CN103456981B - A kind of manufacture method of the copolymer solid electrolyte thin film containing organolithium - Google Patents
A kind of manufacture method of the copolymer solid electrolyte thin film containing organolithium Download PDFInfo
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- CN103456981B CN103456981B CN201310419213.3A CN201310419213A CN103456981B CN 103456981 B CN103456981 B CN 103456981B CN 201310419213 A CN201310419213 A CN 201310419213A CN 103456981 B CN103456981 B CN 103456981B
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Abstract
The invention discloses the manufacture method of a kind of copolymer solid electrolyte thin film containing organolithium; its raw material methylaminobutyric acid lithium uses certain density NaOH aqueous solution under the protection of nitrogen; after N crassitude reactive ketone, add lithium chloride and obtain to displace sodium ion therein.Then the methylaminobutyric acid lithium obtained is obtained target copolymer solid electrolyte thin film containing organolithium respectively through three different double screw extruders from the T-shaped mould extruded molded heat insulation drawing-off of head from the mixture of polymethyl methacrylate and benzene many esters of gallic acid plasticiser with lithium iodide or lithium iodate, in this solid electrolyte film, organolithium and inorganic lithium compound are good with the compatibility of polymer, the charge-discharge performance of the all-solid lithium battery manufactured is stable, there is service life long, discharge and recharge often, the features such as battery capacity is big.
Description
Technical field
The present invention relates to secondary cell, especially polymer solid electrolyte field of thin film fabrication.
Background technology
Battery is used as the power supply of the electrical equipment such as torch and phone very early by people, along with progress and the green wood of science and technology
The discovery of material, it has been developed that Ni-MH battery and lithium battery, along with mobile phone and notebook computer etc. are portable
The appearance of electrical equipment, seems increasingly stronger to the demand of the high performance of battery and miniaturization etc., is full
This demand of foot, lithium-ion type battery is high with energy density, it is possible to the features such as rapid charging progressively cause people
Highest attention, compared with other the battery such as nickel-cadmium cell, and charging high based on battery energy density is rapidly
These features, high-efficient high-capacity three amount high charge number of times is benefited from the novel lithium battery polymer solids of life-span length by people
The expectation of electrolytic thin-membrane strengthens day by day.
In-primary cell or the electrochemical element such as secondary cell and capacitor, it is possible to use liquid electrolyte comes
As the conduction raw material of the new battery of manufacture, but when the electrolyte of liquid has the danger of liquid leakage or lacks long
Between the shortcoming of stability.Owing to solid electrolyte overcomes with liquid electrolyte battery leakage and instability
Shortcoming, is applied to various electrochemical element simultaneously by copolymer solid electrolyte, is realizing the letter that element manufactures
While listization, miniaturization or the lightweight of element self become a reality, and not only do not have the danger that liquid leaks, and
And also provide for the cell device that reliability is high.To this end, in lithium-ion type battery etc., at solid electrolyte
During research and development, light weight and softness, handling ease the research and development of copolymer solid electrolyte the most alive
Carry out with jumping.
Wright in 1973 et al. is found that polyethylene glycol oxide (PEO) and alkali metal lithium, sodium salt complexation first
There is the phenomenon of ion guide electronics, so that solid electrolytic Quality Research one new stage of entrance, but due to
Being limited by material and technological means, the room-temperature conductivity of solid electrolyte greatly differs from each other with actual application needs.
In order to solve this problem, Feuillade etc. first proposed a kind of elastomer of employing and inorganic lithium in 1975
Electrolyte is dissolved by the solvent that can volatilize and forms a kind of mixture solution, then by containing inorganic lithium salt
It is coated on the surface of a kind of solid, forms a kind of gel electrolyte film containing inorganic lithium salt, although later
Further investigation has been made by Abraham etc..Polymer gel is generally defined as one by the polymerization of solvent swell
The thing network system, the network structure of its uniqueness makes gel have the cohesiveness of solid and the dispersion biography of liquid simultaneously
The property led.The nineteen ninety-five U.S. Bellcore company to disclose a kind of new type gel polymer dielectric poly-for researching and developing
The technology of compound lithium ion solid electrolyte battery.Since then, to polymer Li-ion battery solid electricity
Solve Quality Research the most more.Polymer Li-ion battery is developed on the basis of liquid lithium ionic cell
Latest generation lithium ion battery, its constitute be use have ionic conductivity and have concurrently the polymer of barrier film effect-
Electrolyte replaces the electrolyte in liquid lithium ionic cell, and gel electrolyte is by polymer, plasticizer and lithium
The gel polymeric network with appropriate microporous structure that salt is formed by certain method, utilization is fixed on micro-
Liquid electrolyte molecule in structure realizes ionic conduction, and its room-temperature conductivity is typically 10-3S/cm quantity
Level.
