CN103515654B - The manufacture method of a kind of copolymer solid electrolyte - Google Patents
The manufacture method of a kind of copolymer solid electrolyte Download PDFInfo
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- CN103515654B CN103515654B CN201310418975.1A CN201310418975A CN103515654B CN 103515654 B CN103515654 B CN 103515654B CN 201310418975 A CN201310418975 A CN 201310418975A CN 103515654 B CN103515654 B CN 103515654B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The present invention discloses the manufacture method of a kind of copolymer solid electrolyte; its raw material methylamino-butyric acid lithium adopts the certain density NaOH aqueous solution under the protection of nitrogen; after reacting with N-Methyl pyrrolidone, then add lithium chloride and displace sodium ion wherein and obtain. Acetone-methanol solvate that then the methylamino-butyric acid lithium obtained and inorganic lithium etc. are dissolved in certain temperature obtains containing the acetone-methanol solution of methylamino-butyric acid lithium and the polymethylmethacrylate of lithium iodide or lithium iodate, then this dissolution homogeneity is coated on polyvinylidene difluoride (PVDF) semi-permeable membranes, through repeated multiple times coating, make the certain thickness polymer solid electrolyte film containing organolithium. The solid lithium battery being made up of gained dielectric film of the present invention, has long service life, the features such as discharge and recharge number of times is many, and cell container is big.
Description
Technical field
The invention relates to the useful especially polymer solid electrolyte for secondary cell and manufacture field.
Background technology
Battery is used as the power supply of the electrical equipment such as torch and phone very early by people, along with the progress of science and technology and the discovery of novel material, people have developed nickel metal hydride battery and lithium cell, along with the appearance of the portable electronics such as mobile phone and notebook computer, the demand of the high performance and miniaturization etc. of battery is seemed more and more stronger, for meeting this kind of demand, lithium-ion type battery is with energy density height, the feature such as charging can progressively cause showing great attention to of people rapidly, compared with other the battery such as nickel-cadmium cell, based on energy capacity of battery density height and charging these features rapidly, the expectation of the novel lithium battery polymer solid electrolyte film that high-efficient high-capacity three amount high charge number of times benefits from life-span length is strengthened by people day by day.
In primary cell or the electrochemical element such as secondary cell and electrical condenser, it is possible to use liquid electrolyte is used as manufacturing the conduction starting material of new battery, but the ionogen of liquid has the danger of liquid leakage or lacks the shortcoming of long-time stability. Owing to solid electrolyte overcomes with liquid electrolyte battery leakage and unstable shortcoming, copolymer solid electrolyte is applied to various electrochemical element simultaneously, while realizing the simplification that element manufactures, miniaturization or the lightweight of element self become a reality, not only there is no the danger that liquid leaks, but also the cell device providing reliability high. For this reason, in lithium-ion type 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 carry out just actively.
People's Late Cambrian such as Wright in 1973 polyoxyethylene (PEO) and alkali metal lithium, sodium salt complexing have the phenomenon of ion guide electronics, thus make solid electrolytic Quality Research enter a new stage, but need to greatly differ from each other due to the restriction by material and technique means, the room-temperature conductivity of solid electrolyte and practical application. In order to solve this problem, Feuillade etc. first proposed in 1975 and adopt a kind of elastomerics and inorganic lithium ionogen to form a kind of mixture solution by the dissolution with solvents that can volatilize, then by the surface being coated on a kind of solid containing inorganic lithium salt, form a kind of gel electrolyte plasma membrane containing inorganic lithium salt, although having done further investigation by Abraham etc. afterwards. Polymer gel is generally defined as one by the polymer network system of solvent-swollen, and the network structure of its uniqueness makes gel have the sticky poly-property of solid and the dispersion conductivity of liquid simultaneously. Nineteen ninety-five U.S. Bellcore, company disclosed a kind of new type gel polymer dielectric for researching and developing the technology of polymer Li-ion solid state electrolysis electrolyte cell. Since then, to polymer Li-ion battery with solid electrolytic Quality Research just more. Polymer Li-ion battery is the latest generation lithium ion battery developed on the basis of liquid lithium ionic cell, it is formed is adopt the electrolytic solution having ionic conductivity and have concurrently in polymkeric substance-ionogen replacement liquid lithium ionic cell of barrier film effect, gel electrolyte is the gel polymeric network with suitable microvoid structure formed by certain method by polymkeric substance, softening agent and lithium salt, utilizing the liquid electrolyte molecule being fixed in microstructure to realize ionic conduction, its room-temperature conductivity is generally 10-3The S/cm order of magnitude.
