CN103456981A - Manufacturing method of organic lithium-containing polymer solid electrolyte film - Google Patents
Manufacturing method of organic lithium-containing polymer solid electrolyte film Download PDFInfo
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Abstract
The invention discloses a manufacturing method of an organic lithium-containing polymer solid electrolyte film. The raw material methylaminobutyric acid lithium is obtained by reacting a NaOH aqueous solution of a certain concentration with N-methyl pyrrolidone under the protection of nitrogen and then adding lithium chloride to replace sodium ions in the reaction product. The mixtures of the obtained methylaminobutyric acid lithium and lithium iodide or lithium iodate and polymethyl methacrylate and a benzene polycarboxylic acid ester plasticizer are extruded through three different double-screw extruders from T-shaped molds at the heads respectively and then drawn in a thermal insulation manner to obtain a target, i.e., the organic lithium-containing polymer solid electrolyte film. The organic lithium and inorganic lithium compounds in the solid electrolyte film have good compatibility with a polymer; the manufactured all-solid lithium battery has stable charging and discharging performances and has the characteristics of long service life, high charging and discharging frequency, high battery capacity and the like.
Description
Technical field
The present invention relates to secondary cell, especially the 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, the type lithium ion battery is high with energy density, the characteristics such as can charge rapidly progressively cause showing great attention to of people, with other the battery such as nickel-cadmium cell, compare, high and rapid these characteristics of charging based on energy content of battery density, the expectation that people benefit from long novel lithium battery copolymer solid electrolyte film of life-span to high-efficient high-capacity three amount high charge number of times strengthens day by day.
In-primary cell or the electrochemical elements such as 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 that element is manufactured, 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, due to the restriction that is subject to 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, at 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 that will contain inorganic lithium salt, form a kind of gel electrolyte film that contains inorganic lithium salt, although done further investigation by Abraham etc. afterwards.Polymer gel is generally defined as a system of the polymer network by 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 polymer Li-ion battery with the research of 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 have ionic conductivity and to have the barrier film effect concurrently-electrolyte to replace the electrolyte in liquid lithium ionic cell, gel electrolyte is the gelatin polymer network with suitable microcellular structure 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 formed by polymer matrix and doping salt. make salt be dissolved in macromolecule and form homogeneous solution, if must have 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 just is 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 there is strong the interaction between the PPG ether oxygen atom. they also find that the membership that adds of salt significantly improves the PPG glass transition temperature, LiClO
4when content reaches 25%, the T g of PPG (MW2000) is increased to 40 ℃ by-70 ℃. and 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) is with such as lithium salts, such electrolytic salt has formed crystalline complex compound and since showing high ionic conductivity, using PEO or other polyalkylene oxide, also have the polymine that there is equally the ionic dissociation base in molecule or polyphosphazene etc. just to 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 thin film strength or thermal endurance on the contrary significantly, thereby the solid electrolyte that obtains practicality is difficult, if have 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 polymer solid electrolyte of the ABA type triblock copolymer of methoxy poly (ethylene glycol) monomethacrylates (A) and styrene (B) copolymerization as the 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 electrolyte , The melting temperature of the polymer below its 60℃ SPE is typically made of a polymer phase , a polymer and a lithium salt and a solvate salt formed crystalline polymer amorphous form under the action of the ionic conducting mechanism shows: occurs mainly in the amorphous region and due to the proximity of the polymer chain segment motion helps to promote the coordination bonds between polymer Li<sup TranNum= and breakage of the formed Li<sup TranNum= migration provides free volume so as to reduce the degree of crystallinity of the polymer and a glass transition temperature ( Tg ) of the polymer chains to improve flexibility and increase the free volume density helps to achieve high spe without the polymer assn. Line: :anionic generally recognized by the vacancy of dielectric and conductive polymers , on the other hand , ions and ions , there exists a strong interaction between the SPE , in addition to free anions and solvated cations there are solvated ions on 3 closely-overlaps experiment:a aggregates and other ions body which determines the carrier concentration and mobility of the SPE .But, among the solid electrolyte film formed by polymer and lithium salts, electrical conduction mechanism according to lithium salts, under certain voltage, make lithium salts be dissociated into zwitterion, these zwitterions are under the effect of voltage, directional migration occurs, but, play supporting role in solid electrolyte due to polymer, simultaneously, be subject to the restriction of the structure of polymer, if this polymer is crystal structure, can make lithium salts hinder the motion of these zwitterions from separating the zwitterion formed under the effect of voltage, therefore, capacity for the electric conduction quantity that improves solid electrolyte and the battery 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: 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 in 03817326.3, total solids electrolyte particularly, and the copolymer compositions become for the manufacture of this electrolytical matrix is purpose.This polymer solid electrolyte contains copolymer and electrolytic salt, has the block chain A of the repetitive meaned with formula (I) in this copolymer, have with formula (II) (in formula, R
9mean aryl) the block chain B of the repetitive that means and have with formula (III) (in formula, R
13meaning aryl or heteroaryl) the block chain C of the repetitive that means 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, with other polymer, compare, 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 again electrolyte from the motion after solution.