Polyelectrolyte is by the complex of polymer matrix with doping salt formation. salt to be made is dissolved in macromolecule
And forming homogeneous solution, if interaction must be there is between macromolecular chain and salt. macromolecular chain contains electricity
Son gives atom such as oxygen atom, sulphur atom or nitrogen-atoms, and it can be with the cation in salt by L ew is acid
Alkali reaction carries out complexation, so their interaction and is just easy to produce. work as LiClO4It is dissolved in PPG can cause
Volume contraction, salt adds PPG and is made into the volume contraction caused by 10.41% (w t) solution when being equivalent to 25 DEG C
1.90x10 is applied to macromolecule solvent7Pa. this shows at Li+With there is strong phase between PPG ether oxygen atom
Interaction. they also find that the membership that adds of salt makes PPG glass transition temperature significantly improve, LiClO4Content
When reaching 25%, the T g of PPG (MW2000) is increased to 40 DEG C by-70 DEG C. and they think, Li+Can not be by
Big ClO4 -Ion shields very well, thus is easy to occur mutually along macromolecular scaffold with polar ether oxygen atom
Effect, this is beneficial to dissociating of salt. and this effect also makes interchain interaction be occurred, thus leads
Cause the physical crosslinking of macromolecular chain.
Owing to most macromolecular compound is electrical insulator, but from reporting certain macromolecular material, such as
Electrolytic salt as poly(ethylene oxide) (PEO) and such as lithium salts forms crystalline complex and shows height
Ionic conductivity since, with PEO or other polyalkylene oxide, also have there is ion solution the most in the molecule
People is just being caused as the research of the polymer solid electrolyte of substrate from the polymine of base or polyphosphazene etc.
Attention.Particularly report many using polyalkylene oxide as the polymer solid electrolyte of the composition of substrate
Research, recently, the ionic conduction degree of near room temperature is modified to 10-4～10-6S/cm.But, for terrible
To high ion-conductivity, it is necessary to the content of the polyalkylene oxide in raising substrate, this significantly decreases electricity on the contrary
Solve the thin film strength of matter or thermostability, thus it is difficult for obtaining having the solid electrolyte of practicality, then just like
Fruit is at low temperature, and such as less than 0 DEG C, it is also that problem is as polymeric solid electricity that ionic conductivity reduces terrifically
Xie Zhi, it is proposed that to make methoxy poly (ethylene glycol) monomethacrylates (A) by active anionic polymerization
With the ABA type triblock copolymer of styrene (B) copolymerization as the polymer solid electrolyte of substrate base material,
But, as the homopolymer of the methoxy poly (ethylene glycol) monomethacrylates of composition six, despite macromolecule
Quantity of material, but be aqueous in room temperature, for the substrate base material using A-B-A type copolymer as solid electrolyte,
So the content of composition A is restricted, it means that as the PEO region knot in the diffusion transport space of lithium ion
The shape and size of structure are restricted, and ionic conductivity many when actual 40 DEG C is unsatisfactory for 10-6S/cm。
From the point of view of the electrical conduction mechanism of solid electrolyte, at less than 60 DEG C its SPE of melting point polymer generally by being polymerized
The crystalline compound that thing crystalline phase, polymer are formed with lithium salts and the polymer amorphous phase containing solvation salt are constituted to be led
Electricity study mechanism shows under electric field action, ion migration occurs mainly in amorphous phase region again due to polymer
The motion of short range segment helps lend some impetus to polymer and Li+Between the destruction of coordinate bond and be formed as Li+Migration
There is provided free volume therefore to reduce the degree of crystallinity of polymer and glass transition temperature (Tg) improves polymer chain
Compliance and its free volume density that increases both contribute to obtain the SPE of high conduction performance and do not send out with polymer
The anion of raw association is commonly considered as low Jie of another aspect conducted electricity by the directional migration to room
The polymer of electric constant makes to there is strong interaction between ion and ion and result in SPE except certainly
By anion and solvation cation outside there is also solvated ion to Tight ion to three ion aggregation bodies
They determine the concentration of carrier and transfer ability is also to affect SPE conductive capability with other ion aggregation body
Key factor.But, among the solid electrolyte thin film formed by polymer and lithium salts, according to lithium salts
Electrical conduction mechanism, under certain voltage, make lithium salts be dissociated into zwitterion, these zwitterions are at voltage
Under effect, there is directional migration, but, owing to polymer plays supporting role in solid electrolyte, with
Time, limited by the structure of polymer, if this polymer is crystal structure, lithium salts can be made to dissociate shape
The zwitterion become hinders the motion of these zwitterions under the effect of voltage, therefore, in order to improve solid-state
The electric conduction quantity of electrolyte and the capacity of battery manufactured by this electrolyte, on the one hand, needing polymer is without fixed
The form of shape, on the other hand, needs lithium salts to have good dissociating power, to this end, research is a kind of high-effect
Electrolyte is the target of each researcher.
