CN103515654A - Preparation method for polymer solid electrolyte - Google Patents
Preparation method for polymer solid electrolyte Download PDFInfo
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- CN103515654A CN103515654A CN201310418975.1A CN201310418975A CN103515654A CN 103515654 A CN103515654 A CN 103515654A CN 201310418975 A CN201310418975 A CN 201310418975A CN 103515654 A CN103515654 A CN 103515654A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
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- 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
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method for a polymer solid electrolyte. The preparation method comprises the following steps: reacting an NaOH water solution with a certain concentration with N-methyl pyrrolidone under the protection of nitrogen gas and adding lithium chloride for replacing sodium ions to obtain a raw material-lithium methylaminobutyrate; dissolving the obtained lithium methylaminobutyrate, inorganic lithium and the like in an acetone-methanol solvent with a certain temperature to obtain a polymethyl methacrylate acetone-methanol solution containing lithium methylaminobutyrate and lithium iodide or lithium iodate; and repeatedly and uniformly applying the solution to a polyvinylidene fluoride semipermeable membrane for multiple times to obtain an organic lithium-containing polymer solid electrolyte membrane with a certain thickness. A solid lithium battery manufactured by the electrolyte membrane prepared with the method has the characteristics of long service life, high charge/discharge frequency, high battery capacity and the like.
Description
Technical field
The present invention relates to secondary cell, especially polymer solid electrolyte field of thin film fabrication.
Background technology
Battery is the power supply as electrical equipment such as torch and phones by people very early, along with scientific and technological progress and the discovery of new material, people have developed Ni-MH battery and lithium battery, appearance along with portable electronics such as mobile phone and notebook computers, demand to the high performance of battery and miniaturization and etc. seems more and more stronger, for meeting this demand, type lithium ion battery is high with energy density, the feature such as can charge rapidly progressively causes showing great attention to of people, compare with other the battery such as nickel-cadmium cell, high and rapid these features of charging based on energy content of battery density, the expectation that people benefit from long novel lithium battery polymer solid electrolyte film of life-span to high-efficient high-capacity three amount high charge number of times strengthens day by day.
In the electrochemical elements such as-primary cell or secondary cell and capacitor, can use liquid electrolyte to be used as manufacturing the conduction raw material of new battery, but that the electrolyte of liquid have that liquid leaks is dangerous or lack the shortcoming of long stability.Because solid electrolyte has overcome with liquid electrolyte battery leakage and unsettled shortcoming, copolymer solid electrolyte is applied to various electrochemical elements simultaneously, when realizing the simplification of element manufacture, miniaturization or the lightweight of element self become a reality, the danger that does not only have liquid to leak, but also the cell device that reliability is high is provided.For this reason, in type lithium ion battery etc., in the research and development process of solid electrolyte, the research and development of the copolymer solid electrolyte of light weight and softness, handling ease are carried out just actively.
The people such as Wright in 1973 have found that polyethylene glycol oxide (PEO) and alkali metal lithium, sodium salt complexing have the phenomenon of ion guide electronics first, thereby the research that makes solid electrolyte enters a new stage, but owing to being subject to the restriction of material and technological means, the room-temperature conductivity of solid electrolyte and practical application need to greatly differ from each other.In order to address this problem, first Feuillade etc. have proposed to adopt a kind of elastomer and inorganic lithium electrolyte to form a kind of mixture solution by the dissolution with solvents that can volatilize in 1975, then the surface that is coated on a kind of solid of inorganic lithium salt will be contained, form a kind of gel electrolyte membrane that contains inorganic lithium salt, although done further investigation by Abraham etc. afterwards.Polymer gel is generally defined as one by the polymer network system of solvent swell, and its unique network configuration makes gel have the dispersion conductibility of cohesiveness and the liquid of solid simultaneously.Nineteen ninety-five U.S. Bellcore company discloses a kind of new type gel polymer dielectric for researching and developing the technology of polymer Li-ion solid electrolyte battery.Since then, to the research of polymer Li-ion battery use solid electrolyte just more.Polymer Li-ion battery is the latest generation lithium ion battery of developing on the basis of liquid lithium ionic cell, its formation is to adopt the polymer-electrolyte that has ionic conductivity and have barrier film effect concurrently to replace the electrolyte in liquid lithium ionic cell, gel electrolyte is the gelatin polymer network with suitable microcellular structure being formed by certain method by polymer, plasticizer and lithium salts, the liquid electrolyte molecule that utilization is fixed in micro-structural is realized ionic conduction, and its room-temperature conductivity is generally 10
-3the S/cm order of magnitude.
