CN102544634B - Mixed electrolyte and preparation method and application thereof - Google Patents
Mixed electrolyte and preparation method and application thereof Download PDFInfo
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- CN102544634B CN102544634B CN 201110433568 CN201110433568A CN102544634B CN 102544634 B CN102544634 B CN 102544634B CN 201110433568 CN201110433568 CN 201110433568 CN 201110433568 A CN201110433568 A CN 201110433568A CN 102544634 B CN102544634 B CN 102544634B
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Abstract
The invention relates to a mixed electrolyte and a preparation method and an application of the mixed electrolyte. The mixed electrolyte consists of an ionic liquid of dialkyl imidazolium-based diaryliodonium salt and an organic lithium salt that are equimolar. The preparation method comprises the steps of: adding N-methyl imidazole and chlorobutane into a container; then adding solvents of cyclohexane and methylbenzene; performing oil bath, rising temperature, refluxing, cooling and layering; pouring the yellow liquid in the upper layer and filtering and weighing the white crystal in the lower layer; placing the white crystal in the container, adding ethyl acetate and acetonitrile, heating, refluxing and filtering, crystallizing at -15-0 DEG C for 4-8h; re-crystallizing the crystallized product to obtain an intermediate body; dropping LiPF6 aqueous solution slowly into the intermediate body, agitating, and standing still, taking the coarse product in the lower layer and adding AgPF6 for reaction, removing white precipitate after reaction so as to obtain the mixed electrolyte. The mixed electrolyte has the advantages of good lyophobic property, simple preparation method and strongpracticality and can be used to large scale industrialized production. The mixed electrolyte used in lithium air battery can improve the energy density and charge-discharge time of the battery.
Description
Technical field
The present invention relates to the electrolyte technology of preparing, particularly a kind of mixed type electrolyte and its preparation method and application.
Background technology
Lithium-air battery is a kind ofly to do anode with lithium, and with the battery of airborne oxygen as cathode reactant, it is compared with lithium ion battery has higher energy density, because its cathode active material O
2Can directly from surrounding air, obtain and need not be kept in the battery.In theory, because oxygen is as negative electrode, reactant is not limited, the capacity of lithium-air battery only depends on lithium electrode, simultaneously because Li has high theoretical specific capacity, make the theoretical specific energy of lithium-air battery can reach 11,140Wh/kg, this theoretical specific energy is higher than at present all conventional power supply systems.Another principal element that determines the lithium-air battery performance is electrolyte, wherein solid electrolyte and gel electrolyte good reliability and can not occur that electrolyte leakage, specific energy are high, cyclical voltage is wider, but the electrolytical conductivity of most solid and solubility are lower under the room temperature; Organic electrolyte system easily causes the corrosion of negative pole lithium owing to used moisture organic solvent in the preparation, cause the specific capacity of lithium-air battery to descend and the efficiency for charge-discharge reduction; And that ionic liquid has an electrochemical window is wide, not volatile, and the advantage such as can be recycled is applied in novel ion liquid in the electrolyte research of lithium-air battery, has become the research forward position of present multidisciplinary intersection.But the ionic liquid that is applied at present lithium-air battery only rests on the experimental stage, and its hydrophobic performance is poor, the preparation method is complicated, can not carry out large-scale industrial production, has limited its application.
Summary of the invention
But the technical problem to be solved in the present invention provides, and a kind of hydrophobic performance is good, the preparation method is simple, the mixed type electrolyte of practical large-scale industrial production and its preparation method and application.
A kind of mixed type electrolyte, formed by equimolar dialkylimidazolium class hexafluorophosphate ionic liquid and organic lithium salt, described dialkylimidazolium class hexafluorophosphate ionic liquid is 1-methyl-3-butyl imidazole hexafluorophosphate ionic liquid, and described organic lithium salt is lithium hexafluoro phosphate.