In Chinese patent application: describe a kind of to provide thermal characteristics, physical characteristic and ion in 03817326.3
Conductivity is excellent, polymer solid electrolyte close to realistic scale, particularly total solids electrolyte, and
For the purpose of becoming the copolymer compositions of substrate for manufacturing this electrolyte.This polymer solid electrolyte contains
There are copolymer and electrolytic salt, this copolymer has the block chain A of the repetitive represented with formula (I), tool
Have with formula II (in formula, R9Represent aryl) the block chain B of repetitive that represents and having with formula
(III) (in formula, R13Representing aryl or heteroaryl) the block chain C of repetitive that represents is with the order of B, A, C
Arrangement.Needed for this polymer solid electrolyte is also a kind of solid electrolyte of method synthesis using block polymerization
The amorphous polymer wanted, compares with other polymer phase, and this solid electrolyte fully utilizes polymer
Cyberspace structure, thus obtain conducting electrolyte and the battery capacity of corresponding effect, but, polymer
Side chain can hinder the most again the motion after electrolyte dissociation.
Disclose a kind of by the closed pore that impregnated of nonaqueous electrolytic solution at Chinese Patent Application No. code 96197348.X
The NEW TYPE OF COMPOSITE polymeric electrolyte that porous polymer foaming body is made, it includes multiple being limited by hole wall
Closed pore, hole wall constitute with nonaqueous electrolytic solution dipping continuous solid phase parent, formed continuous solid phase micro-
District, plurality of closed pore has been substantially filled with nonaqueous electrolytic solution to form multiple liquid phase micro-areas, they dispersions
In above-mentioned continuous solid phase microcell.This invention compound molecule electrolyte not only has ionic conductance very
String and the highest mechanical strength, and can prevent nonaqueous electrolytic solution from leaking, the therefore electrolyte of this invention
It is advantageously used for various non-aqueous electrochemical device.It is to say, comprise compound molecule of the present invention electrolysis
The non-aqueous electrochemical device of matter not only has excellent electrochemistry, and can maintain electrolyte therein,
To this end, this invention exists clearly disadvantageous in manufacturing process.
In view of the disadvantage mentioned above of prior art, it is an object of the invention to overcome the deficiency of current solid electrolyte,
Using and the good organic lithium salt of polymer compatibility, it is to improve lithium salts dispersibility in the polymer,
And then improve the capacitance of solid electrolyte and charge-discharge velocity, use simultaneously polymethyl methacrylate this
Planting the polymer that side chain is relatively fewer and side chain is short, after reduction lithium salts dissociation, lithium ion and anion are at voltage
The obstruction of the lower movement of effect, thus improve the conductivity of this solid electrolyte and made electricity by this electrolyte
The capacity in pond.
Summary of the invention
The present invention realizes the main technique of goal of the invention and includes as follows.
