TW201131856A - Thiazole compounds as additives in electrolyte solutions in electrochemical cells and batteries - Google Patents

Abstract

The present invention relates to an electrolyte solution comprising at least one solvent as component A, at least one electrolyte as component B and from 0.1 to 20% by weight, based on the total electrolyte solution, of at least one heteroaromatic compound of the general formula (I) as component C, the use of such a compound in electrolyte solutions, the use of such an electrolyte solution in an electrochemical cell or for metal plating, and also electrochemical cells comprising a corresponding electrolyte solution.

Description

201131856 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種電解質溶液，其包含作為組分A之至 少一種溶劑、作為組分B之至少一種電解質、及佔電解質 溶液總重量之0.1至20重量％之作為組分至少一種具通 式（I)之雜芳香族化合物，關於—種該化合物於電解質溶液 中之用途，關於一種該電解質溶液於電化學單元中或於鍍 金屬之用途，亦關於一種含有對應電解質溶液之電化學單 元。 【先前技術】 於先前技術中已知用於電化學單元或用於鍍金屬之電解 質溶液。201131856 VI. Description of the Invention: [Technical Field] The present invention relates to an electrolyte solution comprising at least one solvent as component A, at least one electrolyte as component B, and 0.1% by weight based on the total weight of the electrolyte solution To 20% by weight of at least one heteroaromatic compound of the formula (I) as a component, the use of the compound in an electrolyte solution, and the use of the electrolyte solution in an electrochemical unit or in metal plating Also relates to an electrochemical unit containing a corresponding electrolyte solution. [Prior Art] Electrolytic solutions for electrochemical cells or for metal plating are known in the prior art.

Jeong等人，Eiectrochem. c〇mm 1〇 (2〇〇8)，第 635至 638頁揭示-種避免於濃電解質溶液中形成枝晶狀鐘晶體 之方法。該文獻中所述之電解質溶液包含作為電解質之適 宜經鹽。更進一步，該研究檢測出對應晶體之形成與鐘鹽 LiN(S02C2F5)2濃度之相關性。Jeong et al., Eiectrochem. c〇mm 1〇 (2〇〇8), pages 635 to 638, disclose a method for avoiding the formation of dendritic crystals in concentrated electrolyte solutions. The electrolyte solution described in this document contains a suitable salt as an electrolyte. Further, the study examined the correlation between the formation of the corresponding crystal and the concentration of the bell salt LiN (S02C2F5)2.

Zhang等人，J· 〇f powersources 162 (2〇〇6)，第 13乃至 1394頁揭示可用⑥鋰離子電池之電解質溶液之多種添加 物。建議以例如雜環化合物、與不飽和化合物之碳酸酿、 具有不飽和取代基之芳香族化合物、以及含磷或矽之分子 之有機化合物作為添加物。提出二元叛酸之含棚錯合物為 另一種適宜化合物。 先前技術中之電解質溶液可改善—些方面，例如，避免 152723.doc 201131856 於充電及放電循環期間形成鋰枝晶。更進一步’應提供一 種具有寬電化學電位窗，且對高反應性經具安定性之電解 質溶液。 【發明内容】 因此，本發明之標的為提供一種電解質溶液，利用其可 避免於充電及放電循環中形成鐘枝晶。更進一步，該電解 質溶液在用於可充電電池中或用於鍵金㈣，應具有優越 性能。 該等標的可藉由-種電解質溶液達成，該電解質溶液包 含作為組分A之至少一種溶劑、作為組分B之至少一種電 解質、及佔電解質溶液總重量之〇1至2()重量％之作為組分 C之至少一種通式⑴化合物：Zhang et al., J. 〇f powersources 162 (2〇〇6), pages 13 to 1394 disclose various additives for electrolyte solutions that can be used with 6 lithium ion batteries. As the additive, for example, a heterocyclic compound, a carbonated product with an unsaturated compound, an aromatic compound having an unsaturated substituent, and an organic compound containing a molecule of phosphorus or ruthenium are suggested. It is proposed that the binary tickacid inclusion complex is another suitable compound. Electrolyte solutions of the prior art may improve aspects, for example, avoiding the formation of lithium dendrites during charge and discharge cycles of 152723.doc 201131856. Further, an electrolyte solution having a wide electrochemical potential window and a high reactivity stability should be provided. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an electrolyte solution with which formation of dendrites during charging and discharging cycles can be avoided. Further, the electrolyte solution should have superior performance in use in a rechargeable battery or in a key gold (four). The standard can be achieved by an electrolyte solution comprising at least one solvent as component A, at least one electrolyte as component B, and 〇1 to 2% by weight based on the total weight of the electrolyte solution. At least one compound of the formula (1) as component C:

其中X '又^乂^…及爪具有下列含意 X1、X2相互獨立地為N或CH， X 為 nr1、〇或 s， m 其中X1 R1 為0至4之整數， X及X巾之至少兩者為選自N、〇&s之雜原子， 係自由如下組成之群中選出：氫；可插人至少一 個雜原子的直鏈或分支鏈、飽和或不飽和 烷基；可***至少-個雜原子之經取代或未經: 代之Cs-C〗2·環烷基；經取代或未經取代之C5_C · 152723.doc -4- 201131856 方基；經取代或未經取代之雜芳基；且 基團R係獨立地自由如下組成之群中選出：可***至少 -個雜原子的直鏈或分支鏈、飽和或不飽和Cin 可插^至少—個雜原子之經取代或未經取代之Μ"·環燒 基，經取代或未經取代之c5_c2〇_芳基；經取代或未經取代 之C5-C2。-雜芳基；函素及具有拉電子性質之官能基。 更進步，仏的之達成方法為：藉由於電解 用通式（I)化合物，藉由於電化學單元中或於錄金屬時使用 所述電解質溶液，及藉由包含本發明電解質溶液之電化學 單元。 【實施方式】 本發明電解質溶液包含作為組分A之至少_種溶劑。存 在於本發明電解質溶液中之該至少—種溶劑為彼等熟習此 項技術者熟知，且較佳為非水性溶劑。於—項特別佳之實 施例中，組分A為有機溶劑。 於-項特別佳之實施例中，該至少—種溶劑係自由如下 組成之群中選出：碳酸醋 '内醋、雜環化合物、醋類、醚 類、芳香族化合物及其混合物。 根據本發明之特佳碳酸酯為（例如）自由如下組成之群中 达出.碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯（DMC)、碳 酸二乙酯（DEC)、碳酸甲酯乙酯（EMC)及其混合物。 厌 其他適宜溶劑為内酯，例如γ· 丁内酯、γ_戊内酯及其混 合物。 可根據本發明使用之較佳酯類係選自（例如）具有例如1 152723.doc 201131856 至12個碳原子之一元羧酸之脂肪族酯類，特定言之乙酸乙 醋、丙酸乙酯、丁酸甲酯、丁酸乙酯、甲酸曱酯及其混合 物。 適用於本發明目的之醚類可為直鏈或環狀。直鏈醚例如 係自由以下組成之群中選出：亞曱基二甲基醚（DMM)、伸 乙基二甲基醚（DME)、伸乙基二乙基醚（DEE)及其混合 物。根據本發明之特別適宜之環狀醚例如係自由以下組成 之群中選出：四氫呋喃（THF)、2-曱基四氫呋喃、丨，3-二氧 戊環、4-曱基二氧戊環、2_曱基_U3_:氧戊環及其混 合物。 根據本發明之較佳芳香族化合物例如係自由以下組成之 群中選出：苯、甲苯、氯苯、二甲苯及其混合物。 於一項特別佳之實施例中，於本發明電解質溶液中使用 至少兩種上述化合物之混合物作為溶劑。 丨最佳使用至少-種環狀碳酸酯(例如碳酸乙烯酯)、及至 少一種直鍵碳酸自旨（例如碳酸二乙醋）之混合物作為組分 A。根據本發明較佳使㈣至少兩種上述㈣之混合物中 的混合比可在寬·㈣化1合比可為（例如）1: 10 0 ·· 1，絲 y土 1 .。λ 主 佳20至20 : 1，特別佳為1 : 5至5 : 1。 於本發明電解質溶液φ Β。 買，合液中存在至少-種電解質作為組分 根據本發明，熟 作為本發明電解質 特佳電解質為在 習此項技術者所知之所有電解質均適於 溶液尹之组分Β。 上述溶劑中具有足夠高之溶解度，而可 152723.doc 201131856 製得適宜電解f溶液者。以在本發 溶劑中穿今^ 解質〉谷液之非水性 步：全洛解且完全解離之電解質為特別適宜。更進一 雷離子應在電解質溶液中具有高遷移率。爲了在 解質中解質溶液’特定言之，所用電 中之對應陰離子應對陰極之氧化分解具安定性。更進 步’陰離子應對所用溶劑呈惰性。此外，所用電解質之 兩部份（亦即陽離子部份及險離 性。 丨伪及e離子部份）應對其他組分呈惰 於本發明電解質溶液中，較佳使用其中陽離子為鐘之電 質作為組分Ββ鐘之存在形式較佳為呈氧化㈣之陽離 子。 選擇作為組分Β之根據本發明使用之電 子，以滿足上述要求，特定言之解離性、惰性=離 電解質之特佳陰離子例如係、自由如下組成之群中選出：函 素(例如氟、氣、溴、碘)、氧化物、氫氧化物、陰離子性 硼、磷及/或砷錯合物、三氟甲磺酸根、亞胺、過氯酸根 及其組合。 於本發明之電解質溶液中，特佳使用至少一種自由如下 組成之群中選出之電解質來作為組分Β:齒化鋰（特定言之 氯化鋰LiCl或氟化鋰LiF)、氧化鋰ye '硼、磷、砷錯合 物之鋰鹽（特定言之四氟硼酸鋰、六氟磷酸鋰LiPF6、六氟 石申酸鐘、過氯酸鋰、三氟甲磺酸鋰、亞胺鋰、雙（三氟甲 確醯基）亞胺鋰及其衍生物及混合物。 特佳使用六氟踏酸裡LiPF0來作為本發明電解質溶液中 152723.doc 201131856 之電解質（組分B)。 該至；-種電解質通常係以確保電解質溶液具有足夠高 之導電性之量存在於本發明電解質溶液中1如，該至少 -種電解質在本發明電解質溶液中之濃度為〇」至1〇 卜較佳為〇.2至2m_，特佳為〇5^ &副。 其他所述電解質之相應重量百分比可由熟習此項技術者 計算得出。 本發明電解質溶液包含在每_情況下佔電解質溶液總重 =之0.1至20重量％，較佳m〇重量％，特佳i 〇至3 〇重 直％之至少一種通式（I)化合物作為組分c，Wherein X '又^乂^... and the claws have the following meanings X1, X2 are independently N or CH, X is nr1, 〇 or s, m wherein X1 R1 is an integer from 0 to 4, and at least two of X and X towels Is a hetero atom selected from N, 〇 & s, selected from the group consisting of: hydrogen; a linear or branched chain of at least one hetero atom, a saturated or unsaturated alkyl group; Substituted or unsubstituted: Cs-C 2·cycloalkyl; substituted or unsubstituted C5_C · 152723.doc -4- 201131856 aryl; substituted or unsubstituted heteroaryl And the group R is independently selected from the group consisting of: a straight or branched chain in which at least one hetero atom can be inserted, a saturated or unsaturated Cin can be inserted, or at least one hetero atom is substituted or not Substituted Μ"·cycloalkyl, substituted or unsubstituted c5_c2〇_aryl; substituted or unsubstituted C5-C2. - a heteroaryl group; a functional group and a functional group having a tensile electron property. Further progress is achieved by the use of a compound of the formula (I) by electrolysis, by the use of the electrolyte solution in an electrochemical unit or in the recording of a metal, and by an electrochemical unit comprising the electrolyte solution of the invention . [Embodiment] The electrolyte solution of the present invention contains at least one kind of solvent as component A. The at least one solvent present in the electrolyte solution of the present invention is well known to those skilled in the art and is preferably a non-aqueous solvent. In a particularly preferred embodiment, component A is an organic solvent. In a particularly preferred embodiment of the invention, the at least one solvent is selected from the group consisting of: carbonated vinegar, internal vinegar, heterocyclic compound, vinegar, ether, aromatic compound, and mixtures thereof. The particularly preferred carbonate according to the present invention is, for example, free from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl methyl carbonate (EMC) and mixtures thereof. Other suitable solvents are lactones such as γ·butyrolactone, γ-valerolactone and mixtures thereof. Preferred esters which can be used according to the invention are selected, for example, from aliphatic esters having, for example, 1 152723.doc 201131856 to one of the 12 carbon atoms of a carboxylic acid, in particular ethyl