A kind of mixed type electrolyte preparation method, its concrete steps are as follows:
Step 1: the chloro-normal butane of 1mol N-methylimidazole and 1～2 mol is joined in the container, reflux is installed, add again each 50～100 mL of cyclohexane and toluene and make solvent, controlling first oil bath is 70～90 ℃, rise to 97～102 ℃ after stablizing 8～12 min, the control reflux temperature is 97～102 ℃, behind backflow 22～26 h, the rising oil bath temperature, the control temperature is 107～112 ℃, 10～12 h reflux, stopped heating, then liquid rotating is moved in the container of sealing, cooling 3～5 h layerings, the upper strata is slightly yellowy liquid, lower floor is white crystals, the yellow liquid on upper strata is poured out, white crystals is smashed to pieces carried out suction filtration, the white crystal behind the suction filtration is weighed;
Step 2: white crystal is inserted in the container, add ethyl acetate and acetonitrile and amount to 100～200 mL, the volume ratio of ethyl acetate and acetonitrile is 2:1～3:1, heats under oil bath, oil bath temperature is 70～90 ℃, backflow 20～30 min dissolve white precipitate fully, then filter, remove insoluble matter, filtered rear directly transferring in the sealed beaker, put into refrigerator, at-15～0 ℃ of lower crystallization 4～8 h;
Step 3: the product after the crystallization again by the step 2 recrystallization, is obtained the white crystal of intermediate chloridization 1-methyl-3-butyl imidazole behind 2～4 recrystallizations, drying under reduced pressure is put in the desiccator for subsequent use;
Step 4: will with the equimolar LiPF of chloridization 1-methyl-3-butyl imidazole
6The aqueous solution slowly splashes in the chloridization 1-methyl-3-butyl imidazole, stirring at room 10～12 h, and standing demix 10～30 min take off layer thick product of oily ionic liquid, add and the equimolar AgPF of chloridization 1-methyl-3-butyl imidazole
6React, remove the AgCl white precipitate after reaction is finished, namely obtain BMI-PF
6Ionic liquid and LiPF
6Mixed electrolyte.
The application of a kind of mixed type electrolyte in lithium-air battery.
Beneficial effect of the present invention: lithium salt is relatively high in the resulting mixed type ionic liquid electrolyte of preparation method of the present invention, be conducive to lithium ion at the mass transfer of inside battery, be applied in the lithium-air battery, greatly improved the energy density of battery and discharged and recharged number of times.
Embodiment
The present invention will be further described with specific embodiment for the below.
Embodiment 1
The preparation of mixed type ionic liquid electrolyte
Step 1: the chloro-normal butane of 1mol N-methylimidazole and 1mol is joined in the container, reflux is installed, add again each 50mL of cyclohexane and toluene and make solvent, controlling first oil bath is 70 ℃, rises to 97 ℃ after stablizing 8 min, and the control reflux temperature is 97 ℃, behind the backflow 22h, the rising oil bath temperature, the control temperature is 107 ℃, backflow 10h, stopped heating, then liquid rotating is moved in the container of sealing, cool off 3 h layerings, the upper strata is slightly yellowy liquid, lower floor is white crystals, the yellow liquid on upper strata is poured out, white crystals is smashed to pieces carried out suction filtration, the white crystal behind the suction filtration is weighed.
Step 2: white crystal is inserted in the container, the ethyl acetate that adds and acetonitrile (volume ratio is 2:1) amount to 100 mL, heat under oil bath, oil bath temperature is 70 ℃, backflow 20min, white precipitate is dissolved fully, then filter, in this step, insoluble matter is removed, filtered and directly transferred in the sealed beaker afterwards, put into refrigerator, at-15 ℃ of lower crystallization 4 h.
Step 3: the product after the crystallization is pressed the step 2 recrystallization again.Obtain the white crystal of 1mol intermediate chloridization 1-methyl-3-butyl imidazole (BMICl) behind the secondary recrystallization, drying under reduced pressure is put in the desiccator for subsequent use.
Step 4: with 1mol LiPF
6The aqueous solution slowly splashes in the BMICl aqueous solution, stirring at room 10 h, and standing demix 10 min take off layer thick product of oily ionic liquid, then the AgPF of the molal quantitys such as adding and BMICl
6, the AgCl white precipitate that filters out generation namely obtains BMI-PF
6Ionic liquid and LiPF
6Mixed electrolyte.
The assembling of lithium-air battery
The mixed type electrolyte that makes is placed in the middle of cathode of lithium and the air positive pole, is assembled into lithium-air battery by seal casinghousing.The specific energy of its lithium-air battery can reach 4500 mAh/g, and cycle-index is above 50 times.