At Chinese Patent Application No. code 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 the nonaqueous electrolytic solution dipping, form the continuous solid phase microcell, wherein a plurality of closed pores have been filled nonaqueous electrolytic solution basically 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 on manufacturing process.
Above shortcoming in view of prior art, the objective of the invention is to overcome the deficiency of current solid electrolyte, adopt and the good organic lithium salt of polymer-compatible, it is 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, reduce lithium salts from lithium ion after separating and anion mobile obstruction under the effect of voltage, thereby improve the conductance of this solid electrolyte and made the capacity of battery by this electrolyte.
Summary of the invention
It is as follows that the present invention realizes that the main technique of goal of the invention comprises.
A kind of manufacture method of the copolymer solid electrolyte film containing organolithium, the methylamino butyric acid lithium that to process through high activity and the mixture of inorganic lithium are extruded through double screw extruder, T-shaped mould through head forms the sheet material that thickness is the wide 12～24mm of being of 6～8mm, this solid electrolyte sheet material is clipped in the centre that other two double screw extruders are extruded the polymethyl methacrylate sheet material of same width and thickness, then the insulation path drawing-off that is 100～120 ℃ through excess temperature becomes the thick copolymer solid electrolyte film containing organolithium of the wide and 0.6～1.0mm of 600～1200mm, in solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, the content of lithium in polymer is 6～8%wt, its manufacturing process comprises:
A: high activity methylamino butyric acid lithium preparation:
1) under the protection of nitrogen, the NaOH aqueous solution of 38%wt is added in the 1-METHYLPYRROLIDONE nmp solvent that temperature is 60～80 ℃ slowly, then the programming rate with 0.6～0.8 ℃/min is raised to 100～120 ℃ by temperature, and under this temperature conditions, after backflow 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 ℃, add the solid lithium chloride under this temperature conditions, 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 the back mixing compound, detect the liquid component be evaporated every 5min, in the liquid component evaporated containing the amount of 1-METHYLPYRROLIDONE solvent account for 90% and a large amount of white crystal stop stirring and heating after separating out, and insulation is filtered while hot, the 1-METHYLPYRROLIDONE solvent that is 30 ℃ by temperature after filtering constantly rinses white crystal and leaches thing,
2) by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanolic solution containing white crystal 20～30%wt, and then heating water bath, be raised to 60～70 ℃ by temperature, and then insulation backflow 45min, after reducing the temperature to 20～30 ℃, filters;
4) repeat 3) to after the filter cake cyclic washing that obtains 6～8 times, filter cake to be 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; The gained white powder is that purity is 99～99.95% methylamino butyric acid lithiums;
B: containing the copolymer solid electrolyte film preparation of organolithium
The white powder that the A step is obtained and inorganic lithium powder, by the mol ratio of 3:1, mix in high speed agitator, and the double screw extruder that then input temp is 200～220 ℃ is extruded into sheet material by the head T mould of extruder, the polymethyl methacrylate that then will add many esters of gallic acid of benzene plasticiser input temp respectively is that 268～288 ℃ of two double screw extruders are extruded, in the sheet material blender, the sheet material of organolithium and inorganic lithium mixture is clipped in the middle, the sheet material that formation contains polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, become the copolymer solid electrolyte film containing organolithium through 6～8 grades of two-way drawing-offs, obtain the copolymer solid electrolyte film of object containing organolithium, the high conductivity of its solid electrolyte is 8.12～9.36x10
-3s/cm, electrochemical stability window is 5.1～5.5V.
Described inorganic lithium can be lithium iodide or lithium iodate.
One of described many esters of gallic acid of benzene plasticiser comprises trioctyl trimellitate (TOTM), the own ester of tri trimellitate, PMA four esters, 1,2, in the 4-triisooctyl trimellitate.
Consider the raising yield, described A step the 1) cooling rate with 0.6～0.8 ℃/min of step gained filtrate reduces the temperature to 50～60 ℃, again separate out a large amount of white crystals in filtrate, then under this temperature conditions, filter the white crystal obtain and be incorporated to the 2nd as raw material) in the white crystal of step.The filtrate of corresponding each step recycles.