acetate, ethyl propionate, Methyl butyrate, ethyl butyrate, decyl carboxylate and mixtures thereof. The ethers suitable for the purpose of the present invention may be linear or cyclic. The linear ethers are, for example, selected from the group consisting of: fluorenyl dimethyl ether (DMM), ethyl dimethyl ether (DME), ethyl diethyl ether (DEE), and mixtures thereof. Particularly suitable cyclic ethers according to the invention are, for example, selected from the group consisting of tetrahydrofuran (THF), 2-mercaptotetrahydrofuran, indole, 3-dioxolane, 4-mercaptodioxolane, 2 _曱基_U3_: Oxypentane and mixtures thereof. Preferred aromatic compounds according to the present invention are, for example, selected from the group consisting of benzene, toluene, chlorobenzene, xylene and mixtures thereof. In a particularly preferred embodiment, a mixture of at least two of the above compounds is used as a solvent in the electrolyte solution of the present invention. Preferably, a mixture of at least a cyclic carbonate (e.g., ethylene carbonate) and at least one direct bond (e.g., ethylene carbonate) is used as component A. Preferably, according to the present invention, the mixing ratio of the mixture of at least two of the above (4) may be, for example, 1:10 0 ··1, silk y soil 1 in a width ratio of (4). λ main good 20 to 20: 1, especially preferably 1: 5 to 5: 1. In the electrolyte solution of the present invention φ Β. At least one electrolyte is present as a component in the liquid mixture. According to the present invention, it is known that the electrolyte of the present invention is particularly suitable for all electrolytes known to those skilled in the art. The above solvent has a sufficiently high solubility, and can be prepared by 152723.doc 201131856. It is a non-aqueous step in the solvent of the present invention. It is particularly suitable for the electrolyte which is fully dissolved and completely dissociated. Further, the lightning ions should have a high mobility in the electrolyte solution. In order to decompose the solution in the solution, the corresponding anion in the electricity used should be stable to the oxidative decomposition of the cathode. Further, the anion solution is inert to the solvent used. In addition, the two parts of the electrolyte used (i.e., the cationic portion and the ionic portion and the ruthenium and the e-ionic portion) should be inert to the other components in the electrolyte solution of the present invention, and it is preferred to use the cation as the electric quantity of the clock. As a component, the Ββ clock is preferably present in the form of an oxidized (tetra) cation. The electrons used in accordance with the present invention are selected as components 以满足 to meet the above requirements, specifically dissociation, inertness = a particularly good anion from the electrolyte, for example, a group selected from the group consisting of: a substance (e.g., fluorine, gas) , bromine, iodine), oxides, hydroxides, anionic boron, phosphorus and/or arsenic complexes, triflate, imine, perchlorate and combinations thereof. In the electrolyte solution of the present invention, it is particularly preferred to use at least one electrolyte selected from the group consisting of: lithium hydride (specifically, lithium chloride LiCl or lithium fluoride LiF), lithium oxide ye ' Lithium salt of boron, phosphorus and arsenic complexes (specifically, lithium tetrafluoroborate, lithium hexafluorophosphate LiPF6, hexafluoride acid acid, lithium perchlorate, lithium trifluoromethanesulfonate, lithium imide, bis(trifluoro) Lithium imide and its derivatives and mixtures. It is particularly preferred to use LiPF0 in hexafluorobenzoic acid as the electrolyte (component B) of 152723.doc 201131856 in the electrolyte solution of the present invention. The electrolyte solution is present in the electrolyte solution of the present invention in an amount to ensure that the electrolyte solution has a sufficiently high conductivity. For example, the concentration of the at least one electrolyte in the electrolyte solution of the present invention is 〇" to 1 〇b, preferably 〇.2 to 2m_, particularly preferably 〇5^ & 副. The corresponding weight percentage of other electrolytes can be calculated by those skilled in the art. The electrolyte solution of the present invention contains 0.1 to 20% of the total weight of the electrolyte solution in each case. % by weight, preferably m〇 %, particularly preferably i 〇 to 3 〇 by weight of at least one compound of the formula (I) as component c,