Embodiment 2
The preparation of mixed type ionic liquid electrolyte
Step 1: the chloro-normal butane of 1mol N-methylimidazole and 1.5 mol is joined in the container, reflux is installed, add again each 75 mL of cyclohexane and toluene and make solvent, controlling first oil bath is 80 ℃, rises to 100 ℃ after stablizing 10 min, and the control reflux temperature is 100 ℃, reflux behind 24 h, the rising oil bath temperature, the control temperature is 110 ℃, backflow 11h, stopped heating, then liquid rotating is moved in the container of sealing, cool off 4 h layerings, the upper strata is slightly yellowy liquid, lower floor is white crystals, the yellow liquid on upper strata is poured out, white crystals is smashed to pieces carried out suction filtration, the white crystal behind the suction filtration is weighed.
Step 2: white crystal is inserted in the container, the ethyl acetate and acetonitrile (volume ratio is 2:1) 150 mL that add, heat under oil bath, oil bath temperature is 80 ℃, and 25 min reflux, white precipitate is dissolved fully, then filter, in this step, insoluble matter is removed, filtered and directly transferred in the sealed beaker afterwards, put into refrigerator, at-7 ℃ of lower crystallization 6h.
Step 3: the product after the crystallization is pressed the step 2 recrystallization again.Obtain the white crystal of intermediate chloridization 1-methyl-3-butyl imidazole (BMICl) behind three recrystallizations, drying under reduced pressure is put in the desiccator for subsequent use.
Step 4: will with the equimolar LiPF of chloridization 1-methyl-3-butyl imidazole (BMICl)
6The aqueous solution slowly splashes in the BMICl aqueous solution, stirring at room 11 h, and standing demix 20 min take off layer thick product of oily ionic liquid, then add and the equimolar AgPF of BMICl
6, the AgCl white precipitate that filters out generation namely obtains BMI-PF
6Ionic liquid and LiPF
6Mixed electrolyte.
The assembling of lithium-air battery
The mixed type electrolyte that makes is placed in the middle of cathode of lithium and the air positive pole, is assembled into lithium-air battery by seal casinghousing.The specific energy of its lithium-air battery can reach 4800 mAh/g, and cycle-index is above 60 times.
Embodiment 3
The preparation of mixed type ionic liquid electrolyte
Step 1: the chloro-normal butane of 1mol N-methylimidazole and 2mol is joined in the container, reflux is installed, add again each 100 mL of cyclohexane and toluene and make solvent, controlling first oil bath is 90 ℃, rises to 102 ℃ after stablizing 12 min, and the control reflux temperature is 102 ℃, reflux behind 26 h, the rising oil bath temperature, the control temperature is 112 ℃, backflow 12h, stopped heating, then liquid rotating is moved in the container of sealing, cool off 5 h layerings, the upper strata is slightly yellowy liquid, lower floor is white crystals, the yellow liquid on upper strata is poured out, white crystals is smashed to pieces carried out suction filtration, the white crystal behind the suction filtration is weighed.
Step 2: white crystal is inserted in the container, the ethyl acetate and acetonitrile (volume ratio is 3:1) 200 mL that add, heat under oil bath, oil bath temperature is 90 ℃, backflow 30min, white precipitate is dissolved fully, then filter, in this step, insoluble matter is removed, filtered and directly transferred in the sealed beaker afterwards, put into refrigerator, at 0 ℃ of lower crystallization 8 h.
Step 3: the product after the crystallization is pressed the step 2 recrystallization again.Obtain the white crystal of intermediate chloridization 1-methyl-3-butyl imidazole (BMICl) behind four recrystallizations, drying under reduced pressure is put in the desiccator for subsequent use.
Step 4: will with the equimolar LiPF of chloridization 1-methyl-3-butyl imidazole (BMICl)
6The aqueous solution slowly splashes in the BMICl aqueous solution, stirring at room 12 h, and standing demix 30 min take off layer thick product of oily ionic liquid, then add and the equimolar AgPF of BMICl
6, the AgCl white precipitate that filters out generation namely obtains BMI-PF
6Ionic liquid and LiPF
6Mixed electrolyte.
The assembling of lithium-air battery
The mixed type electrolyte that makes is placed in the middle of cathode of lithium and the air positive pole, is assembled into lithium-air battery by seal casinghousing.The specific energy of its lithium-air battery can reach 4600 mAh/g, and cycle-index is above 55 times.