In products therefrom solid electrolyte film of the present invention, the compatibility of organolithium and inorganic lithium compound and polymer is good, organolithium and inorganic lithium compound being evenly distributed in polymethyl methacrylate, thereby make the charge-discharge performance of the all-solid lithium battery manufactured by this electrolyte stable, be 438Q～638Q useful life, discharging and recharging number of times is 1300～1800 times, and capacity is 180～220mAh/g; It discharges and recharges number of times and useful life and capacitance will improve respectively 38～120% than current lithium battery is corresponding.
The accompanying drawing explanation:
Fig. 1 is technique line of fall schematic diagram of the present invention.
Fig. 2 is the embodiment of the present invention performance table of comparisons.
Embodiment:
Except special declaration, each chemical reagent related in the application is chemical pure.
Embodiment 1
Under the protection of nitrogen, the mol ratio of NaOH:LiCl:NMP of take adds the NaOH aqueous solution of 38%wt in the 1-METHYLPYRROLIDONE organic solvent that temperature is 60 ℃ slowly as 1.00:1.003:3.00, then the programming rate with 0.8 ℃/min is raised to 100 ℃ by temperature, and under this temperature conditions, after backflow insulation 4.5h, then 1.8 ℃/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 ℃, add the solid lithium chloride under this temperature conditions, and after insulation 3h, stop refluxing, start vaporizer goes out the moisture content in the back mixing compound, detect the liquid component be evaporated every 5min, while in the liquid component evaporated, containing the amount of 1-METHYLPYRROLIDONE solvent, accounting for 90%, 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, the 1-METHYLPYRROLIDONE solvent that is 30 ℃ by reaction system same amount temperature during filtration constantly rinses white crystal, the temperature of the colourless filtrate obtained reduces the temperature to 60 ℃ with the cooling rate of 0.8 ℃/min, again separate out a large amount of white crystals in filtrate, then under this temperature conditions, filter, the white crystal obtained 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, after reducing the temperature to 30 ℃, filter, filter cake is stand-by, recycling filtrate, the filter cake cyclic washing obtained 8 times, then insert filter cake in the vacuum drying oven of 110 ℃ after dry 2h, and white crystal becomes the methylamino butyric acid lithium that the white powder that contains the 30%wt crystallization water is purity 99.95% through the Fourier infrared spectrograph analyzing and testing, the methylamino butyric acid lithium that obtains white is dissolved in the 5:1 mass ratio for inorganic lithium powder such as powder and lithium iodides by the mol ratio of 3:1, in high speed agitator, mix, then the double screw extruder that input temp is 200 ℃, by the head T mould of extruder extrude thickness be 6mm wide be the sheet material of 16mm, then will add the polymethyl methacrylate of 3%wt trioctyl trimellitate (TOTM) is that 268 ℃ of two double screw extruders are extruded by temperature respectively, in the sheet material blender, the sheet material of organolithium and inorganic lithium mixture is clipped in the middle, the sheet material that formation contains polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, become to contain through 6 grades of drawing-offs the copolymer solid electrolyte film that 6%wt thickness is the 0.6mm organolithium, the high conductivity of this copolymer solid electrolyte is 8.12x10
-3s/cm, electrochemical stability window is 1.1V, and be 638Q useful life, and discharging and recharging number of times is 1800 times, and capacity is 180mAh/g.