A kind of manufacture method of the copolymer solid electrolyte thin film containing organolithium, the first that will process through high activity
The mixture of aminobutyric acid lithium and inorganic lithium is extruded through double screw extruder, through the T-shaped mould shape of head
Becoming thickness is 6～8mm a width of 12～the sheet material of 24mm, and this solid electrolyte sheet material is clipped in other two double spiral shells
The centre of the polymethyl methacrylate sheet material of same width and thickness extruded by bar extruder, is then passed through temperature
It is that the insulation path drawing-off of 100～120 DEG C becomes that 600～1200mm is wide and 0.6～1.0mm thickness contains organolithium
Copolymer solid electrolyte thin film, in solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, and lithium is in polymerization
Content in thing is 6～8%wt, and its manufacturing process includes:
A: prepared by high activity methylaminobutyric acid lithium:
1) under the protection of nitrogen, the NaOH aqueous solution of 38%wt is added temperature slowly is 60～80
DEG C N-Methyl pyrrolidone nmp solvent in, then with the programming rate of 0.6～0.8 DEG C/min by temperature
It is raised to 100～120 DEG C, and under this temperature conditions, after backflow insulation 3～4.5h, then 1.6～1.8
DEG C/temperature is raised to 180～200 DEG C by min programming rate, and under this temperature conditions, backflow insulation 30～
45min;Then, the cooling rate of reactant mixture 0.6～0.8 DEG C/min is reduced the temperature to 150～160
DEG C, under this temperature conditions, adding solid lithium chloride, the mol ratio of NaOH:LiCl:NMP is 1:1.003:3,
After insulation 2～3h, stop backflow, start to evaporate the moisture content in back mixing compound, steam every 5min detection
The liquid component issued, when the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%
And a large amount of white crystal separate out after stop stirring and heating, and be incubated filtration while hot, be 30 by temperature after filtration
DEG C N-Methyl pyrrolidone solvent constantly rinse white crystal much filtrate；
2) by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanol containing white crystal 20～30%wt
Solution, then heating in water bath, be raised to 60～70 DEG C by temperature, and insulation backflow 45min, then, by temperature
After dropping to 20～30 DEG C, filter；
4) repeat 3) to the filter cake cyclic washing 6 obtained～8 times after, filter cake is inserted the vacuum of 100～110 DEG C
After being dried 2～3h in baking oven, the white powder that white crystal becomes containing 30%～40%wt water of crystallization is stand-by；
Gained white powder be purity be 99～99.95% methylaminobutyric acid lithium；
B: the copolymer solid electrolyte film preparation containing organolithium
White powder step A obtained and inorganic lithium powder are by the mol ratio of 3:1, in high speed agitator
Mix homogeneously, then input temp is the double screw extruder of 200～220 DEG C, by the head T of extruder
Mould is extruded into sheet material；Then the polymethyl methacrylate adding benzene many esters of gallic acid plasticiser is distinguished the most defeated
Entering temperature is 268～288 DEG C of two double screw extruders extrusions, in sheet material blender, by organolithium and nothing
The sheet material of machine lithium mixture is clipped in the middle, and is formed containing polymethyl methacrylate-organolithium and inorganic lithium-poly-
The sheet material of methyl methacrylate, this sheet material input insulation path, become to contain through 6～8 grades of two-way drawing-offs
The copolymer solid electrolyte thin film of machine lithium, obtains the object copolymer solid electrolyte containing organolithium thin
Film, its solid electrolyte high conductivity 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.
Described benzene many esters of gallic acid plasticiser includes the own ester of trioctyl trimellitate (TOTM), tri trimellitate, equal benzene
One of tetracid four ester, 1,2,4-triisooctyl trimellitate.
In view of improve yield, described step A the 1st) step gained filtrate with 0.6～0.8 DEG C/min's
Cooling rate reduces the temperature to 50～60 DEG C, again separates out substantial amounts of white crystal, then in this temperature in filtrate
The white crystal being filtrated to get under the conditions of degree is incorporated to the 2nd as raw material) in the white crystal of step.Corresponding each
The filtrate of step recycles.
The phase of organolithium and inorganic lithium compound and polymer in products therefrom solid electrolyte film of the present invention
Capacitive is good, organolithium and inorganic lithium compound being evenly distributed in polymethyl methacrylate, so that by
The charge-discharge performance of the all-solid lithium battery that this electrolyte manufactures is stable, and service life is 438Q～638Q, fills
Discharge time is 1300～1800 times, and capacity is 180～220mAh/g；Its discharge and recharge number of times and service life
And capacitance will be respectively increased 38～120% accordingly than current lithium battery.