Polyelectrolyte is the complex compound being formed by polymer matrix and doping salt. make salt be dissolved in macromolecule and form homogeneous solution, if must there is interaction between macromolecular chain and salt. macromolecular chain contains electronics and gives atom as oxygen atom, sulphur atom or nitrogen-atoms, it can carry out complexing by L ew is acid-base reaction with the cation in salt, and their interaction is just easy to produce so. work as LiClO
4be dissolved in PPG and can cause volume contraction, salt adds PPG to be made into when the caused volume contraction of 10.41% (w t) solution is equivalent to 25 ℃ to apply 1.90x10 to macromolecule solvent
7pa. this shows at Li
+and between PPG ether oxygen atom, there is strong interaction. they also find that the membership that adds of salt significantly improves PPG glass transition temperature, and when LiClO4 content reaches 25%, the Tg of PPG (MW2000) is increased to 40 ℃ by-70 ℃. they think, Li
+can not be by large ClO
4 -the fine shielding of ion, thereby be easy to interact along macromolecular scaffold and polar ether oxygen atom, this will be conducive to dissociating of salt. and this effect also makes interchain interaction be occurred, thereby causes the physical crosslinking of macromolecular chain.
Because most macromolecular compound is electrical insulator, but certainly report certain macromolecular material, for example poly(ethylene oxide) (PEO) with such as the such electrolytic salt of lithium salts, formed crystalline complex compound and since showing high ionic conductivity, using PEO or other polyalkylene oxide, also have and in molecule, there are equally the polymine of ionic dissociation base or polyphosphazene etc. and just attract much attention as the research of the polymer solid electrolyte of matrix.Particularly reported and manyly usingd polyalkylene oxide as the research of the polymer solid electrolyte of the composition of matrix, recently, the ionic conduction degree of near room temperature is modified to 10
-4～10
-6s/cm.But, in order to obtain high ion-conductivity, just need to improve the content of the polyalkylene oxide in matrix, this reduces electrolyte film strength or thermal endurance on the contrary significantly, thereby the solid electrolyte that obtains practicality is difficult, if had again at low temperature, for example, below 0 ℃, it is also that problem is as polymer solid electrolyte that ionic conductivity reduces terrifically, proposed to using to make the ABA type triblock copolymer of methoxy poly (ethylene glycol) monomethacrylates (A) and styrene (B) copolymerization as the polymer solid electrolyte of matrix base material by active anionic polymerization, but, homopolymers as the methoxy poly (ethylene glycol) monomethacrylates of composition six, although be high molecular weight material, but be aqueous in room temperature, in order to using the matrix base material of A-B-A type copolymer as solid electrolyte, so the content of composition A is restricted, this means as the shape and size of the PEO regional structure in the diffusion transport space of lithium ion restricted, ionic conductivity in the time of actual 40 ℃ is many does not meet 10
-6s/cm.