Claims (2)
1. mixed type electrolyte preparation method is characterized in that concrete steps are as follows:
(1) chloro-normal butane with 1mol N-methylimidazole and 1～2 mol joins in the container, reflux is installed, add again each 50～100 mL of cyclohexane and toluene and make solvent, controlling first oil bath is 70～90 ℃, rise to 97～102 ℃ after stablizing 8～12 min, the control reflux temperature is 97～102 ℃, behind backflow 22～26 h, the rising oil bath temperature, the control temperature is 107～112 ℃, 10～12 h reflux, stopped heating, then liquid rotating is moved in the container of sealing, cooling 3～5 h layerings, the upper strata is slightly yellowy liquid, lower floor is white crystals, the yellow liquid on upper strata is poured out, white crystals is smashed to pieces carried out suction filtration, the white crystal behind the suction filtration is weighed;
(2) white crystal is inserted in the container, add ethyl acetate and acetonitrile and amount to 100～200 mL, the volume ratio of ethyl acetate and acetonitrile is 2:1～3:1, heats under oil bath, oil bath temperature is 70～90 ℃, backflow 20～30 min dissolve white precipitate fully, then filter, remove insoluble matter, filtered rear directly transferring in the sealed beaker, put into refrigerator, at-15～0 ℃ of lower crystallization 4～8 h;
(3) with the product after the crystallization again by step (2) recrystallization, obtain the white crystal of intermediate chloridization 1-methyl-3-butyl imidazole behind 2～4 recrystallizations, drying under reduced pressure is put in the desiccator for subsequent use;
(4) will with the equimolar LiPF of chloridization 1-methyl-3-butyl imidazole
6The aqueous solution slowly splashes in the chloridization 1-methyl-3-butyl imidazole, stirring at room 10～12 h, and standing demix 10～30 min take off layer thick product of oily ionic liquid, add and the equimolar AgPF of chloridization 1-methyl-3-butyl imidazole
6React, remove the AgCl white precipitate after reaction is finished, namely obtain BMI-PF
6Ionic liquid and LiPF
6Mixed electrolyte.
2. the application of mixed type electrolyte according to claim 1 in lithium-air battery.
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| CN101841064A (en) * | 2010-05-20 | 2010-09-22 | 中南大学 | High capacity and Coulomb-efficiency lithium-ion capacitance battery anode system |
| CN102074366A (en) * | 2010-12-30 | 2011-05-25 | 苏州方昇光电装备技术有限公司 | Mixed-type ionic liquid electrolyte as well as preparation method and application thereof |
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| CN101841064A (en) * | 2010-05-20 | 2010-09-22 | 中南大学 | High capacity and Coulomb-efficiency lithium-ion capacitance battery anode system |
| CN102074366A (en) * | 2010-12-30 | 2011-05-25 | 苏州方昇光电装备技术有限公司 | Mixed-type ionic liquid electrolyte as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
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| 1-丁基-3-甲基咪唑离子液体在超级电容器中的应用;金振兴等;《电子元件与材料》;20100930;第29卷(第9期);第66-69页 * |
| JP特开2008-66202A 2008.03.21 |
| 金振兴等.1-丁基-3-甲基咪唑离子液体在超级电容器中的应用.《电子元件与材料》.2010,第29卷(第9期),第66-69页. |
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Inventor after: Zhang Qingguo Inventor after: Cai Kedi Inventor after: Wei Ying Inventor after: Su Mingming Inventor after: Zhang Guangju Inventor after: Jin Zhenxing Inventor after: He Tieshi Inventor after: Zhang Xuelei Inventor before: Zhang Qingguo Inventor before: Cai Kedi Inventor before: Wei Ying Inventor before: Jin Zhenxing Inventor before: He Tieshi Inventor before: Wang Shuanglong Inventor before: Mu Weifang |
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Effective date of registration: 20170704 Address after: Two, No. 3, No. 122000, standard factory, Longcheng hi tech Zone, Longcheng District, Liaoning, Chaoyang City Patentee after: IAONING BROTHER ELECTRONICS TECHNOLOGY CO., LTD. Address before: 121000 No. 19, science and technology road, Jinzhou hi tech Industrial Zone, Liaoning Patentee before: Bohai University |
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Granted publication date: 20131023 Termination date: 20201222 |
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