WO2017024801A1 - 一步法制备用于锂-二硫化亚铁电池的电解液的方法 - Google Patents

一步法制备用于锂-二硫化亚铁电池的电解液的方法 Download PDF

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WO2017024801A1
WO2017024801A1 PCT/CN2016/078129 CN2016078129W WO2017024801A1 WO 2017024801 A1 WO2017024801 A1 WO 2017024801A1 CN 2016078129 W CN2016078129 W CN 2016078129W WO 2017024801 A1 WO2017024801 A1 WO 2017024801A1
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lithium
electrolyte
preparing
battery
ppm
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PCT/CN2016/078129
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English (en)
French (fr)
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祝媛
程琛
王彦斌
刘建华
刘金成
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惠州亿纬锂能股份有限公司
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Priority claimed from CN201510486445.XA external-priority patent/CN105098203B/zh
Priority claimed from CN201510487588.2A external-priority patent/CN105186014B/zh
Application filed by 惠州亿纬锂能股份有限公司 filed Critical 惠州亿纬锂能股份有限公司
Priority to US15/129,310 priority Critical patent/US10050284B2/en
Publication of WO2017024801A1 publication Critical patent/WO2017024801A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents

Definitions

  • the invention belongs to the technical field of lithium primary batteries, relates to an electrolyte for a lithium-iron disulfide battery, and particularly relates to a method for preparing an electrolyte for a lithium-iron disulfide battery in a one-step process.
  • Lithium primary batteries are divided into high voltage and low voltage batteries according to open circuit voltage, open circuit voltage ⁇ 3.0V is high voltage lithium primary battery, such as lithium-thionyl chloride (Li/SOCl 2 ) battery, lithium-manganese dioxide (Li/MnO 2 Battery and lithium-carbon fluoride lithium (Li/CF X ) batteries; open circuit voltage ⁇ 3.0V for low voltage lithium primary batteries, such as lithium-ferrous ferrous sulfide (Li/FeS 2 ) batteries.
  • Li/SOCl 2 lithium-thionyl chloride
  • Li/MnO 2 Battery lithium-manganese dioxide
  • Li/CF X lithium-carbon fluoride lithium
  • Li/FeS 2 battery is a low-voltage lithium primary battery, its working voltage platform is 1.5V, so it is interchangeable with the same size alkaline manganese (Zn/MnO 2 ) battery, nickel hydrogen battery, carbon battery or zinc silver battery. .
  • Li/FeS 2 battery has more excellent performance: Li/FeS 2 battery has higher mass specific energy, and the mass ratio energy of AA type Li/FeS 2 battery reaches 310 W.h/kg, while the same size of alkali manganese
  • the mass ratio energy of (Zn/MnO 2 ) battery, nickel hydrogen battery, carbon battery or zinc silver battery is only 55-154W.h/kg; the low temperature performance of Li/FeS 2 battery is better than ordinary Zn/MnO 2 battery.
  • the Zn/MnO 2 battery is suitable for use at temperatures above 0 °C due to the use of an aqueous electrolyte, while the Li/FeS 2 battery uses an organic electrolyte and can still operate normally at -40 °C. Therefore, Li/FeS 2 batteries have more market prospects.
  • the water destroys the SEI film on the surface of the negative electrode (full name: solid electrolyte interface film), affecting the electrical properties and storage life of the battery, so it is necessary to strictly control the moisture of each part.
  • the water in the electrolyte is difficult to control, such as the solvent of the electrolyte, glycol dimethyl ether (DME), 1,3-dioxolane (DOL) can be controlled by molecular sieve to remove water to control the water does not exceed 10 ppm, but the salt in the electrolyte (mainly anhydrous lithium iodide) is more difficult to remove.
  • anhydrous lithium iodide (LiI) is generally divided into two steps: the first step is to synthesize lithium iodide (LiI. x H 2 O, wherein the value of x is 0.2 to 3) containing crystal water, and the second step is to remove Crystal water of LiI. x H 2 O.
  • CN103137981A firstly prepared lithium iodide solid containing crystal water from elemental iodine, iron powder and lithium hydroxide as raw materials, and then dissolved lithium iodide solid containing crystal water in organic solvent, and then Electrochemical electrolysis was carried out under the action of a catalytic reduction electrode and a metal lithium electrode, and after filtration, the filtrate was filtered, and the organic solvent was removed from the filtrate to obtain anhydrous lithium iodide.
  • Chinese Patent Publication No. CN101565192A mentions that a lithium iodide solution is dehydrated to a lithium iodide powder containing 0.5 to 1 crystal water, and then dehydrated by vacuum heating to obtain anhydrous lithium iodide.
  • LiI. x H 2 O is prone to hydrolysis, oxidation, etc. under high temperature conditions to form impurities such as lithium hydroxide, iodine, and hydriodic acid, so that the two-step method is used (the first step is to prepare LiI. x H 2 O).
