマンガン酸リチウム正極の間にセパレータを挟んで電池を組み立て、ゲル化剤を１０重量％含む電解質を注入した。 A battery was assembled with a separator sandwiched between a graphite negative electrode and a lithium manganate positive electrode, and an electrolyte containing 10% by weight of a gelling agent was injected.
電池を６０℃で２４時間加熱して、電池内部の電解液をゲル化させた。 The battery was heated at 60 ° C. for 24 hours to gel the electrolyte inside the battery.
ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液に黒鉛負極とリチウム金属を浸漬し、短絡して反応させ、黒鉛負極を取り出した。 A graphite negative electrode and lithium metal were immersed in a 1M-LiPF6 / PC: EC electrolyte containing 1% by weight of hexamethylene diisocyanate and short-circuited to obtain a graphite negative electrode.
ヘキサメチレンジイソシアネート７重量％、分子量２４００の２官能ポリオールを４３重量％、分子量２８００の３官能ポリオールを５０重量％、ウレタン化触媒を０．１重量％の割合で１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にゲル化剤が１０重量％となるように配合した。 1M-LiPF6 / PC: EC electrolyte solution in a ratio of 7% by weight of hexamethylene diisocyanate, 43% by weight of a bifunctional polyol having a molecular weight of 2400, 50% by weight of a trifunctional polyol having a molecular weight of 2800, and 0.1% by weight of a urethanization catalyst The gelling agent was blended so as to be 10% by weight.
黒鉛負極とマンガン酸リチウム正極の間にセパレータを挟んで電池を組み立て、ゲル化剤を１０重量％含む電解質を注入した。 A battery was assembled with a separator sandwiched between a graphite negative electrode and a lithium manganate positive electrode, and an electrolyte containing 10% by weight of a gelling agent was injected.
電池を６０℃で２４時間加熱して、電池内部の電解液をゲル化させた。 The battery was heated at 60 ° C. for 24 hours to gel the electrolyte inside the battery.
ヘキサメチレンジイソシアネートを１重量％含む１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にマンガン酸リチウム正極とリチウム金属を浸漬し、時間率０．１Ｃの一定電流で上限電位４Ｖまで充電し、上限電位に到達した後は４Ｖ一定電位で、電流値が時間率１Ｃの０．１％に低下するまで充電し、正極を取り出した。 1M-LiPF6 / PC containing 1% by weight of hexamethylene diisocyanate: A lithium manganate positive electrode and lithium metal were immersed in an EC electrolyte, charged to a maximum potential of 4 V at a constant current of 0.1 C, and reached the maximum potential. Thereafter, the battery was charged at a constant potential of 4 V until the current value decreased to 0.1% of the time rate of 1 C, and the positive electrode was taken out.
ヘキサメチレンジイソシアネート７重量％、分子量２４００の２官能ポリオールを４３重量％、分子量２８００の３官能ポリオールを５０重量％、ウレタン化触媒を０．１重量％の割合で１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液にゲル化剤が１０重量％となるように配合した。 1M-LiPF6 / PC: EC electrolyte solution in a ratio of 7% by weight of hexamethylene diisocyanate, 43% by weight of a bifunctional polyol having a molecular weight of 2400, 50% by weight of a trifunctional polyol having a molecular weight of 2800, and 0.1% by weight of a urethanization catalyst The gelling agent was blended so as to be 10% by weight.
黒鉛負極とマンガン酸リチウム正極の間にセパレータを挟んで電池を組み立て、ゲル化剤を１０重量％含む電解質を注入した。 A battery was assembled with a separator sandwiched between a graphite negative electrode and a lithium manganate positive electrode, and an electrolyte containing 10% by weight of a gelling agent was injected.
電池を６０℃で２４時間加熱して、電池内部の電解液をゲル化させた。
以上の実施例１から１０まで作製した電池を８０°Ｃの温度で時間率１／２Ｃの充放電条件でサイクル試験にかけた。その結果として、初期容量を１００％として１００サイクル後の容量を百分率で表１に示す。
〔比較例１〕
The battery was heated at 60 ° C. for 24 hours to gel the electrolyte inside the battery.
The batteries prepared in Examples 1 to 10 were subjected to a cycle test at a temperature of 80 ° C. under charge / discharge conditions at a time rate of ½ C. As a result, assuming that the initial capacity is 100%, the capacity after 100 cycles is shown in Table 1 as a percentage.
[Comparative Example 1]
黒鉛負極とマンガン酸リチウム正極との間にセパレータを挟んで電池を組み立て、１Ｍ−ＬｉＰＦ６／ＰＣ：ＥＣ電解液を注入した。 A battery was assembled with a separator sandwiched between a graphite negative electrode and a lithium manganate positive electrode, and 1M-LiPF6 / PC: EC electrolyte was injected.
比較例１で作製した電池を８０℃の温度で時間率１／２Ｃの充放電条件でサイクル試験にかけた。その結果として、初期容量を１００％として１００サイクル後の容量を百分率で表１に示す。 The battery prepared in Comparative Example 1 was subjected to a cycle test at a temperature of 80 ° C. under charge / discharge conditions at a time rate of ½ C. As a result, assuming that the initial capacity is 100%, the capacity after 100 cycles is shown in Table 1 as a percentage.
低分子量のイソシアネート化合物を含まない一般的な電解液を用いた比較例１のリチウム二次電池の容量が１００サイクル後に初期容量の８９％に低下するのに対して、本発明の低分子量のソシアネートを反応させた電極を用いた実施例１〜１０のリチウム二次電池はいずれも１００サイクル後の容量が高く維持され、サイクル安定性が優れることが明らかである。これは、電解液に配合した低分子量のイソシアネート化合物が電極活物質と反応して形成されるＳＥＩが充放電反応に対して非常に安定である為と考えられる。
The capacity of the lithium secondary battery of Comparative Example 1 using a general electrolytic solution containing no low molecular weight isocyanate compound is reduced to 89% of the initial capacity after 100 cycles, whereas the low molecular weight socyanate of the present invention is used. It is clear that all the lithium secondary batteries of Examples 1 to 10 using the electrode reacted with the above are kept high in capacity after 100 cycles and have excellent cycle stability. This is presumably because the SEI formed by the reaction of the low molecular weight isocyanate compound blended in the electrolytic solution with the electrode active material is very stable against the charge / discharge reaction.
Claims (10)
A method for producing a lithium secondary battery, comprising mixing a polyol and a urethanization catalyst in the electrolyte solution according to claim 1 and then heating the gel to gel the electrolyte solution.
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