TW474041B - Sulfite additives for nonaqueous electrolyte rechargeable cells - Google Patents
Sulfite additives for nonaqueous electrolyte rechargeable cells Download PDFInfo
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- H—ELECTRICITY
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
Description
474041 五、發明說明(1) 相關申請案參考 本申請案申請範圍以美國臨時申請案序列號第 0 6 / 1 1 7,1 0 5號為基礎,其歸檔於1 9 9 9年1月2 5日。 發明背景 本發明係關於金屬電化學電池,尤其關於可再充電鹼金 屬電池。更詳細而言,本發明係關於以電解液活化之鋰離 子電化學電池,該電解液具有一種取得高充電/放電容 量、長循環壽命及減小第一循環不可逆容量之添加劑。根 據本發明之方法,活化電解液之較佳添加劑為亞硫酸酯化 合物。 鹼金屬可再充電電池一般包括碳質陽極和鋰化陰極。由 於完全充電鋰離子電池中陰極材料具高電勢(Li Co 02對 Li/Li+多至4· 3伏),碳質陽極材料具低電勢(石墨對Li/Li + 為0 . 0 1伏),電解液溶劑系統受到限制。由於碳酸酯溶劑 對一般所用鋰化陰極材料具有高氧化穩定性,對碳質陽極 材料具良好動力學穩定性,所以一般用於鋰離子電池電解 液。為取得最佳性能(高速率能力及長循環壽命),一般在 工業蓄電池中使用含環系碳酸酯(高介電常數溶劑)及低線 性碳酸酯(低黏度溶劑)之混合物之溶劑系統。據悉,以碳 酸為基電解液之電池於室溫提供大於1000次充電/放電循 環。 美國專利申請案序列號第0 9 / 1 3 3,7 9 9號(分配於本文, 以參考之方式併於本文)提出在活化電解液中以一種有機 碳酸酯溶劑之四元混合物用於鋰離子電池,該電池能夠在474041 5. Description of the invention (1) References to related applications The scope of this application is based on the US Provisional Application Serial No. 0 6/1 1 7, 10 5 and it was filed on January 2, 1999. 5th. BACKGROUND OF THE INVENTION The present invention relates to metal electrochemical cells, and more particularly to rechargeable alkaline metal batteries. In more detail, the present invention relates to a lithium ion electrochemical cell activated by an electrolyte having an additive that achieves a high charge / discharge capacity, a long cycle life, and a reduction in the irreversible capacity of the first cycle. According to the method of the present invention, a preferred additive for activating the electrolytic solution is a sulfite compound. Alkaline metal rechargeable batteries typically include a carbonaceous anode and a lithiated cathode. Due to the high potential of the cathode material in Li-ion batteries (Li Co 02 vs. Li / Li + up to 4.3 V), the carbonaceous anode material has low potential (graphite vs. Li / Li + 0.01 V), The electrolyte solvent system is limited. Carbonate solvents are generally used in lithium-ion battery electrolytes because they have high oxidative stability for commonly used lithiated cathode materials and good kinetic stability for carbonaceous anode materials. For best performance (high rate capability and long cycle life), solvent systems containing a mixture of cyclic carbonates (high dielectric constant solvents) and low linear carbonates (low viscosity solvents) are generally used in industrial batteries. It is reported that a battery based on a carbonic acid electrolyte provides more than 1,000 charge / discharge cycles at room temperature. US Patent Application Serial No. 0 9/1 3 3, 7 9 9 (assigned herein by reference and incorporated herein) proposes the use of a quaternary mixture of an organic carbonate solvent for lithium in an activated electrolyte Ion battery, which can
O:\62\62923.ptd 第4頁 474041 五、發明說明(2) 低於-2 0 °C放電,即使低至-4 0 °C亦展示良好循環性能。該 四元溶劑系統包括碳酸1,2 -亞乙酯(E C )、碳酸二曱酯 (DMC)、碳酸曱•乙酯(EMC)及碳酸二乙酯(DEC)。 鋰離子電池設計一般依目標電池應用在一個必要改良領 域至另一個領域權衡。用以上四元溶劑電解液代替一般使 用的;.it溶劑電解液(如1. OM LiPF6/EC : DMC:30 : 70(體積/ 體積),凝固點於-1 1 °C )使鋰離子電池具低溫循環能力係 以初始充電觀間增加第一循環不可逆容量為代價得到(對 於1.0M LiPF6/EC:DMC:EMC:DEC=45:22:24.8:8.2 為65 毫安 小時/克石墨,而對於1.0M LiPF6/EC:DMC = 3 0:7 0為35毫安 小時/克)。由於存在該第一循環不可逆容量,鋰離子電池 一般受陰極限制。因為充電及放電期間穿梭於陽極和陰極 間之所有鋰離子最初來自於鋰化陰極,第一循環不可逆容 量愈大,隨後循環中電池容量愈低,電池效率愈低。因 而,較佳減小或甚至消除鋰離子電池中第一循環不可逆容 量,同時保持該電池之低溫循環能力。 根據本發明,此等目標係藉由於四元溶劑電解液中提供 有機亞硫酸酯獲得。用以等電解液活化鋰離子電池與無亞 硫酸自旨添加劑之同樣四元溶劑電解液活化電池比較,具有 較低第一循環不可逆容量。因此,包括亞硫酸酯添加劑之 電池顯示比對照電池更高的隨後循環容量。本發明電池於 室溫及低溫(如低至約-4 0 °C )之循環性與無亞硫酸酯添加 劑之四元電解質活化一樣佳。 