  • the anhydrous lithium iodide product prepared in the second step except for the crystallization water has low purity and low yield, and the prepared anhydrous LiI also contains a trace amount of water and the like.
  • the preparation method of the Li/FeS 2 battery electrolyte is divided into two steps: in the first step, the anhydrous solvent is uniformly mixed in proportion; in the second step, a certain amount of the prepared or purchased anhydrous lithium iodide is added to the solvent and mixed. Uniform, that is, Li / FeS 2 battery electrolyte.
  • the preparation method has the following problems: First, the preparation or purchase of anhydrous lithium iodide is expensive; second, the method is divided into two steps, which leads to easy introduction of moisture or new impurities in the preparation process.
  • the object of the present invention is to provide a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method, which adopts a one-step method for synthesizing an electrolyte, and does not introduce water in the whole process, and the cost is relatively high. Low, the produced lithium-ferrous ferrous sulfide battery has good performance.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of: adding an iodine-containing precursor to an organic solvent in an inert atmosphere, stirring uniformly, and then adding a lithium-containing precursor to stir the reaction, separating After the solid, an electrolyte for a lithium-iron disulfide battery was obtained.
  • the preparation method of the present invention can be illustrated as follows:
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of: adding an iodine element to an organic solvent in an inert atmosphere at 0 to 5 ° C, stirring uniformly, and then adding lithium aluminum hydride The lithium hydride is stirred and reacted for 1 to 2 hours, and then heated to 40 to 60 ° C to stir the reaction for 2 to 3 hours. After centrifugation and filtration, an electrolyte solution for a lithium-iron disulfide battery is obtained.
  • lithium aluminum hydride or lithium hydride is added in an excessive manner.
  • the molar ratio of the iodine element to lithium aluminum hydride is 2: (1 to 4);
  • the molar ratio of the iodine element to lithium aluminum hydride is 1:1.
  • the molar ratio of the iodine element to lithium hydride is 1: (2-8);
  • the molar ratio of the iodine element to the lithium hydride is 1:4.
  • the inert gas of the inert atmosphere is one of nitrogen or argon;
  • the gas purity of the inert atmosphere is ⁇ 99.99%; the moisture content of the inert atmosphere is ⁇ 10 ppm, and the oxygen content is ⁇ 0.5 ppm.
  • the organic solvent is subjected to dehydration treatment before use.
  • the water content of the dehydrated organic solvent is ⁇ 10 ppm; preferably using a molecular sieve pair
  • the organic solvent is subjected to a dehydration treatment.
  • the organic solvent is a mixed solvent of ethylene glycol dimethyl ether and 1,3-dioxolane; more preferably, the organic solvent is 25 to 45 wt% of ethylene glycol dimethyl ether and 55 ⁇ 75 wt% of a mixed solvent of 1,3-dioxolane.
  • Another one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprises the steps of: adding anhydrous aluminum triiodide to an organic solvent at 40 to 70 ° C in an inert atmosphere and stirring 0.5 to 0.5 After 2 hours, anhydrous lithium hydroxide was added, and the reaction was stirred for 6 to 8 hours, and the electrolytic solution for the lithium-iron disulfide battery was obtained by centrifugation and filtration.
  • the molar ratio of the anhydrous aluminum triiodide to anhydrous lithium hydroxide is 1: (3.6 ⁇ 10);
  • the molar ratio of the anhydrous aluminum triiodide to anhydrous lithium hydroxide is 1:6.
  • the inert gas of the inert atmosphere is one of nitrogen or argon;
  • the gas purity of the inert atmosphere is ⁇ 99.99%; the moisture content of the inert atmosphere is ⁇ 10 ppm, and the oxygen content is ⁇ 0.5 ppm.
  • the organic solvent is subjected to dehydration treatment before use.
  • the water content of the dehydrated organic solvent is ⁇ 10 ppm; preferably, the organic solvent is subjected to dehydration treatment using a molecular sieve.
  • the organic solvent is a mixed solvent of ethylene glycol dimethyl ether and 1,3-dioxolane; more preferably, the organic solvent is 25 to 45 wt% of ethylene glycol dimethyl ether and 55 ⁇ 75wt% 1,3-dioxane A mixed solvent composed of a penta ring.
  • the invention adopts a one-step method to synthesize an electrolyte for a lithium-iron disulfide battery, reduces the process flow, avoids the introduction of new impurities, and saves the production cost.
  • the whole process of the invention does not introduce water, the synthesized lithium iodide does not contain crystal water, avoids the complicated process of crystallization water in lithium iodide, and reduces the production cost.
  • the test result indicates that the prepared electrolyte is made into lithium- The ferrous sulfide battery has good performance.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 25.8 ppm and a conductivity of 25 ⁇ 2 ° C of 2.59 ms/cm.