From the electrical conduction mechanism of solid electrolyte, at the melting point polymer crystalline compound that below 60 ℃, its SPE is formed by polymer crystalline phase, polymer and lithium salts conventionally with form electrical conduction mechanism research containing the polymer amorphous phase of solvation salt and show that under electric field action ion migration mainly occurs in amorphous phase region the motion due to polymer short range segment again and helps lend some impetus to polymer and Li
+between coordinate bond destruction and form Li
+migration provide degree of crystallinity that free volume therefore reduces polymer and glass transition temperature (Tg) to improve the compliance of polymer chain and increase its free volume density all contribute to obtain high conduction performance SPE and not and the polymer of the anion of polymer generation association low-k on the other hand from the directional migration to room that be commonly considered as conducting electricity by make to exist between ion and ion strong interaction and caused in SPE also having solvation except the cation of anion and solvation freely
They have determined that the concentration of charge carrier and transfer ability are also the key factors that affects SPE conductive capability the tight ion pair three ion aggregations of ion pair and other ion aggregation.But, among the solid electrolyte membrane being formed by polymer and lithium salts, according to the electrical conduction mechanism of lithium salts, under certain voltage, make lithium salts be dissociated into zwitterion, these zwitterions are under the effect of voltage, there is directional migration, but, because polymer plays supporting role in solid electrolyte, simultaneously, be subject to the restriction of the structure of polymer, if this polymer is crystal structure, the zwitterion that can make lithium salts dissociation form hinders the motion of these zwitterions under the effect of voltage, therefore, capacity for the battery that improves the electric conduction quantity of solid electrolyte and manufactured by this electrolyte, on the one hand, needing polymer is unbodied form, on the other hand, need lithium salts to there is good dissociating power, for this reason, study the target that a kind of high-effect electrolysis matter is each researcher.
In Chinese patent application 03817326.3, introduced a kind of so that the polymer solid electrolyte that thermal characteristics, physical characteristic and ionic conduction degree are good, approach realistic scale to be provided, total solids electrolyte particularly, and the copolymer compositions becoming for the manufacture of this electrolytical matrix is object.This polymer solid electrolyte contains copolymer and electrolytic salt, has the block chain A of the repetitive representing with formula (I) in this copolymer, have with formula (II) (in formula, R
9represent aryl) the block chain B of the repetitive that represents and have with formula (III) (in formula, R
13representing aryl or heteroaryl) the block chain C of the repetitive that represents arranges with the order of B, A, C.This polymer solid electrolyte is also the synthetic needed amorphous polymer of a kind of solid electrolyte of method that adopts block polymerization, compare with other polymer, this solid electrolyte fully utilizes the cyberspace structure of polymer, thereby obtain conducting electrolyte and the battery capacity of corresponding effect, but the side chain of polymer too much can hinder the motion after electrolyte dissociation again.
At Chinese patent application 96197348.X, a kind of NEW TYPE OF COMPOSITE polyelectrolyte of being made by the closed pore porous polymer foaming body that has flooded nonaqueous electrolytic solution is disclosed, it comprises a plurality of closed pores that limited by hole wall, hole wall has formed the continuous solid phase parent with nonaqueous electrolytic solution dipping, form continuous solid phase microcell, wherein a plurality of closed pores have been filled nonaqueous electrolytic solution substantially to form a plurality of liquid phase micro-areas, and they are dispersed in above-mentioned continuous solid phase microcell.This invention composite polymer electrolyte not only has very high ionic conductance string and very high mechanical strength, and can prevent that nonaqueous electrolytic solution from leaking, so the electrolyte of this invention can be advantageously used in various non-aqueous electrochemical devices.That is to say, the non-aqueous electrochemical device that comprises composite polymer electrolyte of the present invention not only has good electrochemistry, and can maintain electrolyte wherein, and for this reason, this invention exists significantly not enough in manufacturing process.
Summary of the invention
The present invention is in order to overcome the deficiency of current solid electrolyte, adopt and the good organic lithium salt of polymer-compatible, its objective is in order to improve the dispersiveness of lithium salts in polymer, and then capacitance and the charge-discharge velocity of raising solid electrolyte, adopt the polymer that this side chain of polymethyl methacrylate is relatively less and side chain is short simultaneously, be in order to reduce the mobile obstruction under the effect of voltage of lithium ion and anion after lithium salts dissociation, thereby improve the conductance of this solid electrolyte and by this electrolyte, made the capacity of battery.