發明概述O: \ 62 \ 62923.ptd Page 4 474041 V. Description of the invention (2) Discharge below-20 ° C, even if it is as low as-40 ° C, it shows good cycle performance. The quaternary solvent system includes 1,2-ethylene carbonate (EC), dimethyl carbonate (DMC), osmium ethyl ester (EMC), and diethyl carbonate (DEC). Lithium-ion battery design is generally a trade-off based on the target battery application in one necessary improvement area to another. Use the above quaternary solvent electrolyte instead of the commonly used ones; .it solvent electrolyte (such as 1. OM LiPF6 / EC: DMC: 30: 70 (volume / volume), freezing point at -1 1 ° C) The low-temperature cycling capability is obtained at the cost of increasing the irreversible capacity of the first cycle between initial charging observations (for 1.0M LiPF6 / EC: DMC: EMC: DEC = 45: 22: 24.8: 8.2 is 65 mAh / g graphite, while for 1.0M LiPF6 / EC: DMC = 3 0: 7 0 is 35 mAh / g). Because of the irreversible capacity of the first cycle, lithium ion batteries are generally limited by the cathode. Because all the lithium ions that shuttle between the anode and the cathode during charging and discharging are originally from the lithiated cathode, the larger the irreversible capacity in the first cycle, the lower the battery capacity in the subsequent cycles, and the lower the battery efficiency. Therefore, it is preferable to reduce or even eliminate the first cycle irreversible capacity in the lithium ion battery while maintaining the low temperature cycling capability of the battery. According to the present invention, these objects are obtained by providing an organic sulfite in a quaternary solvent electrolyte. Compared with the same quaternary solvent electrolyte activated battery without the sulphurous acid additive, the lithium ion battery used to wait for the electrolyte has a lower first-cycle irreversible capacity. As a result, batteries including sulfite additives showed higher subsequent cycle capacity than control batteries. The cyclability of the battery of the present invention at room temperature and low temperature (such as as low as about-40 ° C) is as good as the activation of the quaternary electrolyte without sulfite additive. Summary of invention
O:\62\62923.ptd 第5頁 474041 五、發明說明(3) 通常我們熟悉,當對以碳陽極構造之鋰離子電池以放電 條件初始施加電勢使電池充電時,由於陽極表面生成鈍化 薄膜,會損失一些永久容量。該永久容量損失稱為第一循 環不可逆容量。然而,該薄膜生成過程相當依賴電池充電 電勢下電解液組分之反應性。該鈍化薄膜之電化學性能亦 決定於該表面薄膜之化學組分。 對鹼金屬系統而言,生成表面薄膜不可避免,尤其對鋰 金屬陽極和以鋰介入之碳陽極,因為鋰對有機電解液具相 當低電勢及高反應性。理想表面薄膜(已知為固態-電解質 中間相(SE I )應電絕緣,且能傳導離子。雖然大多數鹼金 屬(特別為鋰電化學系統)薄足第一需要,但第二需要難以 獲得。此等薄膜之電阻不可忽略不計,因為生成表面層使 在鋰離子電池充電及放電期間產生不可接受的極化作用, 在電池内建立阻抗。另一方面,如果SEI薄膜導電,由於 鋰化碳電極具有低電勢,陽極表面上之電解質分解反應不 會停止。O: \ 62 \ 62923.ptd Page 5 474041 5. Description of the invention (3) Generally, we are familiar with the fact that when a lithium ion battery constructed with a carbon anode is initially charged with a potential under discharge conditions to charge the battery, a passivation film is formed on the anode surface. , Will lose some permanent capacity. This permanent capacity loss is called the first cycle irreversible capacity. However, the film formation process relies heavily on the reactivity of the electrolyte components at the battery charge potential. The electrochemical performance of the passivation film also depends on the chemical composition of the surface film. For alkali metal systems, the formation of surface films is inevitable, especially for lithium metal anodes and carbon anodes with lithium in it, because lithium has a relatively low potential and high reactivity for organic electrolytes. An ideal surface film (known as a solid-electrolyte mesophase (SE I) should be electrically insulating and capable of conducting ions. Although most alkali metals (especially lithium electrochemical systems) are thin enough to meet the first need, the second need is difficult to obtain. The resistance of these films is not negligible because the surface layer is generated to cause unacceptable polarization during charging and discharging of the lithium-ion battery, creating impedance in the battery. On the other hand, if the SEI film is conductive, due to the lithiated carbon electrode With a low potential, the electrolyte decomposition reaction on the anode surface does not stop.