(I) 其中X丨、X2、X3、R2Am具有下列含意: x、X2相互獨立地為N或CH， χ3 為NR〗、〇或s， m 為〇至4之整數， 其令X1、X2及X3中之至少兩者為選自N、〇及8之雜原子， R, 係自由如下組成之群中選出：氫；可***至少一 個雜原子的直鏈或分支鏈、飽和或不飽和 烷基；可***至少一個雜原子之經取代或未經取 代之CyC,2·環烷基；經取代或未經取代之C _ 芳基，·經取代或未經取代之雜芳基，·且 基團R2係獨立地自由如下組成之群中選出：可***至少一 152723.doc 201131856 個雜原子的直鏈或分支鏈、飽和或不飽和ct-c12-烷基，可***至少一個雜原子之經取代或未經取 代之C3-cu-環烷基；經取代或未經取代之c5_Cm_ 方基，經取代或未經取代之雜芳基；鹵素 及具有拉電子性質之官能基。 於一項較佳實施例中，X1為N。 於另一項較佳實施例中，X2為CH。 於另一項較佳實施例中，X3為s或〇,特別佳為s。 於一項特別佳之實施例中，通式(I)化合物中之Χι為N， X2為CH且X3為s。 曰於通式(I)中’讀、指位於芳香族環上之取代基r2之數 量。m較佳為〇、1、？ 1 2 3、或4 ,非常佳為〇、1或2，特定 言之0。 於一項較佳實施例中，基團r2係獨立地自由如下組成之 群中選出：可***至少一個雜原子之直鍵或分支鍵、經取 代或未經取代之C‘·炫基’較佳為CVCV燒基，特佳為 C1_C3-院基’例如甲基、乙基、丙基、經取代或未經取代 -芳基（例如苯基或萘基）、及具有拉電子性質之官 能5 ’例如自由齒素所組成之群中選出之基團，例如氟。 右存在，R1較佳係自由如下組成之群中選出·· 烷 基’特別佳為q-cv炫基》 可存在於R及/或R2上之取代基根據本發明係獨立地自 由如下組成之群令選出：可***至少一個雜原子的直鏈或 分支鏈、飽和或不飽和Cl.Cl2_烧基；可***至少—個雜原 J52723.doc 201131856 :之經取代：未經取代之C3_Ci2_環烧基；經取代或未經取 :之:5 C2。方基，經取代或未經取代之。”。2。_雜芳基；鹵 素及官能基；例如CN;及其混合物。 於項非常佳之實施例中’ X1、X2、X3及m具有下列含 意： X1 為N， X2 為 CH， X 為s， m 為〇， 為組分C通式（I) 亦即’特佳使用通式（Ia)之苯并噻唑作 化合物(I) wherein X丨, X2, X3, R2Am have the following meanings: x, X2 are each independently N or CH, χ3 is NR, 〇 or s, m is an integer from 〇 to 4, which makes X1, X2 and At least two of X3 are heteroatoms selected from the group consisting of N, oxime and 8, and R is selected from the group consisting of: hydrogen; a linear or branched chain, a saturated or unsaturated alkyl group which can be inserted into at least one hetero atom. a substituted or unsubstituted CyC, 2·cycloalkyl group having at least one hetero atom; a substituted or unsubstituted C aryl group, a substituted or unsubstituted heteroaryl group, The group R2 is independently selected from the group consisting of: a linear or branched chain of at least one 152723.doc 201131856 heteroatoms, a saturated or unsaturated ct-c12-alkyl group, which can be inserted into at least one hetero atom. Substituted or unsubstituted C3-cu-cycloalkyl; substituted or unsubstituted c5_Cm_, substituted or unsubstituted heteroaryl; halogen and functional group having electron withdrawing properties. In a preferred embodiment, X1 is N. In another preferred embodiment, X2 is CH. In another preferred embodiment, X3 is s or 〇, particularly preferably s. In a particularly preferred embodiment, in the compound of formula (I), Χι is N, X2 is CH and X3 is s. The term "reading" in the formula (I) refers to the number of substituents r2 located on the aromatic ring. m is preferably 〇, 1,? 1 2 3, or 4, very good for 〇, 1 or 2, specifically 0. In a preferred embodiment, the group r2 is independently selected from the group consisting of: a direct or branched bond capable of inserting at least one hetero atom, a substituted or unsubstituted C'. Preferably, it is a CVCV alkyl group, particularly preferably a C1_C3-hospital group such as a methyl group, an ethyl group, a propyl group, a substituted or unsubstituted-aryl group (for example, a phenyl group or a naphthyl group), and a functional group having a pull-electron property. 'For example, a group selected from the group consisting of free dentates, such as fluorine. R1 is preferably present, and R1 is preferably selected from the group consisting of: alkyl group 'particularly preferably q-cv}. Substituents which may be present on R and/or R2 are independently free according to the present invention as follows. Group order: a linear or branched chain of at least one hetero atom, a saturated or unsaturated Cl.Cl2_alkyl group; at least one miscellaneous J52723.doc 201131856: substituted: unsubstituted C3_Ci2_ Cyclic base; substituted or not taken: 5 C2. Square base, substituted or unsubstituted. ".Heteroaryl; halogen and functional group; for example CN; and mixtures thereof. In the very preferred embodiment, 'X1, X2, X3 and m have the following meanings: X1 is N, X2 is CH, X is s, m is 〇, is component C, general formula (I), that is, 'excellent use of benzothiazole of formula (Ia) as a compound