Embodiment 2
Under the protection of nitrogen, the mol ratio of NaOH:LiCl:NMP of take adds the NaOH aqueous solution of 38%wt in the 1-METHYLPYRROLIDONE organic solvent that temperature is 80 ℃ slowly as 1.00:1.003:3.00, then the programming rate with 0.6 ℃/min is raised to 120 ℃ by temperature, and under this temperature conditions, after backflow insulation 3h, then 1.6 ℃/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 ℃, add the solid lithium chloride under this temperature conditions, and after insulation 2h, stop refluxing, start vaporizer goes out the moisture content in the back mixing compound, detect the liquid component be evaporated every 5min, while in the liquid component evaporated, containing the amount of 1-METHYLPYRROLIDONE solvent, accounting for 90%, 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, the 1-METHYLPYRROLIDONE solvent that is 30 ℃ by reaction system same amount temperature during filtration constantly rinses white crystal, the temperature of the colourless filtrate obtained reduces the temperature to 38 ℃ with the cooling rate of 0.6 ℃/min, again separate out a large amount of white crystals in filtrate, then under this temperature conditions, filter, the white crystal obtained 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, after reducing the temperature to 20 ℃, filter, filter cake is stand-by, recycling filtrate, the filter cake cyclic washing obtained 6 times, then insert filter cake in the vacuum drying oven of 100 ℃ after dry 3h, and white crystal becomes the methylamino butyric acid lithium that the white powder that contains the 40%wt crystallization water is purity 99～% through the Fourier infrared spectrograph analyzing and testing, the methylamino butyric acid lithium that obtains white is dissolved in the 5:1 mass ratio for inorganic lithium powder such as powder and lithium iodates by the mol ratio of 3:1, in high speed agitator, mix, then the double screw extruder that input temp is 220 ℃, by the head T mould of extruder, extruding thickness 8mm wide is the sheet material of 24mm, then will add the polymethyl methacrylate of the own ester of 5%wt tri trimellitate is that 288 ℃ of two double screw extruders are extruded by temperature respectively, in the sheet material blender, the sheet material of organolithium and inorganic lithium mixture is clipped in the middle, the sheet material that formation contains polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, become to contain through 8 grades of drawing-offs the copolymer solid electrolyte film that 8%wt thickness is the 1.0mm organolithium, the high conductivity of this copolymer solid electrolyte is 9.36x10
-3s/cm, electrochemical stability window is 1.5V, and be 438Q useful life, and discharging and recharging number of times is 1300 times, and capacity is 180mAh/g.
Embodiment 3
Under the protection of nitrogen, the mol ratio of NaOH:LiCl:NMP of take adds the NaOH aqueous solution of 38%wt in the 1-METHYLPYRROLIDONE organic solvent that temperature is 7080 ℃ slowly as 1.00:1.003:3.00, then the programming rate with 0.7 ℃/min is raised to 110 ℃ by temperature, and under this temperature conditions, after backflow insulation 4.0h, then 1.7 ℃/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 ℃, add the solid lithium chloride under this temperature conditions, and after insulation 2.5h, stop refluxing, start vaporizer goes out the moisture content in the back mixing compound, detect the liquid component be evaporated every 5min, while in the liquid component evaporated, containing the amount of 1-METHYLPYRROLIDONE solvent, accounting for 90%, 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, the 1-METHYLPYRROLIDONE solvent that is 30 ℃ by reaction system same amount temperature during filtration constantly rinses white crystal, the temperature of the colourless filtrate obtained reduces the temperature to 555 ℃ with the cooling rate of 0.7 ℃/min, again separate out a large amount of white crystals in filtrate, then under this temperature conditions, filter, the white crystal obtained is dissolved in alcohol solvent, form the ethanolic solution containing white crystal 26%wt, then heating water bath, temperature is raised to 638 ℃, insulation backflow 45min, then, after reducing the temperature to 28 ℃, filter, filter cake is stand-by, recycling filtrate, the filter cake cyclic washing obtained 7 times, then insert filter cake in the vacuum drying oven of 108 ℃ after dry 2.6h, and white crystal becomes the methylamino butyric acid lithium that the white powder that contains the 36%wt crystallization water is purity 99.91% through the Fourier infrared spectrograph analyzing and testing, the mol ratio that the methylamino butyric acid lithium white obtained is pressed 3:1 for inorganic lithium powder such as powder and lithium iodide and lithium iodates (each 38%), in high speed agitator, mix, then the double screw extruder that input temp is 218 ℃, by the head T mould of extruder extrude thickness be 9mm wide be the sheet material of 18mm, then will add 1 of 4%wt, 2, the polymethyl methacrylate of 4-triisooctyl trimellitate is that 283 ℃ of two double screw extruders are extruded by temperature respectively, in the sheet material blender, the sheet material of organolithium and inorganic lithium mixture is clipped in the middle, the sheet material that formation contains polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, become to contain through 7 grades of drawing-offs the copolymer solid electrolyte film that 7.1%wt thickness is the 0.8mm 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.
The comparative example 1
Adopt the mol ratio of the inorganic lithium powder such as commercially available chemical pure methylamino butyric acid lithium and lithium iodate by 1:3, in high speed agitator, mix, then the double screw extruder that input temp is 220 ℃, by the head T mould of extruder extrude thickness be 8mm wide be the sheet material of 24mm, then will add the polymethyl methacrylate of PMA four esters is that 283 ℃ of two double screw extruders are extruded by temperature respectively, in the sheet material blender, the sheet material of organolithium and inorganic lithium mixture is clipped in the middle, the sheet material that formation contains polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, become to contain through 8 grades of drawing-offs the copolymer solid electrolyte film that 8%wt thickness is the 1.0mm organolithium, the high conductivity of this copolymer solid electrolyte is 7.82x10
-5s/cm, electrochemical stability window is 1.1V, and be 280Q useful life, and discharging and recharging number of times is 902 times, and capacity is 270mAh/g.