因此,電解液之組分對鹼金屬系統之放電效率具肴相當 影響,尤其對蓄電池之永久容量損失。例如,當用1. 0 Μ LiPF6/EC : DMO 3 0 : 7 0活化蓄電池時,第一循環不可逆容量 接近35毫安小時/克石墨。但用1 . 0MTherefore, the components of the electrolyte have a considerable influence on the discharge efficiency of the alkali metal system, especially the permanent capacity loss of the battery. For example, when 1.0 μM LiPF6 / EC: DMO 3 0: 70 is used to activate the battery, the irreversible capacity of the first cycle is close to 35 mA / g of graphite. But with 1.0M
LiPF6/EC: DM C:EMC:DEC = 45:22 :24.8:8.2 作電解液時,在 同樣循環條件下,發現第一循環不可逆容量近似6 5毫安小 時/克。另外,用碳酸1,2 -亞乙酯及碳酸二曱酯之二元溶 劑電解液活化鋰離子電池不能在小於約-1 1 °C循環。先前LiPF6 / EC: DM C: EMC: DEC = 45: 22: 24.8: 8.2 As electrolyte, under the same cycling conditions, the irreversible capacity of the first cycle was found to be approximately 65 mA / g. In addition, lithium ion batteries activated with a binary solvent electrolyte of 1,2-ethylene carbonate and dimethyl carbonate cannot be cycled at less than about -1 ° C. previously
O:\62\62923.ptd 第6頁 474041 五、發明說明(4) 所參考之專利申請案之四元溶劑電解液能夠使鋰離子電池 於更低溫度循環,顯示以可接受循環效率提供較寬溫度應 用。因此,非常需要在減小第一循環不可逆容量同時,保 持鋰離子電池於約-4 0 °C低溫操作之益處。 根據本發明之方法,該目的系由在上述四元溶劑電解液 中加入亞磷摩酯添加劑取得。而且,可將本發明推廣到其 它非水性有機電解液系統,如二元溶劑和三元溶劑系統及 含線性或環性碳酸酯之混合物以外的電解液系統。例如, 線性或環性醚或酯亦可作為電解液組分。雖然所觀察改良 之準確理由尚不清楚,但可以假設在起初鋰化作用期間, 亞硫酸酯添加劑與存在的電解液組分竟爭反應於碳陽極表 面上。因而所形成SE I薄膜比無亞硫酸酯添加劑形成之薄 膜更為電絕緣,因此,經鋰化之碳電極在其它電解液組分 反應下得到更佳保護。所以,得到較低第一循環不可逆容 量 ° 藉參考以下詳述,本發明之此等及其它目的對熟諳此藝 者將更加明顯。 較佳具體實施例詳述 根據本發明製造之電化學蓄電池包括選自元素周期表 ΙΑ、IIA、或IIIB族之陽極活性材料,包括驗金屬鋰、 鈉、鉀等。較佳陽極活性材料包括鋰。 在電化學蓄電池系統中,陽極電極包括能夠引入及脫出 鹼金屬(較佳為鋰)之材料。較佳碳質陽極包括任何形式能 夠可逆保留鋰種類之碳,如焦炭、石墨、乙炔墨、炭黑、O: \ 62 \ 62923.ptd Page 6 474041 V. Description of the invention (4) The quaternary solvent electrolyte of the patent application referred to enables the lithium-ion battery to cycle at a lower temperature, showing that it can provide a better cycle efficiency at an acceptable cycle efficiency. Wide temperature applications. Therefore, it is highly desirable to reduce the irreversible capacity of the first cycle while maintaining the benefits of lithium-ion batteries operating at a low temperature of about -40 ° C. According to the method of the present invention, this object is achieved by adding a phosphoromorphate additive to the above-mentioned quaternary solvent electrolyte. Furthermore, the present invention can be extended to other non-aqueous organic electrolyte systems, such as binary and ternary solvent systems and electrolyte systems other than mixtures containing linear or cyclic carbonates. For example, linear or cyclic ethers or esters can also be used as electrolyte components. Although the exact reason for the improvement observed is not clear, it can be assumed that during the initial lithiation, the sulfite additive competes with the electrolyte components present to react on the carbon anode surface. Therefore, the SE I film formed is more electrically insulating than the film formed without a sulfite additive, and therefore, the lithiated carbon electrode is better protected under the reaction of other electrolyte components. Therefore, to obtain a lower first cycle irreversible capacity ° With reference to the following detailed description, these and other objects of the present invention will be more apparent to those skilled in the art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An electrochemical battery manufactured according to the present invention includes an anode active material selected from Group IA, IIA, or IIIB of the Periodic Table of Elements, including lithium, sodium, potassium, and the like. Preferred anode active materials include lithium. In electrochemical battery systems, the anode electrode includes a material capable of introducing and removing an alkali metal, preferably lithium. Preferred carbonaceous anodes include any form of carbon that can reversibly retain lithium species, such as coke, graphite, acetylene ink, carbon black,