Its main technique comprises:
A manufacturing process for polymer solid electrolyte film, in its solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, and the content of lithium in polymer is 6～8%wt, and the manufacturing process that should contain the copolymer solid electrolyte of organolithium comprises:
A: high activity methylamino butyric acid lithium preparation:
1) under the protection of nitrogen, it is in the 1-METHYLPYRROLIDONE nmp solvent of 60～80 ℃ that the NaOH aqueous solution of 38%wt is added to temperature slowly, then the programming rate with 0.6～0.8 ℃/min is raised to 100～120 ℃ by temperature, and under this temperature conditions, reflux after insulation 3～4.5h, then 1.6～1.8 ℃/min programming rate is raised to 180～200 ℃ by temperature, and under this temperature conditions, insulation 30～45min refluxes, then, the cooling rate of 0.6～0.8 ℃/min of reactant mixture is reduced the temperature to 150～160 ℃, under this temperature conditions, add solid lithium chloride, the mol ratio of NaOH:LiCl:NMP is 1:1.003:3, after insulation 2～3h, stop refluxing, start vaporizer goes out the moisture content in back mixing compound, every 5min, detect the liquid component being evaporated, while accounting for 90% containing the amount of 1-METHYLPYRROLIDONE solvent in the liquid component evaporating, after having a large amount of white crystals to separate out, stop stirring and heating simultaneously, and insulation is while hot filtered under this temperature conditions, during filtration, with the 1-METHYLPYRROLIDONE solvent that reaction system same amount temperature is 30 ℃, constantly rinse white crystal,
2). by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanolic solution containing white crystal 20～30%wt, then heating water bath, is raised to 60～70 ℃ by temperature, and insulation backflow 45min, then, reduces the temperature to after 20～30 ℃, filters;
3). repeat 2), to after the filter cake cyclic washing that obtains 6～8 times, filter cake is inserted in the vacuum drying oven of 100～110 ℃ after dry 2～3h, it is stand-by that white crystal becomes the white powder that contains 30%～40%wt crystallization water; Through Fourier infrared spectrograph analyzing and testing gained white powder, be methylamino butyric acid lithium, purity is 99～99.95%;
The preparation of the acetone of the polymethyl methacrylate of B, organolithium and inorganic lithium-methanol solution
The white that A is obtained is that powder and inorganic lithium powder are dissolved in acetone-methyl alcohol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formation contains the solution that solid content is 2～3%wt, in temperature, be under the condition of 50～65 ℃, stirring and refluxing 2～3h, then, add plexiglass powder and 3～5% benzene polyacid ester type compounds in formula, thereby making organolithium and the inorganic lithium content in polymethyl methacrylate is 6～8%wt, in temperature, be under the condition of 50～55 ℃, stirring and refluxing 2～3h, polymethyl methacrylate is wherein dissolved among acetone-methyl alcohol mixed solvent completely, stand-by,
C, containing the copolymer solid electrolyte preparation of organolithium
By B) obtain being coated in Kynoar pellicle surface containing the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after acetone-methanol solvate is wherein evaporated completely, send out again and repeatedly apply 16～18 times, then form the solid electrolyte film containing the polymethyl methacrylate of organolithium and inorganic lithium, finally this solid electrolyte film is placed in to temperature and is the dry 2～2.5h of vacuum drying oven of 50～55 ℃, make the copolymer solid electrolyte object containing organolithium, the high conductivity of resulting polymers solid electrolyte is 8.12～9.36x10
-3s/cm, electrochemical stability window is 1.1～1.5V.
The high conductivity of the copolymer solid electrolyte that technique of the present invention obtains is 8.12～9.36x10
-3s/cm, electrochemical stability window is 5.1～5.5V, and the battery making is 450Q～650Q, and discharging and recharging number of times is 1300～1800 times, and capacity is 180～220mAh/g.
Accompanying drawing explanation
Fig. 1: the process chart of solid electrolyte of the present invention
Fig. 2: the correlated performance table of solid electrolyte of the present invention.
Embodiment:
Except special declaration, each chemical reagent relating in the application is chemical pure.