  • Example 1 Method for preparing electrolyte for lithium-ferrous disulfide battery by one-step method, method and step thereof
  • Example 1 was essentially the same except that 0.5 mol of lithium aluminum hydride was replaced by 2 mol of lithium hydride.
  • the prepared electrolyte was tested to have a water content of 22.8 ppm and a conductivity of 25 ⁇ 2 ° C of 2.25 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 17.8 ppm and a conductivity of 25 ⁇ 2 ° C of 8.5 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure are basically the same as those of the third embodiment, except that 1 mol of lithium aluminum hydride is replaced by 4 mol of lithium hydride;
  • the electrolyte was tested to have a water content of 15.8 ppm and a conductivity of 25 ⁇ 2 ° C of 7.75 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure are basically the same as those of the third embodiment, except that 1 mol of lithium aluminum hydride is replaced by 2 mol of lithium aluminum hydride;
  • the obtained electrolyte was tested to have a water content of 12.8 ppm and a conductivity of 25 ⁇ 2 ° C of 8.9 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure are basically the same as those of the third embodiment, except that 1 mol of lithium aluminum hydride is replaced by 4 mol of lithium hydride;
  • the electrolyte was tested to have a water content of 9.7 ppm and a conductivity of 25 ⁇ 2 ° C of 8.35 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure of which are basically the same as those of the third embodiment, except that the temperature is changed to 0 ° C under the condition of 0 ° C;
  • the obtained electrolyte was tested to have a water content of 16.9 ppm and a conductivity of 25 ⁇ 2 ° C of 7.9 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure of which are basically the same as those of the embodiment 4, except that the method is changed to 0 ° C under the condition of 0 ° C;
  • the obtained electrolyte was tested to have a water content of 14.3 ppm and a conductivity of 25 ⁇ 2 ° C of 7.8 ms/cm.
  • a method for preparing an electrolyte for a lithium-iron disulfide battery by a one-step method the method and the procedure are basically the same as those of the third embodiment, except that a 1 mol of lithium aluminum hydride is slowly added and stirred for 1 hour, and 1 mol of hydrogenation is slowly added.
  • the aluminum lithium was stirred for 2 hours; the prepared electrolyte was tested to have a water content of 13.9 ppm and a conductivity of 25 ⁇ 2 ° C of 8.7 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure of which are basically the same as those of the embodiment 4, except that a 4 mol of lithium hydride is slowly added and stirred for 1 hour, and 4 mol of lithium hydride is slowly added.
  • the reaction was stirred for 2 hours; the prepared electrolyte was tested to have a water content of 16.3 ppm and a conductivity of 25 ⁇ 2 ° C of 7.7 ms/cm.
  • Example 3 Method for preparing electrolyte for lithium-ferrous disulfide battery by one-step method, method and step thereof
  • Example 3 is basically the same, except that the temperature is further raised to 40 ° C, the stirring reaction is adjusted for 2 h, and the temperature is further raised to 60 ° C to stir the reaction for 2 h; the prepared electrolyte is tested, and the water content is 15.8 ppm, 25 ⁇ 2 ° C.
  • the conductivity is 8.5 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure are basically the same as those of the fourth embodiment, except that the temperature is further raised to 40 ° C, the stirring reaction is carried out for 2 hours, and the temperature is further increased to 60 ° C for stirring.
  • the reaction was carried out for 2 h; the prepared electrolyte was tested to have a water content of 15.3 ppm and a conductivity of 25 ⁇ 2 ° C of 7.9 ms/cm.
  • a method for preparing an electrolyte for a lithium-iron disulfide battery by a one-step method the method and the procedure are basically the same as those of the third embodiment, except that the temperature is further raised to 40 ° C, the stirring reaction is carried out for 2 hours, and the temperature is further increased to 40 ° C for stirring.
  • the reaction was carried out for 3 h; the prepared electrolyte was tested to have a water content of 14.8 ppm and a conductivity of 25 ⁇ 2 ° C of 8.4 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure are basically the same as those of the embodiment 4, except that the temperature is further raised to 40 ° C, the stirring reaction is carried out for 2 hours, and the temperature is further increased to 40 ° C for stirring.
  • the reaction was carried out for 3 h; the prepared electrolyte was tested to have a water content of 15.5 ppm and a conductivity of 25 ⁇ 2 ° C of 7.7 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure are basically the same as those of the third embodiment, except that the ethylene glycol dimethyl ether in the mixed solution accounts for 25 wt%, 1 , 3-dioxolane accounted for 75 wt%, in which the ethylene glycol dimethyl ether accounted for 45 wt%, 1,3-dioxolane accounted for 55 wt%; the prepared electrolyte was tested, Conductance with a water content of 15.2 ppm and 25 ⁇ 2 ° C The rate is 8.1 ms/cm.