O:\62\62923.ptd 第7頁 474041 、發明說明(5) 玻璃化Π。石黑具相當高的保留-鋰容量,所以特 佳古^ 慮碳之形態,礙質材料纖維特別有益,因為纖維 ί ^ ί機械性能,使之製造成能夠經受重復充電/放電 ^ 之剛性電極。另外,碳纖維之高表面積允許快速 Ϊ $ ^電速率。化學蓄電池陽極所用較佳碳質材料描述 於ϋ洚(Takeuchi)等人的美國專利第5,443,928號,其 内谷分=及以參考之方式併於本文。 旦〇般蓄電池陽極係藉混合約90至97重量%石墨與約3至1〇 重量%黏附劑材料製造,較佳為氟樹脂粉末,如聚四氟乙 = 聚偏二氟乙烯⑽F)、聚伸乙基四氟乙烯 y 聚醯胺和聚亞醯胺及其混合物。該電極活化混合 上It : Ϊ電器上提供,如由鑄、®、滾軋或其它使活性混 ° 之方法於鎳、不透鋼或銅箔或絲網上提供。 =極元件進一步具有與陽極集電器材料相同之擴展片或 ^ ^如鎳,且由焊接與之形成整體。並由焊接接觸至負 包/>又裝置中導電金屬之電池殼。另外,碳質電極可形成一 些其它幾何體,如筒形、圓柱形或丸狀,&改變低表 池設計.。 畜電池之陰極較佳包括在空氣中穩定及易於處理之鋰化 材料。此類空氣一穩定鋰化陰極材料之實例包括金屬釩、 ,、鉻、銅、鉬、鈮、鐵、鎳、鈷和錳之氧化物、硫化 物、硒化物及碲化物。較佳氧化物包括UNi〇2、UMn2〇2、 i〇o〇2 L iC〇。92Sn0。8 02 及L iC〇卜xN ix〇2。 在製成用於加入電化學電池之電極前,鋰化活性材 474041O: \ 62 \ 62923.ptd page 7 474041, description of the invention (5) vitrified Π. Ishiguro has a relatively high retention-lithium capacity, so it is particularly beneficial to consider the form of carbon, which hinders the use of high-quality material fibers, because the mechanical properties of the fiber make it a rigid electrode that can withstand repeated charging / discharging ^ . In addition, the high surface area of carbon fibers allows fast electrical rates. A preferred carbonaceous material for use in a chemical battery anode is described in U.S. Patent No. 5,443,928 to Takeuchi et al., Which is divided by reference and incorporated herein by reference. Denier battery anodes are manufactured by mixing about 90 to 97% by weight of graphite and about 3 to 10% by weight of adhesive material, preferably a fluororesin powder, such as polytetrafluoroethylene = polyvinylidene fluoride (F), poly Ethylenetetrafluoroethylene y Polyamine and polyimide and mixtures thereof. The electrode activation mix is provided on It: Ϊ electrical appliances, such as by casting, ®, rolling or other methods of active mixing ° provided on nickel, impervious steel or copper foil or wire mesh. The pole element further has the same expansion sheet or anode material as the anode current collector, such as nickel, and is integrally formed by welding. And the battery case is contacted by welding with a conductive metal in the device. In addition, carbonaceous electrodes can be formed into a number of other geometries, such as cylindrical, cylindrical, or pellet-shaped, & change the design of the low cell. Cathode cathodes preferably include lithiated materials that are stable in the air and easy to handle. Examples of such air-stabilized lithiated cathode materials include the oxides, sulfides, selenides, and tellurides of the metals vanadium, aluminum, chromium, copper, molybdenum, niobium, iron, nickel, cobalt, and manganese. Preferred oxides include UNi02, UMn202, io02 L iC0. 92Sn 0.82 and L iC 0 x x ix 02. Lithium active material 474041 before making electrode for electrochemical cell
佳與導電性添加劑人。 炭黑和/或石,黑::電性添加劑包括乙炔黑、 金屬作主道。s與上述活性材料混合時,亦用粉末狀 外勺括rf電稀釋劑。如錄、銘、鈦及*錄鋼。該電極另 夕^括=樹脂黏附劑,較佳為粉末狀,如ptfe、pvdf參 、 聚酿胺和聚亞醯胺及其混合物。 ^使該蓄電池放電,陰極鋰離子係藉由施加外部產生 ϊϊίΐ質陽極使電池再充電。施加再充電電勢用以自陰 * β 出鹼金屬離子,並通過電解液進入碳質陽極,使 奴%極餘和。戶斤{旱Ι〗·ρ 厅付Ll;電極可具有〇· 1和1· ο間之X值。隨 後對電池提供電勢,以正常方式放電。Better with conductive additives. Carbon black and / or stone, black: Electrical additives include acetylene black and metal as the main channel. When s is mixed with the above active materials, powdered outer spoons also include rf electric diluents. Such as Lu, Ming, Titanium and * Lu steel. In addition, the electrode includes a resin adhesive, preferably in a powder form, such as ptfe, pvdf, polyamine, polyimide, and a mixture thereof. ^ The battery is discharged, and the cathode lithium ion is recharged by applying an externally generated anode. A recharging potential is applied to produce alkali metal ions from the anion * β and enter the carbonaceous anode through the electrolyte, so that the percentage is extremely small. Households {Dr. 1} · ρ Hall pay Ll; the electrode may have an X value between 0.1 and 1. The battery is then supplied with a potential and discharged in the normal manner.