Process comparative example known in conjunction with Fig. 2 data: the activity of methylamino butyric acid lithium and its manufacturing process close association adopt the present invention's active copolymer solid electrolyte film of processing the raw material acquisition used to have better performance characteristic.
Claims (4)
1. the manufacture method containing the copolymer solid electrolyte film of organolithium, the methylamino butyric acid lithium that to process through high activity and the mixture of inorganic lithium are extruded through double screw extruder, T-shaped mould through head forms the sheet material that thickness is the wide 12～24mm of being of 6～8mm, this solid electrolyte sheet material is clipped in the centre that other two double screw extruders are extruded the polymethyl methacrylate sheet material of same width and thickness, then the insulation path drawing-off that is 100～120 ℃ through excess temperature becomes the thick copolymer solid electrolyte film containing organolithium of the wide and 0.6～1.0mm of 600～1200mm, in solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, the content of lithium in polymer is 6～8%wt, its manufacturing process comprises:
A: high activity methylamino butyric acid lithium preparation:
1) under the protection of nitrogen, the NaOH aqueous solution of 38%wt is added in the 1-METHYLPYRROLIDONE nmp solvent that temperature is 60～80 ℃ slowly, then the programming rate with 0.6～0.8 ℃/min is raised to 100～120 ℃ by temperature, and under this temperature conditions, after backflow 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 ℃, add the solid lithium chloride under this temperature conditions, 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 the back mixing compound, detect the liquid component be evaporated every 5min, in the liquid component evaporated containing the amount of 1-METHYLPYRROLIDONE solvent account for 90% and a large amount of white crystal stop stirring and heating after separating out, and insulation is filtered while hot, the 1-METHYLPYRROLIDONE solvent that is 30 ℃ by temperature after filtering constantly rinses white crystal and leaches thing,
2) by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanolic solution containing white crystal 20～30%wt, and then heating water bath, be raised to 60～70 ℃ by temperature, and then insulation backflow 45min, after reducing the temperature to 20～30 ℃, filters;
4) repeat 3) to after the filter cake cyclic washing that obtains 6～8 times, filter cake to be 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; The gained white powder is that purity is 99～99.95% methylamino butyric acid lithiums;
B: containing the copolymer solid electrolyte film preparation of organolithium
The white powder that the A step is obtained and inorganic lithium powder, by the mol ratio of 3:1, mix in high speed agitator, and the double screw extruder that then input temp is 200～220 ℃ is extruded into sheet material by the head T mould of extruder, the polymethyl methacrylate that then will add many esters of gallic acid of benzene plasticiser input temp respectively is that 268～288 ℃ of two double screw extruders are extruded, in the sheet material blender, the sheet material of organolithium and inorganic lithium mixture is clipped in the middle, the sheet material that formation contains polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, become the copolymer solid electrolyte film containing organolithium through 6～8 grades of two-way drawing-offs, obtain the copolymer solid electrolyte film of object containing organolithium, the high conductivity of its solid electrolyte is 8.12～9.36x10
-3s/cm, electrochemical stability window is 5.1～5.5V.
2. a kind of manufacture method of the copolymer solid electrolyte film containing organic lithium according to claim 1, is characterized in that, described inorganic lithium can be lithium iodide or lithium iodate.
3. a kind of manufacture method of the copolymer solid electrolyte film containing organic lithium according to claim 1, it is characterized in that this many esters of gallic acid of benzene plasticiser is trioctyl trimellitate (TOTM), the own ester of tri trimellitate, PMA four esters, 1, one of 2,4-triisooctyl trimellitate.
4. a kind of manufacture method of the copolymer solid electrolyte film containing organic lithium according to claim 1, it is characterized in that, described A step the 1) cooling rate with 0.6～0.8 ℃/min of step gained filtrate reduces the temperature to 50～60 ℃, again separate out a large amount of white crystals in filtrate, then under this temperature conditions, filter the white crystal obtain and be incorporated to the 2nd as raw material) in the white crystal of step.
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| CN114075125A (en) * | 2020-08-13 | 2022-02-22 | 上海漫关越水处理有限公司 | Long-chain alkyl fluorine-containing sulfonate ionic membrane compound for blocking water permeation of lithium-air battery |
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| 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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