Under the protection of nitrogen, the mol ratio of NaOH:LiCl:NMP of take adds the NaOH aqueous solution of 50%wt in the 1-METHYLPYRROLIDONE organic solvent that temperature is 60 ℃ slowly as 1.00:1.003:3.00, then the programming rate with 1.8 ℃/min is raised to 100 ℃ by temperature, and under this temperature conditions, reflux after insulation 4.5h, then 2.8 ℃/min programming rate is raised to 180 ℃ by temperature, and under this temperature conditions, insulation 45min refluxes, then, the cooling rate of 0.8 ℃/min of reactant mixture is reduced the temperature to 150 ℃, under this temperature conditions, add solid lithium chloride, and be incubated after 3h, stop refluxing, start vaporizer goes out the moisture content in back mixing compound, every 5min, detect the liquid component being evaporated, while accounting for 90% containing the amount of 1-METHYLPYRROLIDONE solvent in the liquid component evaporating, after having a large amount of white crystals to separate out, stop stirring and heating simultaneously, and insulation is while hot filtered under this temperature conditions, during filtration, with the 1-METHYLPYRROLIDONE solvent that reaction system same amount temperature is 30 ℃, constantly rinse white crystal, the temperature of the colourless filtrate obtaining reduces the temperature to 60 ℃ with the cooling rate of 0.8 ℃/min, in filtrate, again separate out a large amount of white crystals, then under this temperature conditions, filter, the white crystal obtaining is dissolved in alcohol solvent, form the ethanolic solution containing white crystal 30%wt, then heating water bath, temperature is raised to 70 ℃, insulation backflow 45min, then, reduce the temperature to after 30 ℃, filter, filter cake is stand-by, recycling filtrate, the filter cake cyclic washing obtaining 8 times, then inserts filter cake in the vacuum drying oven of 110 ℃ after dry 2h, and it is the methylamino butyric acid lithium of purity 99.95% through Fourier infrared spectrograph analyzing and testing that white crystal becomes white powder, the methylamino butyric acid lithium white obtaining is that the inorganic lithium powder such as powder and lithium iodide are dissolved in acetone-methyl alcohol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formation contains the solution that solid content is 2%wt, in temperature, be under the condition of 65 ℃, stirring and refluxing 3h, then, add plexiglass powder and 5% trioctyl trimellitate (TOTM) compound in formula, thereby making methylamino butyric acid lithium and the lithium iodide content in polymethyl methacrylate is 6%wt, in temperature, be under the condition of 50 ℃, stirring and refluxing 3h, polymethyl methacrylate is wherein dissolved among acetone-methyl alcohol mixed solvent completely, obtain applying and Kynoar pellicle surface containing the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after acetone-methanol solvate is wherein evaporated completely, again apply the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 18 times, then form the solid electrolyte film containing the polymethyl methacrylate of organolithium and inorganic lithium, finally this solid electrolyte film is placed in to temperature and is the dry 2h of vacuum drying oven of 55 ℃, so just made the polymer solid electrolyte film containing organolithium.The high conductivity of this copolymer solid electrolyte is 8.12x10
-3s/cm, electrochemical stability window is 1.1V, and be 650Q useful life, and discharging and recharging number of times is 1800 times, and capacity is 180mAh/g.
Under the protection of nitrogen, the mol ratio of NaOH:LiCl:NMP of take adds the NaOH aqueous solution of 50%wt in the 1-METHYLPYRROLIDONE organic solvent that temperature is 80 ℃ slowly as 1.00:1.003:3.00, then the programming rate with 1.6 ℃/min is raised to 120 ℃ by temperature, and under this temperature conditions, reflux after insulation 3h, then 2.6 ℃/min programming rate is raised to 200 ℃ by temperature, and under this temperature conditions, insulation 30min refluxes, then, the cooling rate of 0.6 ℃/min of reactant mixture is reduced the temperature to 160 ℃, under this temperature conditions, add solid lithium chloride, and be incubated after 2h, stop refluxing, start vaporizer goes out the moisture content in back mixing compound, every 5min, detect the liquid component being evaporated, while accounting for 90% containing the amount of 1-METHYLPYRROLIDONE solvent in the liquid component evaporating, after having a large amount of white crystals to separate out, stop stirring and heating simultaneously, and insulation is while hot filtered under this temperature conditions, during filtration, with the 1-METHYLPYRROLIDONE solvent that reaction system same amount temperature is 30 ℃, constantly rinse white crystal, the temperature of the colourless filtrate obtaining reduces the temperature to 50 ℃ with the cooling rate of 0.6 ℃/min, in filtrate, again separate out a large amount of white crystals, then under this temperature conditions, filter, the white crystal obtaining is dissolved in alcohol solvent, form the ethanolic solution containing white crystal 20%wt, then heating water bath, temperature is raised to 60 ℃, insulation backflow 45min, then, reduce the temperature to after 20 ℃, filter, filter cake is stand-by, recycling filtrate, the filter cake cyclic washing obtaining 6 times, then inserts