  • a method for preparing an electrolyte for a lithium-sulfide ferrous battery by a one-step method the method and the procedure of which are basically the same as those of the embodiment 4, except that the ethylene glycol dimethyl ether in the mixed solution accounts for 25 wt%, 1 , 3-dioxolane accounted for 75 wt%, in which the ethylene glycol dimethyl ether accounted for 45 wt%, 1,3-dioxolane accounted for 55 wt%; the prepared electrolyte was tested,
  • the water content was 15.9 ppm and the conductivity at 25 ⁇ 2 ° C was 7.4 ms/cm.
  • the electrolytic solutions prepared in Examples 1 to 16 were respectively used to prepare a 1.5 V primary lithium battery to prepare a wound cylindrical AA-type lithium-iron disulfide battery, and the electrolyte injection amount of the single-cell battery was 1.8 g.
  • the prepared lithium-iron disulfide battery was used to test the capacity of the new battery and the capacity of the battery after the new electricity was stored at 60 ° C for 30 days.
  • the capacity test method is to discharge with a constant current of 200 mA, and the cutoff voltage is 0.8V.
  • Example 6 3101 3095 0.52%
  • Example 7 3114 3098 0.51%
  • Example 8 3121 3104 0.54%
  • Example 9 3127 3109 0.58%
  • Example 10 3142 3122 0.64%
  • Example 11 3125 3108 0.54%
  • Example 12 3109 3091 0.58%
  • Example 13 3113 3098 0.48%
  • Example 14 3126 3109 0.54%
  • Example 15 3116 3100 0.51%
  • Example 16 3085 0.55%
  • the lithium-iron disulfide battery prepared by using the electrolyte prepared in Examples 1-16 of the present invention has a new capacity, a capacity after 30 days of storage at 60 ° C, and a self-discharge rate. Both are close and there is no obvious difference. It is indicated that the electrolyte prepared by the present invention can be applied to a lithium-iron disulfide battery.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 17.4 ppm and a conductivity of 25 ⁇ 2 ° C of 2.37 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 22.2 ppm and a conductivity of 25 ⁇ 2 ° C of 7.5 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 23.8 ppm and a conductivity of 25 ⁇ 2 ° C. 7.8ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 28.9 ppm and a conductivity of 25 ⁇ 2 ° C of 8.0 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 25.6 ppm and a conductivity of 25 ⁇ 2 ° C of 7.9 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution contains 45 wt% of ethylene glycol dimethyl ether and 55 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 24.3 ppm and a conductivity of 25 ⁇ 2 ° C of 7.8 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 21.9 ppm and a conductivity of 25 ⁇ 2 ° C of 8.8 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 22.6 ppm and a conductivity of 25 ⁇ 2 ° C of 4.8 ms/cm.
  • a one-step method for preparing an electrolyte for a lithium-iron disulfide battery comprising the steps of:
  • the mixed solution accounts for 25 wt% of ethylene glycol dimethyl ether and 75 wt% of 1,3-dioxolane, and the mixed solution is dehydrated by molecular sieve to a water content of ⁇ 10 ppm before use.
  • the prepared electrolyte was tested to have a water content of 21.5 ppm and a conductivity of 25 ⁇ 2 ° C of 5.5 ms/cm.
  • the electrolytes prepared in Examples 17 to 25 were respectively used to prepare a 1.5 V primary lithium battery, and a coiled cylindrical AA type lithium-disulfide battery was prepared according to a conventional method and other conventional components, and an electrolyte solution of a single battery was prepared.
  • the amount of liquid was 1.8 g.
  • the prepared lithium-iron disulfide battery was used to test the capacity of the new battery and the capacity of the battery after the new electricity was stored at 60 ° C for 30 days.
  • the capacity test method is to discharge with a constant current of 200 mA, and the cutoff voltage is 0.8V.
  • the lithium-iron disulfide battery prepared by using the electrolyte prepared in Examples 17 to 25 of the present invention has a new capacity, a capacity after 30 days of storage at 60 ° C, and a self-discharge rate. Both are close and there is no obvious difference. It is indicated that the electrolyte prepared by the present invention can be applied to a lithium-iron disulfide battery.