Accompanying drawing illustrates:
Fig. 1 is present invention process line of fall schematic diagram.
Fig. 2 is embodiment of the present invention performance synopsis.
Detailed description of the invention:
In addition to special declaration, each chemical reagent related in the application is chemical pure.
Embodiment 1
Under the protection of nitrogen, with the mol ratio of NaOH:LiCl:NMP for 1.00:1.003:3.00 by 38%wt
NaOH aqueous solution add in the N-Methyl pyrrolidone organic solvent that temperature is 60 DEG C slowly, then
With the programming rate of 0.8 DEG C/min, temperature is raised to 100 DEG C, and under this temperature conditions, backflow insulation 4.5h
After, then temperature is raised to 180 DEG C by 1.8 DEG C/min programming rate, and under this temperature conditions, backflow is protected
Temperature 45min, then, reduces the temperature to 150 DEG C by the cooling rate of 0.8 DEG C/min of reactant mixture,
Add solid lithium chloride under this temperature conditions, and after being incubated 3h, stop backflow, start to evaporate back mixing and close
Moisture content in thing, detects the liquid component being evaporated, when containing in the liquid component evaporated every 5min
When the amount of N-Methyl pyrrolidone solvent accounts for 90%, there is a large amount of white crystal stop stirring after separating out and add simultaneously
Heat, and under this temperature conditions, it is incubated filtration while hot, during filtration, reaction system same amount temperature is 30
DEG C N-Methyl pyrrolidone solvent constantly rinse white crystal, the temperature of the colourless filtrate obtained is with 0.8 DEG C
The cooling rate of/min reduces the temperature to 60 DEG C, again separates out substantial amounts of white crystal, then exist in filtrate
Filtering under this temperature conditions, the white crystal obtained is dissolved in alcohol solvent, forms the 30%wt Han white crystal
Ethanol solution, then heating in water bath, temperature is raised to 70 DEG C, insulation backflow 45min, then, by temperature
After degree drops to 30 DEG C, filtering, filter cake is stand-by, recycles filtrate；The filter cake cyclic washing obtained 8 times,
Then being inserted by filter cake after being dried 2h in the vacuum drying oven of 110 DEG C, white crystal becomes containing 30%wt crystallization
The white powder of water is detected as the methylaminobutyric acid lithium of purity 99.95% through Fourier infrared spectrograph analysis；
The methylaminobutyric acid lithium white obtained is that the inorganic lithium powder such as powder and lithium iodide is dissolved in by the mol ratio of 3:1
5:1 mass ratio, mix homogeneously in high speed agitator, then input temp is the twin-screw extrusion of 200 DEG C
Machine, is extruded, by the head T mould of extruder, the sheet material that thickness is a width of 16mm of 6mm, then will add 3%wt
The polymethyl methacrylate of trioctyl trimellitate (TOTM) is 268 DEG C of two double screw extruders by temperature respectively
Extrusion, in sheet material blender, is clipped in the middle the sheet material of organolithium and inorganic lithium mixture, and formation contains
Polymethyl methacrylate-organolithium and the sheet material of inorganic lithium-polymethyl methacrylate, the input of this sheet material is protected
Temperature path, becomes containing the copolymer solid electrolyte that 6%wt thickness is 0.6mm organolithium through 6 grades of drawing-offs
Thin film；The high conductivity of this copolymer solid electrolyte is 8.12x10-3S/cm, electrochemical stability window
For 1.1V, service life is 638Q, and discharge and recharge number of times is 1800 times, and capacity is 180mAh/g.