山1種蓄電池結構在陽極加入電池前以活性鹼材料介入 碳質材料。在此情形下,該陰極體可為固體,#包括但不 限於二氧化錳、氧化釩銀、氧化釩銀銅、二硫化鈦、氧化 銅硫化銅、硫化鐵、二硫化鐵及氟化碳。但該方法受到 與處理電池外鋰化碳有關問題妨礙。A kind of battery structure is intercalated with carbonaceous materials with active alkali materials before the anode is added to the battery. In this case, the cathode body may be solid, including, but not limited to, manganese dioxide, silver oxide vanadium, silver copper oxide vanadium, titanium disulfide, copper oxide copper sulfide, iron sulfide, iron disulfide, and carbon fluoride. However, this method has been hampered by issues related to handling lithium lithiated carbon outside the battery.
本發明之蓄電池包括於陽極和陰活性電極間提供物理分 離之隔離層。該隔離層為防止極間電性短路之電絕緣材 料,該隔離層材料不與陽極和陰活性材料發生化學反應, 不與電解液反應性’且不溶於電解液。而且,該分離層材 料具有足夠孔隙度,以在電池電化學反應期間使電解液流 動通過。該隔離層一般為片狀,且置於陽極和陰極之間。 當陽極以蛇線形結構折疊,且具有多個插入陽極疊層中間 之陰極板並於電池殼接收時,或者電極組成物卷成^形A 圓柱形π膠輥”裝置時,即為此種事例。The storage battery of the present invention includes an isolation layer that provides physical separation between the anode and the cathode active electrode. The isolation layer is an electrically insulating material that prevents an electrical short between electrodes. The isolation layer material does not chemically react with the anode and the cathode active material, is not reactive with the electrolyte solution, and is insoluble in the electrolyte solution. Moreover, the separation layer material has sufficient porosity to allow the electrolyte to flow through during the electrochemical reaction of the battery. The isolation layer is generally sheet-shaped and is placed between the anode and the cathode. This is the case when the anode is folded in a serpentine structure and has multiple cathode plates inserted in the middle of the anode stack and received in the battery case, or when the electrode composition is rolled into a ^ -shaped A cylindrical π rubber roller "device. .
474041 五、發明說明(7) 說明性分離層材料包括織自聚伸乙基四氟乙烯和聚伸乙 基氣二氟乙稀之氟聚性纖維之織物,可單獨使用或用氟聚 性微孔薄膜層合。其它適用隔離層材料包括無織玻璃、聚 丙烯、聚乙烯、玻璃纖維材料、陶瓷、商業上在ΖΙΤΕχ [化 塑(Che mp last)公司]名義下獲得之聚四氟乙烯薄膜、商業 上在CELGARD[塞勒尼期塑料公司(Celanese pUstic474041 V. Description of the invention (7) Illustrative separation layer materials include woven fabrics of fluoropolymer fibers made of poly (ethylenetetrafluoroethylene) and poly (ethylene) difluoroethylene, which can be used alone or with fluoropolymers. Laminated porous film. Other suitable insulating layer materials include non-woven glass, polypropylene, polyethylene, fiberglass materials, ceramics, PTFE film commercially obtained under the name of ΙΤΕχ [Che mp last company], and commercially available in CELGARD [Celanese pUstic
Company, Inc.)]名義下獲得之聚丙烯薄膜以及商業上在 DEXIGLAS[C· H·德斯特(Dexter),Di v•,德斯 下獲得之薄膜。 我 因,陰極材料之高電勢(Lii xC〇〇2對u/u+為高達4· 3伏) 以及陽極材料之低電勢(石墨對Li/U+為〇〇1伏), 解液溶劑系:統活化鹼金屬電化學電池(特別為完全充電鋰 離子電池)¾到非常限制。根據本發明,冑用非水性電解 於非水性溶劑組成,更佳由鹼金屬鹽溶於有 糸)及至少一種環系碳酸醋,該碳酸一产 酉曰選自碳酸二甲酯(DMC)、 。t (DPC)、碳酸曱· Γ 乙Se(DEC)、碳酸二丙酯 ..曰(EMC)、碳酸甲•丙酯(MPC)和碳酸 丙醋(PC曰)、碳ϋ混合物t,環系碳酸醋選自碳酸1,2-亞 碳酸1,2-亞乙。及、破酸U2—亞丁醋(BC)和 那Θ日及其化合物。