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Abstract

本发明属于锂一次电池技术领域，公开了一步法制备用于锂-二硫化亚铁电池的电解液的方法。所述方法包括如下步骤：在惰性气氛中，将含碘前体加入有机溶剂中搅拌均匀，然后加入含锂前体搅拌反应，分离固体后即得到用于锂-二硫化亚铁电池的电解液。所述制备方法采用一步法合成用于锂-二硫化亚铁电池的电解液，整个制备过程不引进水分，成本较低，采用本发明方法制得的电解液制成的锂-二硫化亚铁电池性能良好。

Description

一步法制备用于锂-二硫化亚铁电池的电解液的方法 技术领域
本发明属于锂一次电池技术领域，涉及用于锂-二硫化亚铁电池的电解液，具体涉及一步法制备用于锂-二硫化亚铁电池的电解液的方法。
背景技术
锂一次电池按开路电压分为高压和低压两类电池，开路电压≥3.0V为高压锂一次电池，如锂-亚硫酰氯(Li/SOCl2)电池、锂-二氧化锰(Li/MnO2)电池和锂-氟化碳锂(Li/CFX)电池；开路电压＜3.0V为低压锂一次电池，如锂-二硫化亚铁(Li/FeS2)电池。
由于Li/FeS2电池为低压锂一次电池，其工作电压平台为1.5V，因此与相同尺寸的碱锰(Zn/MnO2)电池、镍氢电池、碳性电池或锌银电池具有互换性。但Li/FeS2电池具有更多优异的性能：Li/FeS2电池具有更高的质量比能量，AA型Li/FeS2电池的质量比能量达310W.h/kg，而相同尺寸的碱锰(Zn/MnO2)电池、镍氢电池、碳性电池或锌银电池的质量比能量仅为55～154W.h/kg；Li/FeS2电池的低温性能较普通Zn/MnO2电池更优，Zn/MnO2电池因采用水系电解液致使合适的使用场合为0℃以上，而Li/FeS2电池采用有机电解液，在-40℃的条件下依然可以正常工作。因此，Li/FeS2电池更具有市场前景。
由于Li/FeS2电池负极为锂或锂合金，水份会破坏负极表面的SEI膜(全称：固体电解质界面膜)，影响电池的电性能和储存寿命，故需严格控制各部分的水份。其中，电解液中的水份较难控制，如电解液的溶剂乙二醇二甲醚(DME)、1，3-二氧戊环(DOL)可以通过分子筛除水将水份控制在不超过10ppm，但电解液中的盐(主要为无水碘化锂)的水份却较难除去。
目前，制备无水碘化锂(LiI)一般分为两步：第一步合成含结晶水的碘化锂(LiI.xH2O，其中x的值为0.2～3)，第二步除去LiI.xH2O的结晶水。公布号为CN103137981A的中国发明专利首先以单质碘、铁粉、氢氧化锂为原料，制备了含结晶水的碘化锂固体，然后将含结晶水的碘化锂固体溶于有机溶剂，再在催化还原电极和金属锂电极作用下进行电化学电解，电解结束后过滤，滤液除去有机溶剂得到无水碘化锂。公开号为CN101565192A的中国发明专利中提到将碘化锂溶液脱水至含有0.5～1个结晶水的碘化锂粉末，然后再经真空加热脱水处理，即得到无水碘化锂。
而由于LiI.xH2O在高温条件下极易发生水解、氧化等反应生成氢氧化锂、碘单质、氢碘酸等杂质，使得用两步法(第一步制备LiI.xH2O，第二步除结晶水)制备的无水碘化锂产品存在纯度低、收率低，加之制备的无水LiI还含有微量水等缺点。无水LiI纯度低和水份高的缺点直接影响Li/FeS2电池的电性能，更严重会造成制作的电池报废；而无水LiI的收率低导致配制的电解液成本更高。
目前，Li/FeS2电池电解液的配制方法分为两步：第一步，将无水溶剂按比例混合均匀；第二步，将一定量制备或购买的无水碘化锂加入溶剂中混合均匀，即得Li/FeS2电池电解液。该配制方法存在的问题为：一是制备或购买无水碘化锂价格昂贵；二是该方法分为二步导致配制过程易引入水分或新的杂质。
发明内容
为了克服现有技术的缺点与不足，本发明的目的在于提供一步法制备用于锂-二硫化亚铁电池的电解液的方法，该方法采用一步法合成电解液，整个过程不引进水分，成本较低，所制成的锂-二硫化亚铁电池性能良好。
本发明的目的通过下述技术方案实现：
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：在惰性气氛中，将含碘前体加入有机溶剂中搅拌均匀，然后加入含锂前体搅拌反应，分离固体后即得到用于锂-二硫化亚铁电池的电解液。
具体地，本发明所述的制备方法可以阐述如下：
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：在惰性气氛中，在0～5℃下，将碘单质加入有机溶剂中搅拌均匀，然后加入氢化铝锂或氢化锂搅拌反应1～2h，再升温至40～60℃搅拌反应2～3h，离心、过滤即得到用于锂-二硫化亚铁电池的电解液。
在上述制备方法中，所进行的反应的方程式为：
2I2+LiAlH4＝LiI+2H2↑+AlI3↓，
或：I2+2LiH＝2LiI+H2↑。
为了使反应方程式向着生成碘化锂(LiI)的方向进行，氢化铝锂或氢化锂采用过量投加的方式。
优选的，所述碘单质与氢化铝锂的摩尔比为2∶(1～4)；
更优选的，所述碘单质与氢化铝锂的摩尔比为1∶1。
优选的，所述碘单质与氢化锂的摩尔比为1∶(2～8)；
更优选的，所述碘单质与氢化锂的摩尔比为1∶4。
所述惰性气氛的惰性气体为氮气或氩气中的一种；
为使制备过程中不引入杂质及水分，所述惰性气氛的气体纯度为≥99.99％；所述惰性气氛的水分含量≤10ppm，氧气含量≤0.5ppm。
为尽量减少所制备的电解液中的水分，所述有机溶剂在使用前进行脱水处理。
优选的，经脱水处理后的有机溶剂的水含量≤10ppm；优选采用分子筛对 所述有机溶剂进行脱水处理。
优选的，所述有机溶剂为乙二醇二甲醚和1，3-二氧戊环的混合溶剂；更优选的，所述有机溶剂为由25～45wt％的乙二醇二甲醚与55～75wt％的1，3-二氧戊环组成的混合溶剂。
另一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：在惰性气氛中，在40～70℃下，将无水三碘化铝加入有机溶剂中搅拌0.5～2小时，然后加入无水氢氧化锂，搅拌反应6～8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液。