Embodiment 2
Under the protection of nitrogen, with the mol ratio of NaOH:LiCl:NMP for 1.00:1.003:3.00 by 38%wt
NaOH aqueous solution add in the N-Methyl pyrrolidone organic solvent that temperature is 80 DEG C slowly, then
With the programming rate of 0.6 DEG C/min, temperature is raised to 120 DEG C, and under this temperature conditions, backflow insulation 3h
After, then temperature is raised to 200 DEG C by 1.6 DEG C/min programming rate, and under this temperature conditions, backflow is protected
Temperature 30min, then, reduces the temperature to 160 DEG C by the cooling rate of 0.6 DEG C/min of reactant mixture,
Add solid lithium chloride under this temperature conditions, and after being incubated 2h, stop backflow, start to evaporate back mixing and close
Moisture content in thing, detects the liquid component being evaporated, when containing in the liquid component evaporated every 5min
When the amount of N-Methyl pyrrolidone solvent accounts for 90%, there is a large amount of white crystal stop stirring after separating out and add simultaneously
Heat, and under this temperature conditions, it is incubated filtration while hot, during filtration, reaction system same amount temperature is 30
DEG C N-Methyl pyrrolidone solvent constantly rinse white crystal, the temperature of the colourless filtrate obtained is with 0.6 DEG C
The cooling rate of/min reduces the temperature to 38 DEG C, again separates out substantial amounts of white crystal, then exist in filtrate
Filtering under this temperature conditions, the white crystal obtained is dissolved in alcohol solvent, forms the 20%wt Han white crystal
Ethanol solution, then heating in water bath, temperature is raised to 60 DEG C, insulation backflow 45min, then, by temperature
After degree drops to 20 DEG C, filtering, filter cake is stand-by, recycles filtrate；The filter cake cyclic washing obtained 6 times,
Then being inserted by filter cake after being dried 3h in the vacuum drying oven of 100 DEG C, white crystal becomes containing 40%wt crystallization
The white powder of water is detected as the methylaminobutyric acid lithium of purity 99～% through Fourier infrared spectrograph analysis；
The methylaminobutyric acid lithium white obtained is that the inorganic lithium powder such as powder and lithium iodate is dissolved in by the mol ratio of 3:1
5:1 mass ratio, mix homogeneously in high speed agitator, then input temp is the twin-screw extrusion of 220 DEG C
Machine, is extruded the sheet material of a width of 24mm of thickness 8mm, then will add 5%wt by the head T mould of extruder
The polymethyl methacrylate of the own ester of tri trimellitate is 288 DEG C of two double screw extruders by temperature respectively
Extrusion, in sheet material blender, is clipped in the middle the sheet material of organolithium and inorganic lithium mixture, and formation contains
Polymethyl methacrylate-organolithium and the sheet material of inorganic lithium-polymethyl methacrylate, the input of this sheet material is protected
Temperature path, becomes containing the copolymer solid electrolyte that 8%wt thickness is 1.0mm organolithium through 8 grades of drawing-offs
Thin film；The high conductivity of this copolymer solid electrolyte is 9.36x10-3S/cm, electrochemical stability window
For 1.5V, service life is 438Q, and discharge and recharge number of times is 1300 times, and capacity is 180mAh/g.
Embodiment 3
Under the protection of nitrogen, with the mol ratio of NaOH:LiCl:NMP for 1.00:1.003:3.00 by 38%wt
NaOH aqueous solution add in the N-Methyl pyrrolidone organic solvent that temperature is 7080 DEG C slowly, so
After with the programming rate of 0.7 DEG C/min, temperature is raised to 110 DEG C, and under this temperature conditions, backflow insulation
After 4.0h, then temperature is raised to 190 DEG C by 1.7 DEG C/min programming rate, and under this temperature conditions, returns
Stream insulation 40min, then, reduces the temperature to 155 DEG C by the cooling rate of 0.7 DEG C/min of reactant mixture,
Under this temperature conditions, add solid lithium chloride, and after being incubated 2.5h, stop backflow, start to evaporate anti-