一船將右地#私 類電池化學所用夕堂銥勝★ 有機反酸S日用於此 不 高氡化藉^ 解質溶劑系、统,因為對陰極材料展 〜疋,對陽極材料展示良好動力學稃定& 解液包㈣:DMC:EMC:DE;t=混合Company, Inc.)] and films obtained under the name DEXIGLAS [C.H. Dexter, Div., Des. Due to the high potential of the cathode material (up to 4.3 V for u / u + for Lii x CO2) and the low potential of the anode material (0.01 V for graphite / Li / U +), the solution solvent system: Activated alkali metal electrochemical cells (especially fully charged lithium-ion batteries) are extremely limited. According to the present invention, rhenium is composed of non-aqueous electrolyte in a non-aqueous solvent, and is more preferably composed of an alkali metal salt dissolved in rhenium) and at least one ring-based carbonate vinegar, which is selected from dimethyl carbonate (DMC), . t (DPC), thorium carbonate · Γ ethyl Se (DEC), dipropyl carbonate: (EMC), methyl propyl carbonate (MPC) and propyl carbonate (PC), carbon tritium mixture t, ring system The carbonated vinegar is selected from the group consisting of ethylene carbonate and ethylene carbonate. And, acid breaking U2-butylene vinegar (BC) and that Θ and its compounds. Yichuan will use the right ground #private battery chemistry institute Xitang Iridium ★ organic anti-acid S will be used for this high-grade chemical solution ^ Solvent solvent system, because the cathode material exhibition ~ ~, good display of anode material Kinetic Determination & Solution Packing: DMC: EMC: DE; t = Mixed
474041 五、發明說明(8) 物。各種碳酸酯溶劑所用最佳體積百分數範圍包括約1 0 % 至約50%EC、約5%至約75%DMC、約5 %至約5 0 %EMC以及約3% 至約4 5 %DEC。含該四元碳酸酯混合物之電解液顯示低於 -5 0 °C凝固點,以此混合物活化之鋰離子電池於室溫具良 好循環性能,於低於-2 0 °C溫度具良好放電和放電/充電循 環性能。 用作自陽極至陰極及再返回傳輸鹼金屬離子媒介物之鋰 鹽包括LiPF6、LiBF4、Li AsF6、LiSbF6、LiC104、Li A1C14、 LiGaCl4、LiC(S02CF3)3、LiN03、LiN(S02CF3)2、LiSCN、 Li03SCF2CF3、LiC6F5S03、Li02CCF3、LiS03F、LiB(C6H5)4 和 LiCF3S03及其混合物。適用鹽濃度一般介於約0. 8至1. 5莫 拉(molar)之間。 _本發明在電解液中提供至少一種有機亞硫酸酯添加劑。 該亞硫酸酯添加劑具有通式VOS ( = 0) (OR2),其中R1和R2可 相同或不同,且二者可為氫原子或含1至12個碳原子之有 機基團,其中若R2关Η, R1至少具有結構(R3) ( R4) ( R5) C -, 至少R3為芳族取代基或不飽和有機基團或無機基團,且其 中若R4和R5之任何保留基團為飽和有機基團,該飽和有機 基團含1至1 1個碳原子。 用以下物質作為電解液添加劑時,將發現最大效果,其 包括亞硫酸二稀丙S旨、亞硫酸甲·〒S旨、亞硫酸乙•节 酯、亞硫酸丙·〒S旨、亞硫酸丁 •节酯、亞硫酸戊· Τ 酉旨、亞硫酸曱•稀丙S旨、亞硫酸乙•烯丙S旨、亞硫酸丙· 稀丙醋、亞硫酸丁 •稀丙S旨、亞硫酸戊•烯丙S旨、亞硫酸474041 V. Description of the invention (8). The optimal volume percentage ranges for various carbonate solvents include about 10% to about 50% EC, about 5% to about 75% DMC, about 5% to about 50% EMC, and about 3% to about 45% DEC. The electrolyte containing the quaternary carbonate mixture shows a freezing point below -50 ° C. The lithium ion battery activated by this mixture has good cycle performance at room temperature, and good discharge and discharge at temperatures below -20 ° C. / Charging cycle performance. Lithium salts used as mediators to transport alkali metal ions from anode to cathode and back again include LiPF6, LiBF4, Li AsF6, LiSbF6, LiC104, Li A1C14, LiGaCl4, LiC (S02CF3) 3, LiN03, LiN (S02CF3) 2, LiSCN , Li03SCF2CF3, LiC6F5S03, Li02CCF3, LiS03F, LiB (C6H5) 4 and LiCF3S03 and mixtures thereof. The applicable salt concentration is generally between about 0.8 to 1.5 moles. The present invention provides at least one organic sulfite additive in the electrolyte. The sulfite additive has the general formula VOS (= 0) (OR2), wherein R1 and R2 may be the same or different, and the two may be a hydrogen atom or an organic group containing 1 to 12 carbon atoms. Η, R1 has at least the structure (R3) (R4) (R5) C-, at least R3 is an aromatic substituent or an unsaturated organic group or an inorganic group, and if any of the retention groups of R4 and R5 is a saturated organic Group, the saturated organic group contains 1 to 11 carbon atoms. The following substances will be found to be most effective when used as electrolyte additives, which include propylene disulfite, methyl sulfite, ethyl sulfite, ethyl benzyl sulfite, propyl sulfite, hydrazine, and butyl sulfite. • Bentyl esters, pentyl sulfite, thiocyanate, sulfite, propylene disulfide, ethyl sulfite, allyl sulfide, propyl sulfite, acetic acid, butyl sulfite, butyl sulfide, pentyl sulfite • Allyl S purpose, sulfurous acid