在上述制备方法中，所进行的反应的方程式为：
AlI3+3LiOH＝3LiI+Al(OH)3↓。
为了使反应方程式向着生成碘化锂(LiI)的方向进行，无水氢氧化锂采用过量投加的方式。
优选的，所述无水三碘化铝与无水氢氧化锂的摩尔比为1∶(3.6～10)；
更优选的，所述无水三碘化铝与无水氢氧化锂的摩尔比为1∶6。
所述惰性气氛的惰性气体为氮气或氩气中的一种；
为使制备过程中不引入杂质及水分，所述惰性气氛的气体纯度为≥99.99％；所述惰性气氛的水分含量≤10ppm，氧气含量≤0.5ppm。
为尽量减少所制备的电解液中的水分，所述有机溶剂在使用前进行脱水处理。
优选的，经脱水处理后的有机溶剂的水含量≤10ppm；优选采用分子筛对所述有机溶剂进行脱水处理。
优选的，所述有机溶剂为乙二醇二甲醚和1，3-二氧戊环的混合溶剂；更优选的，所述有机溶剂为由25～45wt％的乙二醇二甲醚与55～75wt％的1，3-二氧 戊环组成的混合溶剂。
本发明相对于现有技术具有如下的优点及效果：
1、本发明采用一步法合成用于锂-二硫化亚铁电池的电解液，减少工艺流程，避免了新杂质的引入，节约成产成本。
2、本发明整个过程不引进水分，合成的碘化锂不含结晶水，避免了除碘化锂中结晶水的复杂工艺，降低了生产成本，测试结果表明所制备的电解液制成锂-二硫化亚铁电池性能良好。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在0℃条件下，将0.5mol无水碘单质加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌均匀；然后缓慢加入0.5mol氢化铝锂搅拌反应1h，再升温至40℃搅拌反应2h，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为25.8ppm，25±2℃的电导率为2.59ms/cm。
实施例2
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与 实施例1的基本相同，区别在于将0.5mol的氢化铝锂换为2mol的氢化锂。
对所制得的电解液进行测试，其水含量为22.8ppm，25±2℃的电导率为2.25ms/cm。
实施例3
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在0℃条件下，将1mol无水碘单质加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌均匀；然后缓慢加入1mol氢化铝锂搅拌反应1小时，再升温至40℃搅拌反应2h，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为17.8ppm，25±2℃的电导率为8.5ms/cm。
实施例4
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将1mol的氢化铝锂换为4mol的氢化锂；对所制得的电解液进行测试，其水含量为15.8ppm，25±2℃的电导率为7.75ms/cm。
实施例5
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将1mol的氢化铝锂换为2mol的氢化铝锂；对所制得的电解液进行测试，其水含量为12.8ppm，25±2℃的电导率为8.9ms/cm。
实施例6
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将1mol的氢化铝锂换为4mol的氢化锂；对所制得的电解液进行测试，其水含量为9.7ppm，25±2℃的电导率为8.35ms/cm。
实施例7
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将在0℃条件下换为在5℃条件下；对所制得的电解液进行测试，其水含量为16.9ppm，25±2℃的电导率为7.9ms/cm。
实施例8
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例4的基本相同，区别在于将在0℃条件下换为在5℃条件下；对所制得的电解液进行测试，其水含量为14.3ppm，25±2℃的电导率为7.8ms/cm。
实施例9
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将缓慢加入1mol氢化铝锂搅拌反应1小时换为缓慢加入1mol氢化铝锂搅拌反应2小时；对所制得的电解液进行测试，其水含量为13.9ppm，25±2℃的电导率为8.7ms/cm。
实施例10
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例4的基本相同，区别在于将缓慢加入4mol氢化锂搅拌反应1小时换为缓慢加入4mol氢化锂搅拌反应2小时；对所制得的电解液进行测试，其水含量为16.3ppm，25±2℃的电导率为7.7ms/cm。
实施例11
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与 实施例3的基本相同，区别在于将再升温至40℃搅拌反应2h调整为再升温至60℃搅拌反应2h；对所制得的电解液进行测试，其水含量为15.8ppm，25±2℃的电导率为8.5ms/cm。
实施例12
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例4的基本相同，区别在于将再升温至40℃搅拌反应2h换为再升温至60℃搅拌反应2h；对所制得的电解液进行测试，其水含量为15.3ppm，25±2℃的电导率为7.9ms/cm。
实施例13
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将再升温至40℃搅拌反应2h换为再升温至40℃搅拌反应3h；对所制得的电解液进行测试，其水含量为14.8ppm，25±2℃的电导率为8.4ms/cm。