filter cake in the vacuum drying oven of 100 ℃ after dry 3h, and it is the methylamino butyric acid lithium of purity 99～% through Fourier infrared spectrograph analyzing and testing that white crystal becomes white powder, the methylamino butyric acid lithium white obtaining is that the inorganic lithium powder such as powder and lithium iodate are dissolved in acetone-methyl alcohol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formation contains the solution that solid content is 3%wt, in temperature, be under the condition of 50 ℃, stirring and refluxing 3h, then, add plexiglass powder and the own ester compounds of 3% tri trimellitate in formula, thereby making methylamino butyric acid lithium and lithium iodide or the lithium iodate content in polymethyl methacrylate is 8%wt, in temperature, be under the condition of 55 ℃, stirring and refluxing 2h, polymethyl methacrylate is wherein dissolved among acetone-methyl alcohol mixed solvent completely, obtain applying and Kynoar pellicle surface containing the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after acetone-methanol solvate is wherein evaporated completely, again apply the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 16 times, then form the solid electrolyte film containing the polymethyl methacrylate of organolithium and inorganic lithium, finally this solid electrolyte film is placed in to temperature and is the dry 2.5h of vacuum drying oven of 55 ℃, so just made the polymer solid electrolyte film containing organolithium.The high conductivity of this copolymer solid electrolyte is 9.36x10
-3s/cm, electrochemical stability window is 1.5V, and be 450Q useful life, and discharging and recharging number of times is 1300 times, and capacity is 180mAh/g.
Under the protection of nitrogen, the mol ratio of NaOH:LiCl:NMP of take adds the NaOH aqueous solution of 50%wt in the 1-METHYLPYRROLIDONE organic solvent that temperature is 7080 ℃ slowly as 1.00:1.003:3.00, then the programming rate with 1.7 ℃/min is raised to 110 ℃ by temperature, and under this temperature conditions, reflux after insulation 4.0h, then 2.7 ℃/min programming rate is raised to 190 ℃ by temperature, and under this temperature conditions, insulation 40min refluxes, then, the cooling rate of 0.7 ℃/min of reactant mixture is reduced the temperature to 155 ℃, under this temperature conditions, add solid lithium chloride, and be incubated after 2.5h, stop refluxing, start vaporizer goes out the moisture content in back mixing compound, every 5min, detect the liquid component being evaporated, while accounting for 90% containing the amount of 1-METHYLPYRROLIDONE solvent in the liquid component evaporating, after having a large amount of white crystals to separate out, stop stirring and heating simultaneously, and insulation is while hot filtered under this temperature conditions, during filtration, with the 1-METHYLPYRROLIDONE solvent that reaction system same amount temperature is 30 ℃, constantly rinse white crystal, the temperature of the colourless filtrate obtaining reduces the temperature to 555 ℃ with the cooling rate of 0.7 ℃/min, in filtrate, again separate out a large amount of white crystals, then under this temperature conditions, filter, the white crystal obtaining is dissolved in alcohol solvent, form the ethanolic solution containing white crystal 26%wt, then heating water bath, temperature is raised to 650 ℃, insulation backflow 45min, then, reduce the temperature to after 28 ℃, filter, filter cake is stand-by, recycling filtrate, the filter cake cyclic washing obtaining 7 times, then inserts filter cake in the vacuum drying oven of 108 ℃ after dry 2.6h, and it is the methylamino butyric acid lithium of purity 99.91% through Fourier infrared spectrograph analyzing and testing that white crystal becomes white powder, the methylamino butyric acid lithium white obtaining is that the inorganic lithium powder such as powder and lithium iodide and lithium iodate (each 50%) are dissolved in acetone-methyl alcohol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formation contains the solution that solid content is 2.5%wt, in temperature, be under the condition of 60 ℃, stirring and refluxing 2.8h, then, add the plexiglass powder and 4%1 in formula, 2, 4-triisooctyl trimellitate compound, thereby making methylamino butyric acid lithium and lithium iodide and lithium iodate (each the 50%) content in polymethyl methacrylate is 6.8%wt, in temperature, be under the condition of 53 ℃, stirring and refluxing 2.6h, polymethyl methacrylate is wherein dissolved among acetone-methyl alcohol mixed solvent completely, obtain applying and Kynoar pellicle surface containing the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after acetone-methanol solvate is wherein evaporated completely, again apply the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 17 times, then form the solid electrolyte film containing the polymethyl methacrylate of organolithium and inorganic lithium, finally this solid electrolyte film is placed in to temperature and is the dry 2.3h of vacuum drying oven of 3 ℃, so just made the polymer solid electrolyte film containing organolithium.The high conductivity of this copolymer solid electrolyte is 8.83x10
-3s/cm, electrochemical stability window is 1.3V, and be 584Q useful life, and discharging and recharging number of times is 1531 times, capacity 200mAh/g.