因此本發明之一項極佳實施例提供一種根據本發明之 電解質溶液’其中苯并噻唑係如通式⑴化合物。 於一項特佳實施例中，本發明電解質溶液僅係由組分 A、B及C組成，組分a、8及(：量總計為1〇〇重量％。 於—項非常佳之實施例中，本發明提供一種電解質溶 其L3如下物質：作為組分A之至少一種環狀碳酸酯 (例如碳酸乙烯酯）、及至少一種直鏈碳酸酯（例如碳酸二乙 自曰）的混合物、作為組分B之六氟磷酸鋰LiPF6、及作為組 刀C之苯并噻唑，於各種情形中，其含量均如上所述。 本發明亦提供一種通式（I)化合物於電解質溶液中之用 途。特定言之’本發明提供用於電化學單元中之通式⑴化 152723.doc 201131856 合物之上述用途。 通式（I)化合物之較佳實施例以上應用中已提及，最佳使 用苯并η塞。坐作爲通式（I)化合物。 熟習此項技術者已熟知電化學單元，特定言之其結構及 所包含之組分。通式（I)化合物最佳用於電池中，特定言之 可充電電池。電池之一般結構闡述在例如「Lithium i〇n batteries: Science and Technologies, Gholam-Abbas Nazri Gianfranco Pistoia，2009」中。該等電化學單元通常包含 電解質、至少一個陽極（例如經陽極）、陰極（例如銅陰 極）、鋰、及適宜絕緣元件及連接物。 更進一步’本發明提供一種根據本發明之用途，其中通 式（I)化合物用於鑛金屬。 熟習此項技術者已熟知鍍金屬之方法，且其闡述在例如 「Praktische Galvanotechnikj , P. W. Jelinek，Eugen G.Accordingly, an excellent embodiment of the present invention provides an electrolyte solution according to the present invention, wherein the benzothiazole is a compound of the formula (1). In a particularly preferred embodiment, the electrolyte solution of the present invention consists solely of components A, B, and C, and components a, 8 and (: total amount is 1% by weight. In a very preferred embodiment) The present invention provides an electrolyte in which L3 is as follows: a mixture of at least one cyclic carbonate (for example, ethylene carbonate) as component A, and at least one linear carbonate (for example, diethylhexyl carbonate) as a group Lithium hexafluorophosphate LiPF6 and B benzothiazole as group knife C are in various cases as described above. The present invention also provides the use of a compound of the formula (I) in an electrolyte solution. The present invention provides the above-described use of the compound of the formula (1) 152723.doc 201131856 for use in an electrochemical unit. Preferred Embodiments of the Compound of the Formula (I) As mentioned above, the use of a benzopyrene plug is preferred. Sitting as a compound of the formula (I). The electrochemical unit, in particular its structure and the components contained therein, are well known to those skilled in the art. The compounds of the formula (I) are preferably used in batteries, in particular rechargeable. Battery The structure is described, for example, in "Lithium i〇n batteries: Science and Technologies, Gholam-Abbas Nazri Gianfranco Pistoia, 2009." The electrochemical cells typically comprise an electrolyte, at least one anode (eg, via an anode), and a cathode (eg, a copper cathode). Further, the present invention provides a use according to the invention, wherein the compound of the formula (I) is used in a mineral metal. The method of metallizing is well known to those skilled in the art and Explained in, for example, "Praktische Galvanotechnikj, PW Jelinek, Eugen G.

