摘要
氟是最活泼、电负性最强的非金属元素,将氟原子引入到有机物中会显著地改善它的物理和化学性质。有机物中引入氟原子的方法很多,但多数为污染较大、装置复杂、操作危险、且需要多步反应的化学氟化方法。而电化学氟化方法作为新兴的氟化方法,可以在温和的条件下将氟原子直接引入到有机物中,较其它氟化方法具有明显的优势。电化学氟化通常分为全氟化和选择性氟化两大类。
本论文主要研究了氯代二异丙基膦的电化学全氟化,咪唑的电化学选择氟化及氯代二异丙基膦氟化产物作为锂离子二次电池电解质的应用。
本论文分三部分。第一部分:以镁与氯代异丙烷反应合成异丙基氯化镁,异丙基氯化镁与三氯化磷合成氯代二异丙基膦,得到合成氯代二异丙基膦的最佳反应条件为:温度:-30℃～-35℃,反应时间:1.25h,物料配比:PCl_3:i-C_3H_7Cl=1:1.8(物质的量之比)。在超声波照射条件下,氯代二异丙基膦收率为80.1%。以三乙胺和氟化氢为原料,四氯化碳为溶剂,合成三乙胺三氟化氢,合成最佳方法为将三乙胺四氯化碳溶液,滴加到温度0～5℃,不断搅拌的无水氟化氢中。
第二部分:采用圆桶式电解槽,以镍为阳极和不锈钢为阴极,电解温度0～5℃,电解槽电压4.7～5.3V,电流密度0.15～0.35A·dm~(-2),电化学氟化氯代二异丙基膦得到氟化二异丙基膦酸。采用单室玻璃电解槽,以碳为阳极和阴极,电解温度10～20℃,电解槽电压为1.1～1.3V,电流密度0.20～0.35A·dm~(-2),电化学氟化咪唑得到氟化咪唑。
第三部分:氟化二异丙基膦酸与氟化锂在碳酸乙烯酯(EC)和碳酸二甲酯(DMC)混合溶剂中反应得到氟化二异丙基膦酸锂溶液,此溶液过滤可直接作为锂离子二次电池电解液。考察电解液得电导率、抗水性及氧化分解电位。以LiCoO_2为正极,锂片为负极组装两电极模拟电池体系,测试得到电池的放电平台为3.7 V;电池的首次放电比容量为107mA·h·g~(-1);当循环放电40次后,容量衰减较快,电池循环50周后,效率仍保持102%。交流阻抗图谱表明电解液放电时的阻抗约为140Ω。氟化二异丙基膦酸锂有望成为新型锂离子二次电池的电解质盐。
Fluorin is the most vivacious,and the strongest electronegative of all nonmatal elements.When fluorin is imported into organic compounds,their chemical and physical properties can be significantly changed.The pharmaceutical has series of special properties such as mimesis effect,lipophilic effect and stability etc.,which result in less toxicity,better metabolizability,longer pharmic effect and higher curative effect,when fluorin element or groups containing fluorin are imported into pharmaceutical.Although many methods of preparation of fluoroorganics have been developed to date,they often have unavoidable didadvantages such as complicated equipment,toxic reagents,hazardous operation,serious pollution,and multistep routs in chemical fluorination.Electrochemical fluorination,as a novel fluorination method,can import fluorin into organic compounds directly under mild conditions. Electrochemical fluorination can be classified into two sorts:perfluorination and selective fluorination.
Electrochemical fluorination of Chlorodiisopropylphosphine and imidazole,and the product of fluorinated Chlorodiisopropylphosphine as electrolyte of Lithium ion secondary batteries were studied in the paper.
The paper is comprised of three parts.The first part:Isopropylmagnesium Chloride is provided by the reaction of Magnesium and Isopropyl chlorides.Then Isopropylmagnesium Chloride and Phosphorus Trichloride make Chlorodiisopropylphosphine.The optimal reaction conditions are as follows: -30℃～-35℃,1.25 hour,PCl_3:i-C_3H_7Cl=1:1.8.The reactor was irradiated in the ultrasound.The yield was increased to 80.1%.Triethylamine tris(hydrogen fluoride) is synthesized,using triethylamine and anhydrous hydrogen fluoride as starting materials and carbon tetrachloride as the solvent.The optimal reaction conditions are as follows:0～5℃,dripping triethylamine and tetrachloride carbon solution toAHF under mix round.
The second part:Under the conditions that the temperature is about 0～-5℃,the cell voltage is 4.7～5.3V,the current density is 0.15～0.35A·dm~(-2),nickel as anode, stainless steel as cathode.Preparation of Fluorinated Alkylphosphorane is carried out by utilizing the typical tubby electrobath.Under the conditions that the temperature is about 10～20℃,the cell voltage is 1.1～1.3V,the current density is 0.20～0.35A·dm~(-2),carbon as anode and cathode.Preparation of Fluorinated imidazole is carried out by utilizing the only one room vitreous electrobath.
The third part:Fluorinated Alkylphosphoranes are reacted with LiF in organic solvent of EC and DME This solution can be used directly as electrolyte after filtering.Study on the chemical and electrochemical characters about the electrolyte.
The electrolyte was studied by a secondary cell testing system.Using LiCoO_2 as anode,Li as cathode,it was found that the discharge platform was3.7V,initial discharge capacity was 107mA·h·g~(-1) and efficiency still remained 102%after cycled 50 timeswhile capacity decreased largely after 40 times.The electrochemical impedance spectroscopy diagram showedthat the electrolyte electrochemical impedance was nearly 140Ω.The results indicated that the lithium perfluoroalkylphosphonate was expected to be the new electrolyte salt of lithiumion rechargeable batteries.
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