实施例14
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例4的基本相同，区别在于将再升温至40℃搅拌反应2h换为再升温至40℃搅拌反应3h；对所制得的电解液进行测试，其水含量为15.5ppm，25±2℃的电导率为7.7ms/cm。
实施例15
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例3的基本相同，区别在于将所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％换为所述混合溶液中乙二醇二甲醚占45wt％，1，3-二氧戊环占55wt％；对所制得的电解液进行测试，其水含量为15.2ppm，25±2℃的电导 率为8.1ms/cm。
实施例16
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，其方法和步骤与实施例4的基本相同，区别在于将所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％换为所述混合溶液中乙二醇二甲醚占45wt％，1，3-二氧戊环占55wt％；对所制得的电解液进行测试，其水含量为15.9ppm，25±2℃的电导率为7.4ms/cm。
实验测试：
将实施例1～16制备的电解液分别用于制备1.5V一次锂电，制成卷绕式圆柱AA型锂-二硫化亚铁电池，单支电池的电解液注液量为1.8g。
制备的锂-二硫化亚铁电池用于测试新电电池的容量与新电在60℃条件下存放30天后电池的容量。容量测试方法为用恒流200mA放电，截止电压为0.8V。
另外，购买市场上同型号的锂-二硫化亚铁电池作为对照组，进行相同条件的测试，结果如表1所示。
表1实施例和对照组的容量数据对比
组别 新电容量/mAh 60℃存放30天后的容量/mAh 自放电率/％
对照组 3120 3104 0.51％
实施例1 3087 3071 0.52％
实施例2 3099 3084 0.48％
实施例3 3112 3105 0.55％
实施例4 3132 3121 0.38％
实施例5 3120 3117 0.42％
实施例6 3101 3095 0.52％
实施例7 3114 3098 0.51％
实施例8 3121 3104 0.54％
实施例9 3127 3109 0.58％
实施例10 3142 3122 0.64％
实施例11 3125 3108 0.54％
实施例12 3109 3091 0.58％
实施例13 3113 3098 0.48％
实施例14 3126 3109 0.54％
实施例15 3116 3100 0.51％
实施例16 3102 3085 0.55％
由表1可看出，用本发明实施例1-16制备的电解液制成锂-二硫化亚铁电池与对照组电池相比，新电容量、60℃存放30天后的容量及自放电率均接近，没有明显的差别。说明本发明制备的电解液可以应用于锂-二硫化亚铁电池。
实施例17
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将0.5mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入1.8mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为17.4ppm，25±2℃的电导率为2.37ms/cm。
实施例18
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氩气为惰性气体、氧含量为0.5ppm、水分含量10ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入3.6mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为22.2ppm，25±2℃的电导率为7.5ms/cm。
实施例19
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入3.6mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为23.8ppm，25±2℃的电导率为 7.8ms/cm。
实施例20
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入10mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为28.9ppm，25±2℃的电导率为8.0ms/cm。
实施例21
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入6mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为25.6ppm，25±2℃的电导率为7.9ms/cm。
实施例22
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入6mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占45wt％，1，3-二氧戊环占55wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为24.3ppm，25±2℃的电导率为7.8ms/cm。
实施例23
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在70℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入3.6mol无水氢氧化锂搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为21.9ppm，25±2℃的电导率为8.8ms/cm。