Lenze Verlag，2005中。使用通式⑴化合物可使例如鋰應用 於適且基材上’例如銅基材。 更進一步，本發明提供一種本發明電解質溶液於電化學 單元或於鍍金屬中之用途。本發明之電解質溶液之較佳實 施例及電化學單元或鍍金屬之細節已闡述於上文中。 圖1顯示於EC/DEC電解質中使用3重量％苯并噻唑時之循 裱伏安圖（實例1)。單位為mA之電流示於y軸上，且單位為 mV之電勢示於X軸上。 圖2顯示u/NCA單元之循環性能圖（實例3)。單位為 mAh/g之電容示於y軸上，且循環次數示於χ軸上。 152723.doc 201131856 於該圖示中：Lenze Verlag, 2005. The use of the compound of the formula (1) allows, for example, lithium to be applied to a suitable substrate, such as a copper substrate. Still further, the invention provides the use of an electrolyte solution of the invention in an electrochemical unit or in metal plating. Preferred embodiments of the electrolyte solution of the present invention and details of the electrochemical unit or metal plating are set forth above. Figure 1 shows a cyclic voltammogram (Example 1) when 3% by weight of benzothiazole was used in the EC/DEC electrolyte. The current in mA is shown on the y-axis, and the potential in mV is shown on the X-axis. Figure 2 shows the cycle performance plot of the u/NCA unit (Example 3). The capacitance in mAh/g is shown on the y-axis and the number of cycles is shown on the χ axis. 152723.doc 201131856 In the illustration:

不含苯并噻唑之電解質之cc， 含有苯并噻唑之電解質之CC 不含笨并嘆唾之電解質之DC 含有苯并噻唑之電解質之DC 貫線· 虛線： 含三角形之實線·· 含三角形之虛線： 此處’ CC為「充電電流 的電流。DC為「放電電流 流。 ’亦即對電池充電時所施加 ’亦即放電期間所施加之電 圖3顯示C/NMC單元之猶環性能圖（實例4)。單位為 mAh/g之電容示於y軸上，且循環次數示於X抽上。 於該圖示中：Cc of benzothiazole-free electrolyte, CC of benzothiazole-containing electrolyte, DC without electrolytes, and DC of electrolyte containing benzothiazole · Dotted line: solid line with triangle · triangle The dotted line: Here 'CC is the current of the charging current. DC is the "discharge current flow. 'that is, when the battery is charged", that is, the electricity applied during the discharge. Figure 3 shows the performance of the C/NMC unit. Figure (Example 4). The capacitance in mAh/g is shown on the y-axis and the number of cycles is shown on X. In this illustration:

實，線·· 電解質之CCReal, line·· Electrolyte CC

含三角形之實線： 電解質之DC 關於CC及DC之定義，請參見上文。 實例 實例1 藉由循環伏安法（CV)測定電化學電位窗 於塗覆塑膠之玻璃容器中進行該實驗。工作電極（WE)為 面積為0.04 cm2之鉑環電極，且參考電極（RE)為鋰金屬， 且位於工作電極附近。相對電極（CE)為鋰片。所用之電解 質洛液為體積比為1 : 3之碳酸乙烯酯（EC)與碳酸二乙酽 (DEC)之混合物。將5重量％苯并噻唑加入該電解質溶液 中。電解質為LiPFe，於所述溶液中存在J莫耳。所用之掃 描速率為20 mV/s ’掃描範圍為相對於Li/U+為·〇 5 v至$ 152723.doc 201131856 V。4.8 v時之電化學電位窗示於圖丨中。 實例2 鍍鋰及形態 於覆有塑膠之玻璃容器中進行電化學鍍鋰實驗。相對電 極及工作電極為面積為3.〇Cm2之鋰片。鋰金屬作為參考電 極。對工作電極提供1 mA/cm2之恒定陰極電流。於相同條 件下，測試由碳酸乙稀酯及碳酸二乙酯（1 : 3 v/v)及$重量 %苯并噻唑組成之電解質及對照電解質。 對照試驗產生對片體之黏附性不佳之極鬆散鋰沉積物。 使用笨并噻唑作為添加物之實驗產生黏附性良好之極緊 密、微細之沉積物。經計算得知，電流效率為98〇/〇。 實驗3 單元循環 #於Swagelok 3_電極單元中，將鋰落以陽極用於集流器銅 泊上。覆有鋁集流器2NCA(Li_Ni_c〇氧化物）作為陰極材 料’鋰再次用作參考電極。於氬氣氛圍下，將單元組裝於 手套相中，且所有組件已於真空烘箱中120oC下乾燥過 仪i使早兀於3 ¥與4 2 v之間於1(：以下循環。測試含有及 3有笨并噻唑之電解質。圖2顯示苯并噻唑改善單元之 循環性能。 ^另—項測試中，NMC(Li_Ni_Mn_c〇氧化物）用作陰極 材料*石墨㈣陽極材料。保持⑽㈣仏設置及測試條 件。圖3顯示於苯并嚷。坐存在下之安定性，其顯示苯并嗟 唑對石墨陽極不存在任何副作用。 152723.doc 13 201131856 【圖式簡單說明】 圖1顯示於EC/DEC電解質中使用3重量％苯并噻唑時之循 環伏安圖（實例1)。 圖2顯示Li/NCA單元之循環性能圖（實例3)。 圖3顯示C/NMC單元之循環性能圖（實例4)。 152723.doc •14-Solid line with triangle: DC of electrolyte For the definition of CC and DC, please see above. EXAMPLES Example 1 Electrochemical potential window was determined by cyclic voltammetry (CV). The experiment was carried out in a plastic coated glass container. The working electrode (WE) is a platinum ring electrode having an area of 0.04 cm2, and the reference electrode (RE) is lithium metal and is located near the working electrode. The opposite electrode (CE) is a lithium sheet. The electrolyte solution used was a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:3. 5% by weight of benzothiazole was added to the electrolyte solution. The electrolyte is LiPFe and J mole is present in the solution. The scanning rate used was 20 mV/s Å. The scanning range was 〇 5 v to $ 152723.doc 201131856 V with respect to Li/U+. The electrochemical potential window at 4.8 v is shown in Figure 。. Example 2 Lithium plating and morphology Electrochemical lithium plating experiments were carried out in a glass container covered with plastic. The opposite electrode and the working electrode are lithium sheets having an area of 3. 〇Cm2. Lithium metal is used as the reference electrode. A constant cathode current of 1 mA/cm2 is supplied to the working electrode. The electrolyte consisting of ethylene carbonate and diethyl carbonate (1:3 v/v) and $% by weight of benzothiazole and a control electrolyte were tested under the same conditions. The control test produced extremely loose lithium deposits that were poorly adherent to the sheet. Experiments using stupid and thiazole as additives produced extremely tight, fine deposits with good adhesion. It is calculated that the current efficiency is 98 〇 / 〇. Experiment 3 Unit Cycle #In the Swagelok 3_electrode unit, lithium was dropped on the anode for the collector copper. An aluminum current collector 2NCA (Li_Ni_c〇 oxide) was coated as a cathode material. Lithium was again used as a reference electrode. The unit was assembled into the glove phase under an argon atmosphere, and all the components were dried in a vacuum oven at 120oC to make it between 3 ¥ and 4 2 v at 1 (: the following cycle. 3 There is a stupid and thiazole electrolyte. Figure 2 shows that benzothiazole improves the cycle performance of the unit. ^In another test, NMC (Li_Ni_Mn_c〇 oxide) is used as the cathode material * graphite (four) anode material. Keep (10) (four) 仏 set and test Conditions. Figure 3 shows the stability of benzopyrene in the presence of sit-up, which shows that benzoxazole does not have any side effects on the graphite anode. 152723.doc 13 201131856 [Simple illustration of the diagram] Figure 1 shows the EC/DEC electrolyte Cyclic voltammogram when using 3% by weight of benzothiazole (Example 1) Figure 2 shows the cycle performance diagram of Li/NCA unit (Example 3) Figure 3 shows the cycle performance of C/NMC unit (Example 4) 152723.doc •14-