Moisture content in mixture, detects the liquid component being evaporated, when the liquid component evaporated every 5min
In when accounting for 90% containing the amount of N-Methyl pyrrolidone solvent, have a large amount of white crystal to stop stirring after separating out simultaneously
And heating, and under this temperature conditions, it being incubated filtration while hot, during filtration, reaction system same amount temperature is
The N-Methyl pyrrolidone solvent of 30 DEG C constantly rinses white crystal, and the temperature of the colourless filtrate obtained is with 0.7
DEG C/cooling rate of min reduces the temperature to 555 DEG C, again separates out substantial amounts of white crystal, then in filtrate
Filtering under this temperature conditions, the white crystal obtained is dissolved in alcohol solvent, forms the 26%wt Han white crystal
Ethanol solution, then heating in water bath, temperature is raised to 638 DEG C, insulation backflow 45min, then, by temperature
After degree drops to 28 DEG C, filtering, filter cake is stand-by, recycles filtrate；The filter cake cyclic washing obtained 7 times,
Then being inserted by filter cake after being dried 2.6h in the vacuum drying oven of 108 DEG C, white crystal becomes containing 36%wt
The white powder of water of crystallization is detected as the methylamino fourth of purity 99.91% through Fourier infrared spectrograph analysis
Acid lithium；The methylaminobutyric acid lithium white obtained is powder and the inorganic lithium such as lithium iodide and lithium iodate (each 38%)
Powder presses the mol ratio of 3:1, mix homogeneously in high speed agitator, and then input temp is 218 DEG C double
Screw extruder, is extruded, by the head T mould of extruder, the sheet material that thickness is a width of 18mm of 9mm, then
By the polymethyl methacrylate adding the 1,2,4-triisooctyl trimellitate of 4%wt by temperature it is respectively
283 DEG C of two double screw extruders extrusion, in sheet material blender, by organolithium and inorganic lithium mixture
Sheet material is clipped in the middle, and is formed containing polymethyl methacrylate-organolithium and inorganic lithium-poly-methyl methacrylate
The sheet material of ester, this sheet material input insulation path, becoming containing 7.1%wt thickness through 7 grades of drawing-offs is 0.8mm
The copolymer solid electrolyte thin film of organolithium；The high conductivity of this copolymer solid electrolyte is
8.83x10-3S/cm, electrochemical stability window is 1.3V, and service life is 584Q, and discharge and recharge number of times is 1531
Secondary, capacity 200mAh/g.
Comparative example 1
Use the inorganic lithium powder such as commercially available chemical pure methylaminobutyric acid lithium and lithium iodate by the mol ratio of 1:3,
Mix homogeneously in high speed agitator, then input temp is the double screw extruder of 220 DEG C, by extruder
Head T mould extrusion thickness is the sheet material of a width of 24mm of 8mm, then will add the poly-of PMA four ester
Methyl methacrylate is 283 DEG C of two double screw extruders extrusions by temperature respectively, in sheet material blender,
The sheet material of organolithium and inorganic lithium mixture is clipped in the middle, is formed containing polymethyl methacrylate-organic
Lithium and the sheet material of inorganic lithium-polymethyl methacrylate, this sheet material input insulation path, through 8 grades of drawing-offs
Become containing the copolymer solid electrolyte thin film that 8%wt thickness is 1.0mm organolithium；This polymer solids electricity
The high conductivity solving matter is 7.82x10-5S/cm, electrochemical stability window is 1.1V, and service life is
280Q, discharge and recharge number of times is 902 times, and capacity is 270mAh/g.
Through comparative example and combine Fig. 2 data and understand: the activity of methylaminobutyric acid lithium and its manufacturing process
Close association, the copolymer solid electrolyte thin film using activity used by the present invention to process raw material acquisition has more
Good performance characteristic.