实施例24
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌0.5小时；然后加入3.6mol无水氢氧化锂 搅拌反应8小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为22.6ppm，25±2℃的电导率为4.8ms/cm。
实施例25
一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：
在纯度≥99.99％的氮气为惰性气体、氧含量为0.5ppm、水分含量1.5ppm氛围的手套箱中，在40℃条件下，将1mol无水三碘化铝加入1L的乙二醇二甲醚与1，3-二氧戊环的混合溶液中搅拌2小时；然后加入3.6mol无水氢氧化锂搅拌反应6小时，离心、过滤即得所述用于锂-二硫化亚铁电池的电解液；
其中，所述混合溶液中乙二醇二甲醚占25wt％，1，3-二氧戊环占75wt％，混合溶液使用前均经分子筛脱水至水含量≤10ppm。
对所制得的电解液进行测试，其水含量为21.5ppm，25±2℃的电导率为5.5ms/cm。
实验测试：
将实施例17～25制备的电解液分别用于制备1.5V一次锂电，按照常规方法与其它常规组分制成卷绕式圆柱AA型锂-二硫化亚铁电池，单支电池的电解液注液量为1.8g。
制备的锂-二硫化亚铁电池用于测试新电电池的容量与新电在60℃条件下存放30天后电池的容量。容量测试方法为用恒流200mA放电，截止电压为0.8V。
另外，购买市场上同型号的锂-二硫化亚铁电池作为对照组，进行相同条件 的测试，结果如表2所示。
表2实施例和对照组的容量数据对比
组别 新电容量/mAh 60℃存放30天后的容量/mAh 自放电率/％
对照组 3120 3104 0.51％
实施例17 3058 3045 0.43％
实施例18 3112 3098 0.45％
实施例19 3102 3085 0.55％
实施例20 3152 3135 0.54％
实施例21 3144 3129 0.48％
实施例22 3121 3105 0.51％
实施例23 3170 3152 0.57％
实施例24 3081 3066 0.49％
实施例25 3092 3075 0.55％
由表2可看出，用本发明实施例17～25制备的电解液制成锂-二硫化亚铁电池与对照组电池相比，新电容量、60℃存放30天后的容量及自放电率均接近，没有明显的差别。说明本发明制备的电解液可以应用于锂-二硫化亚铁电池。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种一步法制备用于锂-二硫化亚铁电池的电解液的方法，包括如下步骤：在惰性气氛中，将含碘前体加入有机溶剂中搅拌均匀，然后加入含锂前体搅拌反应，分离固体后即得到用于锂-二硫化亚铁电池的电解液。
  2. 根据权利要求1所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其包括如下步骤：在惰性气氛中，在0～5℃下，将碘单质加入有机溶剂中搅拌均匀，然后加入氢化铝锂或氢化锂搅拌反应1～2h，再升温至40～60℃搅拌反应2～3h，离心、过滤即得到用于锂-二硫化亚铁电池的电解液。
  3. 根据权利要求2所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述碘单质与氢化铝锂的摩尔比为2∶(1～4)，优选为1∶1；
    优选地，所述碘单质与氢化锂的摩尔比为1∶(2～8)，优选为1∶4。
  4. 根据权利要求2所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述惰性气氛的惰性气体为氮气或氩气中的一种；
    优选地，所述惰性气氛的气体纯度为≥99.99％；所述惰性气氛的水分含量≤10ppm，氧气含量≤0.5ppm。
  5. 根据权利要求2所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述有机溶剂在使用前进行脱水处理。
  6. 根据权利要求2所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述有机溶剂为乙二醇二甲醚和1，3-二氧戊环的混合溶剂；优选地，所述有机溶剂为由25～45wt％的乙二醇二甲醚与55～75wt％的1，3-二氧戊环组成的混合溶剂。
  7. 根据权利要求1所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其包括如下步骤：在惰性气氛中，在40～70℃下，将无水三碘化铝加入有机溶剂中搅拌0.5～2小时，然后加入无水氢氧化锂，搅拌反应6～8小时，离 心、过滤即得所述用于锂-二硫化亚铁电池的电解液。
  8. 根据权利要求7所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述无水三碘化铝与无水氢氧化锂的摩尔比为1∶(3.6～10)，优选为1∶6。
  9. 根据权利要求7所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述惰性气氛的惰性气体为氮气或氩气中的一种；
    优选地，所述惰性气氛的气体纯度为≥99.99％；所述惰性气氛的水分含量≤10ppm，氧气含量≤0.5ppm。
  10. 根据权利要求7所述的一步法制备用于锂-二硫化亚铁电池的电解液的方法，其特征在于：所述有机溶剂在使用前进行脱水处理；优选地，经脱水处理后的有机溶剂的水含量≤10ppm；
    优选地，采用分子筛对所述有机溶剂进行脱水处理；
    优选地，所述有机溶剂为乙二醇二甲醚和1，3-二氧戊环的混合溶剂；优选地，所述有机溶剂为由25～45wt％的乙二醇二甲醚与55～75wt％的1，3-二氧戊环组成的混合溶剂。
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