O:\62\62923.ptd 第11頁 474041 五、發明說明(9) -- 單曱S曰、亞硫暖單乙酯、亞硫酸單丙酯、亞硫酸單 亞硫酸單戊自曰、亞硫酸單丙酯、亞硫酸單苄酯 二苄酯及其混合物。 亞硫酸 上述化合物僅用於示範,未用於限制。熟於此藝 谷易5忍識來自上述通式範圍之亞硫酸酯化合物,該化人2 將作為電解液添加劑減少電壓彡遲。 化合物 雖然不願爻一些特定機理約束,但可以相信,由於 酸醋添加劑包含至少一個含c(sp2或叩3)—c(sp3)鍵單元^硫 不飽和’且該鍵單元以C(sp3)碳直接連接-0S02〜官处 團’所以彳艮容易在氧和至少一個R1及^之間成鍵,該2炉 酸醋中間體能夠有效與其它電解質溶劑或溶質竟爭,與1 反應並生成亞硫酸鹽(如亞硫酸鋰),或在陽極表面 硫酸酯還原產物之鋰鹽。 風亞 事實上可以相信,由於陽極表面反應平衡,亞硫酸艘或 陽極表面上亞硫酸酯(鹽)還原產物之鋰鹽提供電荷離域。 該平衡使龜離子經由鋰離子交換機制很容易自一個分子遷 移至另一個分子。如此實現有益離子傳導。因此,可以相 # ’該有機亞硫酸酯化合物比其它亞硫酸烷酯和亞硫酸環 醋(如亞疏酸1,2-亞乙酯及亞硫酸1,2 -亞丙酯)更能有效與 電解液中其它溶劑竟爭,生成更為離子傳導及電性絕緣之 薄膜。所以,應相信,碳質電極表面保護層之化學組分及 可能形態將由伴隨優勢改變至電池循環環性能優勢。 本文所述電池裝置較佳為”纏繞元件電池”形式。即,所 製造陽極、陰極及隔離層在”膠輥”型結構或,I纏繞元件電O: \ 62 \ 62923.ptd Page 11 474041 V. Description of the invention (9)-Monosulfonium S, monothionyl sulfite, monopropyl sulfite, monopentyl sulfite, monopentyl sulfite Monopropyl sulfate, monobenzyl sulfite, dibenzyl ester and mixtures thereof. The above compounds are used for demonstration only and are not intended to be limiting. Known in this art, Gu Yi 5 can bear the sulfite compounds from the above general formula range, and the Hua Ren 2 will be used as an electrolyte additive to reduce the voltage delay. Although the compound is not willing to be bound by some specific mechanisms, it is believed that since the acid and vinegar additive contains at least one c (sp2 or 叩 3) -c (sp3) bond unit ^ sulfur unsaturated 'and the bond unit is C (sp3) The carbon is directly connected to -0S02 ~ Guanji ', so it is easy to form a bond between oxygen and at least one R1 and ^. The 2 furnace acid vinegar intermediate can effectively compete with other electrolyte solvents or solutes, react with 1 and generate Sulfite (such as lithium sulfite), or lithium salt of sulfate reduction products on the anode surface. Feng Ya In fact, it is believed that due to the equilibrium reaction on the anode surface, the lithium salt of the sulfite (sulfite) reduction product on the anode surface provides charge delocalization. This equilibrium makes it easy for turtle ions to migrate from one molecule to another via a lithium ion exchange mechanism. This achieves beneficial ion conduction. Therefore, it can be said that the organic sulfite compound is more effective than other alkyl sulfites and cyclic sulfite (such as 1,2-ethylene sulfite and 1,2-propylene sulfite). Other solvents in the electrolyte compete for a thin film that is more ionically conductive and electrically insulating. Therefore, it is believed that the chemical composition and possible morphology of the surface protective layer of the carbonaceous electrode will change from the accompanying advantages to the performance advantages of the battery cycle ring. The battery device described herein is preferably in the form of a "wound element battery". That is, the anodes, cathodes, and separators manufactured in