Claims (4)
1. a manufacture method for the copolymer solid electrolyte thin film containing organolithium, the first ammonia that will process through high activity
The mixture of base butanoic acid lithium and inorganic lithium is extruded through double screw extruder, and the T-shaped mould through head forms thickness
Degree is 6～8mm a width of 12～the sheet material of 24mm, and this solid electrolyte sheet material is clipped in other two twin-screw extrusions
The centre of the polymethyl methacrylate sheet material of same width and thickness extruded by machine, be then passed through temperature be 100～
The insulation path drawing-off of 120 DEG C becomes that 600～1200mm is wide and 0.6～1.0mm thickness contains the polymer solids of organolithium
Electrolytic thin-membrane, in solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, lithium content in the polymer
Being 6～8%wt, its manufacturing process includes:
A: prepared by high activity methylaminobutyric acid lithium:
1) under the protection of nitrogen, the NaOH aqueous solution of 38%wt is slowly added into the N-methyl that temperature is 60～80 DEG C
In ketopyrrolidine nmp solvent, then with the programming rate of 0.6～0.8 DEG C/min temperature is raised to 100～
120 DEG C, and under this temperature conditions, after backflow insulation 3～4.5h, then 1.6～1.8 DEG C/min heats up speed
Temperature is raised to 180～200 DEG C by degree, and under this temperature conditions, backflow insulation 30～45min, then, will
The cooling rate of reactant mixture 0.6～0.8 DEG C/min reduces the temperature to 150～160 DEG C, in this temperature conditions
Lower addition solid lithium chloride, the mol ratio of NaOH:LiCl:NMP is 1:1.003:3, after insulation 2～3h, stops
Backflow, starts the moisture evaporating in reactant mixture, detects the liquid component being evaporated every 5min,
When the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%, there is a large amount of white brilliant simultaneously
Body stops stirring and heating after separating out, and is incubated filtration, reactant during filtration under this temperature conditions while hot
Be same amount temperature be that the N-Methyl pyrrolidone nmp solvent of 30 DEG C constantly rinses white crystal；
2) by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanol containing white crystal 20～30%wt molten
Liquid, then heating in water bath, be raised to 60～70 DEG C by temperature, insulation backflow 45min, then, reduces the temperature to
After 20～30 DEG C, filter；
3) to 2) after the filter cake cyclic washing 6 that obtains～8 times, filter cake is inserted in the vacuum drying oven of 100～110 DEG C
After being dried 2～3h, the white powder that white crystal becomes containing 30%～40%wt water of crystallization is stand-by；In Fu
Leaf infrared spectrometer analysis detection gained white powder is methylaminobutyric acid lithium, and purity is 99～99.95%；
B: the copolymer solid electrolyte film preparation containing organolithium
White powder step A obtained and inorganic lithium powder are by the mol ratio of 3:1, and in high speed agitator, mixing is all
Even, then input temp is the double screw extruder of 200～220 DEG C, the head T mould of extruder be extruded into
Sheet material；Then by the polymethyl methacrylate input temp respectively adding benzene many esters of gallic acid plasticiser be 268～
288 DEG C of two double screw extruders extrusions, in sheet material blender, by organolithium and the sheet of inorganic lithium mixture
Material is clipped in the middle, and is formed containing polymethyl methacrylate-organolithium and inorganic lithium-polymethyl methacrylate
Sheet material, this sheet material input insulation path, become the polymer solids containing organolithium through 6～8 grades of two-way drawing-offs
Electrolytic thin-membrane, the gained target copolymer solid electrolyte thin film containing organolithium, its solid electrolyte conducts electricity
Rate is 8.12～9.36x10-3S/cm, electrochemical stability window is 5.1～5.5V.
A kind of manufacture method of the copolymer solid electrolyte thin film containing organic lithium,
It is characterized in that, described inorganic lithium can be lithium iodide or lithium iodate.
A kind of manufacture method of the copolymer solid electrolyte thin film containing organic lithium,
It is characterized in that this benzene many esters of gallic acid plasticiser includes the own ester of trioctyl trimellitate (TOTM), tri trimellitate, equal benzene
One of tetracid four ester, 1,2,4-triisooctyl trimellitate.
A kind of manufacture method of the copolymer solid electrolyte thin film containing organic lithium,
It is characterized in that, the 1st of described step A) in step, gained filtrate will with the speed of 0.6～0.8 DEG C/min
Temperature drops to 50～60 DEG C, again separates out substantial amounts of white crystal, then mistake under this temperature conditions in filtrate
The white crystal that obtains of filter is incorporated to the 2nd as raw material) in the white crystal of step.
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| CN101045762A (en) * | 2007-03-29 | 2007-10-03 | 复旦大学 | Organic inorganic composite polymer electrolyte and preparation method and application thereof |
| CN101183727A (en) * | 2007-12-06 | 2008-05-21 | 哈尔滨工业大学 | All solid state electrolyte and preparing method and application of the same |
| CN101276658A (en) * | 2008-05-21 | 2008-10-01 | 北京化工大学 | Inorganic/organic nano composite solid electrolyte and method of preparing the same |
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| CN101045762A (en) * | 2007-03-29 | 2007-10-03 | 复旦大学 | Organic inorganic composite polymer electrolyte and preparation method and application thereof |
| CN101183727A (en) * | 2007-12-06 | 2008-05-21 | 哈尔滨工业大学 | All solid state electrolyte and preparing method and application of the same |
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