Comparative example 1
The inorganic lithium powder such as commercially available chemical pure methylamino sodium butyrate white powder and lithium iodate are dissolved in acetone-methyl alcohol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formation contains the solution that solid content is 3%wt, in temperature, be under the condition of 65 ℃, stir back 2.3h, then, add the plexiglass powder and 4%1 in formula, 2, 4-triisooctyl trimellitate compound, thereby make methylamino sodium butyrate and lithium iodide or the lithium iodate content 8%wt in polymethyl methacrylate, in temperature, be under the condition of 50～55 ℃, stirring and refluxing 2～3h, polymethyl methacrylate is wherein dissolved among acetone-methyl alcohol mixed solvent completely, obtain applying and Kynoar pellicle surface containing the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after acetone-methanol solvate is wherein evaporated completely, again apply the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 18 times, then form the solid electrolyte film containing the polymethyl methacrylate of organolithium and inorganic lithium, finally this solid electrolyte film is placed in to temperature and is the dry 2.5h of vacuum drying oven of 55 ℃, so just made the polymer solid electrolyte film containing organic sodium.The high conductivity of this copolymer solid electrolyte is 9.10x10
-6s/cm, electrochemical stability window is 1.0V, and the battery making is 80Q, and discharging and recharging number of times is 302 times, and capacity is 1.3mAh/g.
Claims (3)
1. a manufacturing process for polymer solid electrolyte film, in its solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, the content of lithium in polymer is 6～8%wt, should comprise containing manufacturing process of the copolymer solid electrolyte of organolithium:
A: high activity methylamino butyric acid lithium preparation:
1) under the protection of nitrogen, it is in the 1-METHYLPYRROLIDONE nmp solvent of 60～80 ℃ that the NaOH aqueous solution of 38%wt is added to temperature slowly, then the programming rate with 0.6～0.8 ℃/min is raised to 100～120 ℃ by temperature, and under this temperature conditions, reflux after insulation 3～4.5h, then 1.6～1.8 ℃/min programming rate is raised to 180～200 ℃ by temperature, and under this temperature conditions, insulation 30～45min refluxes, then, the cooling rate of 0.6～0.8 ℃/min of reactant mixture is reduced the temperature to 150～160 ℃, under this temperature conditions, add solid lithium chloride, the mol ratio of NaOH:LiCl:NMP is 1:1.003:3, after insulation 2～3h, stop refluxing, start vaporizer goes out the moisture content in back mixing compound, every 5min, detect the liquid component being evaporated, while accounting for 90% containing the amount of 1-METHYLPYRROLIDONE solvent in the liquid component evaporating and after having a large amount of white crystals to separate out, stop stirring and heating, and insulation is while hot filtered under this temperature conditions, during filtration, with the 1-METHYLPYRROLIDONE solvent that reaction system same amount temperature is 30 ℃, constantly rinse white crystal filter cake,
2). by 1) the white crystal filter cake that obtains is dissolved in alcohol solvent, forms the ethanolic solution containing white crystal 20～30%wt, then heating water bath, is raised to 60～70 ℃ by temperature, and insulation backflow 45min, then, reduces the temperature to after 20～30 ℃, filters;
3). repeat 2), to after the filter cake cyclic washing that obtains 6～8 times, filter cake is inserted in the vacuum drying oven of 100～110 ℃ after dry 2～3h, it is stand-by that white crystal becomes the white powder that contains 30%～40%wt crystallization water; Through Fourier infrared spectrograph analyzing and testing gained white powder, be methylamino butyric acid lithium, purity is 99～99.95%;