第12頁 474041 五、發明說明(10) ^ 一 2賤’’中纏繞’使陽極位於輥外,與負性殼結構中電池殼 生電性接觸。用適當上部和下部絕緣體將纏繞電池組插 輛適合大小尺寸之金屬殼,該金屬殼可包括不銹鋼、軟 4 、錄鎳軟鋼、鈦或鋁材料,但不僅限於此,只要金屬材 料與電池組分相容即可。 電池頭包括金屬圓盤體,該圓盤體第一孔接納玻璃—金 破封接/終端針形進料槽,第二孔用於填充電解液。所用 TA壤為具多至約50重量%矽之防腐蝕類型,如CABAL 12、 較佳3勺或FUSITE 425或FUSITE 435。正性終端針形進料槽 瓸匕括鈦,但鉬、鋁、鎳合金或不銹鋼亦可使用。電池 2括j電化學電池其它組件具有相容性之元#,且能抗 針,雷=引線係焊接至玻璃-金屬封接中之正性終端 、十 電池頭糸焊接至含雷搞綠夕Μι* 七 一種I—f % # μ t 3電極線之殼上。隨後,用包含至少 種上述亞硫酸g曰添加劑電解 密閉熔接一不銹鈿填電池,於填充孔上 以上裝配描述負性殼電池,且電,一 j封。 結構。熟諳此藝者應瞭帛,本發明之^不範電池之較佳 以正性殼結構製造。 不轨電化學系統亦可 亞硫酸酯添加劑所用濃度限制 約〇· 20莫耳/升。添加劑濃度若小於為2〇· 001莫耳/升至 益效果將不明顯。另一方面,如 、、40 ·0 〇丨莫耳/升,有 莫耳/升,由於生成較厚陽極表果宝添加劑濃度大於約0.20 低,電池較高内阻之有害作用將消專膜及電解液電導降 應瞭解、熟於此藝者可在不 :+加劑之有益效果。Page 12 474041 V. Description of the invention (10) ^ 1 2 "In the middle winding" so that the anode is located outside the roller and is in electrical contact with the battery case in the negative case structure. Insert the wound battery pack into a metal case of a suitable size with appropriate upper and lower insulators. The metal case may include stainless steel, soft steel, nickel soft steel, titanium, or aluminum, but it is not limited to this, as long as the metal material and battery components Just compatible. The battery head includes a metal disc body. The first hole of the disc body receives the glass-gold seal / terminal pin-shaped feed slot, and the second hole is used to fill the electrolyte. The TA soil used is a corrosion-resistant type with up to about 50% by weight silicon, such as CABAL 12, preferably 3 scoops or FUSITE 425 or FUSITE 435. Positive terminal needle feed troughs include titanium, but molybdenum, aluminum, nickel alloy or stainless steel can also be used. Batteries, including other components of electrochemical cells, are compatible, and are resistant to needles. Lightning leads are welded to positive terminals in glass-to-metal seals. Ten battery heads are welded to thunder. Μι * Seven kinds of I—f% # μ t 3 on the shell of the electrode wire. Subsequently, a stainless steel filled battery was electrolytically sealed and welded with at least one of the above-mentioned sulfurous acid additives, and a negative shell battery was assembled and filled on the filled hole. structure. Those skilled in the art should understand that the non-standard battery of the present invention is preferably manufactured with a positive shell structure. The off-track electrochemical system can also limit the concentration of sulfite additives used to about 0.20 mol / l. If the additive concentration is less than 0.001 mol / l, the effect will not be obvious. On the other hand, such as, 40 · 0 〇 丨 Moore / liter, there are Moore / liter, due to the formation of a thicker anode surface Guobao additive concentration is greater than about 0.20 low, the harmful effects of higher internal resistance of the battery will eliminate the film And the electrolyte conductivity drop should be understood, and those skilled in this art can not: + the beneficial effects of additives.
開本發明申請專利範圍界 474041 五、發明說明(π) 定之主旨和範圍内對本發明作出各種改進 第14頁Open the scope of patent application for this invention 474041 V. Make various improvements to this invention within the spirit and scope of the invention description (π) Page 14
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US09/490,355 US6350542B1 (en) | 1999-01-25 | 2000-01-24 | Sulfite additives for nonaqueous electrolyte rechargeable cells |
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KR100873270B1 (en) | 2006-10-25 | 2008-12-11 | 주식회사 엘지화학 | Non-aqueous electrolyte and electrochemical device comprising the same |
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