Claims (1)

201131856 七、申請專利範圍： 1. 一種電解質溶液’其包含作為組分A之至少一種溶劑、 作為組分B之至少一種電解質、及佔電解質溶液總重量 之0.1至20重量％之作為組分c之至少一種通式（I)化合 ’ 物，201131856 VII. Patent application scope: 1. An electrolyte solution comprising at least one solvent as component A, at least one electrolyte as component B, and 0.1 to 20% by weight based on the total weight of the electrolyte solution as component c At least one compound of the formula (I), 其中X1、X2、X3、112及m具有下列含意： X1、X2 相互獨立地為N或CH， X3 為 NR1、Ο 或 S， m 為〇至4之整數， 其中X 、X2及X3中之至少兩去或、鹿ήχτ 王^啕#為選自Ν、〇及S之雜原 係自由如下組成之群中選出 Κ 個雜原子的直鏈或分支鏈、飽和或不飽和C1 c12-烧基，·可***至少一個雜原子之經取代; 未經取代之c3-c12-環炫基；經取代或未經取刊 :rr基;經取代或未經取代〜 基團R2係獨立地自由如下組成之群 -個雜原子的直鏈或分支鏈、經取代：二少 代之c,-cI2-烷基；可***至少—個雜原子經取 取代或未經取代之c3_Cl2_環燒基；經取代= 152723.doc 201131856 、星取代之C5-C2〇-芳基；經取代或未經取代之 雜芳基；_素及具有拉電子性質之官能 基。 2. 月求項1之電解質溶液，其中該溶劑（組分Α)係自由如 下組成之群中選出：碳酸酯、雜環化合物、酯類、醚 類'芳香族化合物及其混合物。 3. 如請求们或2之電解f溶液，其中該至少_ ㈣係自由如下組成之群中選出：齒化鐘、氧化：: 硼碟、石申錯合物之鐘鹽、過氣酸鐘、三氟甲項酸經、 :胺鋰、雙(三氟甲磺醯基)亞胺鋰 '其衍生物及其混合 物。 4. 5. =或2之電㈣溶液’其中存在笨并-作為 一種於電解質溶液中使用如請求項ι所定義 合物之方法。 通 之通式（I)化 6. =求項5之方法…該電解質溶液係用於電化學單 7.8. 元中 如凊求項5之方法，其中 -種於電化學單…該電解質溶液係用於鍍金屬。 電解質溶液之方法。 ㊉使用如-求項“戈2之 152723.docWherein X1, X2, X3, 112 and m have the following meanings: X1, X2 are each independently N or CH, X3 is NR1, Ο or S, and m is an integer from 〇 to 4, wherein at least X, X2 and X3 The two or the deer ήχ 王 Wang ^ 啕 # is selected from the group consisting of Ν, 〇 and S. The linear or branched chain, saturated or unsaturated C1 c12-alkyl group of the hetero atom is selected from the group consisting of: · Substitutable at least one hetero atom; unsubstituted c3-c12-cyclohexyl; substituted or unreported: rr group; substituted or unsubstituted ~ group R2 is independently freely composed as follows a straight or branched chain of a hetero atom, substituted: two lower generations of c, -cI2-alkyl; a c3_Cl2_cycloalkyl group which may be substituted with at least one hetero atom or substituted or unsubstituted; Substitution = 152723.doc 201131856, a star-substituted C5-C2 fluorene-aryl group; a substituted or unsubstituted heteroaryl group; a phenyl group and a functional group having a tensile electron property. 2. The electrolyte solution of claim 1, wherein the solvent (component oxime) is selected from the group consisting of carbonates, heterocyclic compounds, esters, ethers, aromatic compounds, and mixtures thereof. 3. If the request or the electrolytic f solution of 2, the at least _ (four) is selected from the group consisting of: toothing clock, oxidation:: boron disc, Shishen complex compound bell salt, gas clock, Trifluoromethane acid, : lithium amine, lithium bis(trifluoromethanesulfonyl)imide, its derivatives, and mixtures thereof. 4. 5. = or 2 (4) solution 'where stupid and - as a method of using the compound as defined in claim ι in the electrolyte solution. By the general formula (I) 6. The method of claim 5, the electrolyte solution is used in the electrochemical single 7.8. The method of claim 5, wherein the electrolyte solution is Used for metal plating. Method of electrolyte solution. Ten use as - seeking item "Ge 2 152723.doc