The preparation of the acetone of the polymethyl methacrylate of B, organolithium and inorganic lithium-methanol solution
The white that A is obtained is that powder and inorganic lithium powder are dissolved in acetone-methyl alcohol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formation contains the solution that solid content is 2～3%wt, in temperature, be under the condition of 50～65 ℃, stirring and refluxing 2～3h, then, add plexiglass powder and 3～5% benzene polyacid ester type compounds in formula, thereby making organolithium and the inorganic lithium content in polymethyl methacrylate is 6～8%wt, in temperature, be under the condition of 50～55 ℃, stirring and refluxing 2～3h, polymethyl methacrylate is wherein dissolved among acetone-methyl alcohol mixed solvent completely, stand-by,
C, containing the copolymer solid electrolyte preparation of organolithium
By B) obtain being coated in Kynoar pellicle surface containing the acetone-methanol solution of the polymethyl methacrylate of organolithium and inorganic lithium, after acetone-methanol solvate is wherein evaporated completely, send out again and repeatedly apply 16～18 times, then form the solid electrolyte film containing the polymethyl methacrylate of organolithium and inorganic lithium, finally this solid electrolyte film is placed in to temperature and is the dry 2～2.5h of vacuum drying oven of 50～55 ℃, make the copolymer solid electrolyte object containing organolithium, the high conductivity of resulting polymers solid electrolyte is 8.12～9.36x10
-3s/cm, electrochemical stability window is 1.1～1.5V.
2. the manufacturing process of polymer solid electrolyte film according to claim 1, is characterized in that, described inorganic lithium can be lithium iodide or lithium iodate.
3. the manufacturing process of polymer solid electrolyte film according to claim 1, it is characterized in that, described benzene polyacid ester type compound is a kind of of following material: trioctyl trimellitate (TOTM), the own ester of tri trimellitate, PMA four esters, 1,2,4-triisooctyl trimellitate.
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| CN106450443A (en) * | 2016-09-30 | 2017-02-22 | 上海空间电源研究所 | Dual-lithium-salt compounded PEO-based polymer electrolyte and preparation method therefor |
| CN109167090A (en) * | 2018-08-28 | 2019-01-08 | 长沙矿冶研究院有限责任公司 | A kind of film build method of polymer-based solid state electrolyte |
| CN114478328A (en) * | 2020-10-27 | 2022-05-13 | 上海漫关越水处理有限公司 | Ionic membrane compound of lithium air battery tert-aryl ether diene difluoromethyl sulfonate |
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| US20070248888A1 (en) * | 2004-06-04 | 2007-10-25 | Idemitsu Kosan Co., Ltd. | High-Performance All-Solid Lithium Battery |
| CN102299376A (en) * | 2011-06-24 | 2011-12-28 | 中国科学院宁波材料技术与工程研究所 | Polymer solid electrolyte membrane and preparation method thereof |
| CN103208651A (en) * | 2013-03-26 | 2013-07-17 | 中南大学 | Siloxane-based solid electrolyte and preparation and application thereof |
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| US20070160911A1 (en) * | 2004-02-12 | 2007-07-12 | Masahiro Tatsumisago | Lithium ion conducting sulfide based crystallized glass and method for production thereof |
| US20070248888A1 (en) * | 2004-06-04 | 2007-10-25 | Idemitsu Kosan Co., Ltd. | High-Performance All-Solid Lithium Battery |
| CN102299376A (en) * | 2011-06-24 | 2011-12-28 | 中国科学院宁波材料技术与工程研究所 | Polymer solid electrolyte membrane and preparation method thereof |
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| CN106450443A (en) * | 2016-09-30 | 2017-02-22 | 上海空间电源研究所 | Dual-lithium-salt compounded PEO-based polymer electrolyte and preparation method therefor |
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