Polymer electrolyte is by the complex compound of polymer matrix with doping salt formation. salt will be made to be dissolved in polymer and form homogeneous solution, if must there is interaction between macromolecular chain and salt. macromolecular chain contains electronics and gives atom such as Sauerstoffatom, sulphur atom or nitrogen-atoms, it can carry out complexing with the positively charged ion in salt by Lewis acid-base reaction, and so their interaction just is easy to produce. work as LiClO4Being dissolved in PPG and can cause volumetric shrinkage, salt adds PPG and is made into when the volumetric shrinkage caused by 10.41% (wt) solution is equivalent to 25 DEG C and applies 1.90x10 to macromolecule solvent7Pa. this shows at Li+And there is strong interaction between PPG ether oxygen atom. they also find that the membership that adds of salt makes PPG second-order transition temperature significantly improve, and when LiClO4 content reaches 25%, the Tg of PPG (MW2000) is increased to 40 DEG C by-70 DEG C. they think, Li+Can not by big ClO4 -Ion shields very well, is thus easy to interact along macromolecular scaffold and polar ether Sauerstoffatom, and this will be conducive to dissociating of salt. and this kind of effect also makes interchain interaction be occurred, thus causes the physical crosslinking of macromolecular chain.
Owing to the macromolecular compound of major part is electrical insulator, but from certain macromolecular material of report, such as polyethylene oxide (PEO) and such as electrolytic salt as lithium salt have just attracted much attention using PEO or other polyalkylene oxide, the polymine equally in the molecule in addition with ionic dissociation base or polyphosphonitrile etc. as the research of the polymer solid electrolyte of matrix since forming the complex compound of crystallinity and showing high ionic conductivity. Particularly reporting the research of the polymer solid electrolyte of many compositions using polyalkylene oxide as matrix, recently, the ionic conduction degree near room temperature is modified to 10-4��10-6S/cm. but, in order to obtain high ion-conductivity, the content of the polyalkylene oxide just needing to improve in matrix, this reduces intensity or the thermotolerance of dielectric film on the contrary significantly, thus the solid electrolyte obtaining having practicality is difficult, if had again at low temperature, such as less than 0 DEG C, it is also that problem is as polymer solid electrolyte that ionic conductivity extremely reduces, propose the polymer solid electrolyte of ABA type triblock copolymer as matrix base material to be made methoxy poly (ethylene glycol) monomethacrylates (A) and vinylbenzene (B) copolymerization by active anionic polymerization, but, as the homopolymer of the methoxy poly (ethylene glycol) monomethacrylates of composition six, although being high molecular weight material, but it is aqueous in room temperature, in order to the matrix base material using A-B-A type multipolymer as solid electrolyte, so the content of composition A is restricted, this means that the shape and size of the PEO domain structure in the diffusion transport space as lithium ion are restricted, ionic conductivity when actual 40 DEG C is many does not meet 10-6S/cm��
From the electrical conduction mechanism of solid electrolyte, at melting point polymer less than 60 DEG C its SPE usually by the crystalline compound of polymkeric substance crystalline phase, polymkeric substance and lithium salt formation with form electrical conduction mechanism research containing the polymkeric substance amorphous phase of solvation salt and show that under electric field action ion migration mainly occurs in amorphous phase region motion due to polymkeric substance short range segment again and contributes to promoting polymkeric substance and Li+Between the destruction of coordinate bond and be formed as Li+Migration provide free volume therefore reduce the degree of crystallinity of polymkeric substance and second-order transition temperature (Tg) improve polymer chain kindliness and increase its free volume density all contribute to obtaining high conduction performance SPE and not and the negatively charged ion of polymkeric substance generation association the polymkeric substance of another aspect low-k from the directional migration to room that be commonly considered as being conducted electricity by make to also exist between ion and ion strong interaction and result in and except the positively charged ion of negatively charged ion and solvation freely, also there is solvation in SPE.
The tight ion pair three ion aggregation body of ion pair and other ion aggregation body they have determined that the concentration of current carrier and transfer ability are also the important factors affecting SPE conductive capability. but, among the solid electrolyte membrane by polymkeric substance and lithium salt formation, electrical conduction mechanism according to lithium salt, under certain voltage, lithium salt is made to be dissociated into zwitterion, these zwitterions are under the effect of voltage, there is directional migration, but, owing to polymkeric substance plays supporting role in solid state electrolyte, simultaneously, it is subject to the restriction of the structure of polymkeric substance, if this polymkeric substance is crystalline structure, the zwitterion that lithium salt dissociation can be made to be formed hinders the motion of these zwitterions under the effect of voltage, therefore, in order to the electric conduction quantity that improves solid state electrolyte and the capacity of battery manufactured by this ionogen, on the one hand, polymkeric substance is needed to be unbodied form, on the other hand, lithium salt is needed to have good dissociation ability, for this reason, study the target that a kind of high-effect ionogen is each investigator.
Chinese patent application 03817326.3 describe a kind of to provide the polymer solid electrolyte of thermal property, physical property and ionic conduction degree practical level excellent, close, particularly total solids ionogen, and become for the manufacture of for the purpose of the copolymer compositions of the matrix of this ionogen. This polymer solid electrolyte contains multipolymer and electrolytic salt, has embedding section of chain A of the repeating unit represented with formula (I) in this multipolymer, have with formula II (in formula, R9Represent aryl) the embedding section of chain B of repeating unit that represent and have with formula III (in formula, R13Representing aryl or heteroaryl) the embedding section of chain C of repeating unit that represent arrange with the order of B, A, C. This polymer solid electrolyte is also adopt the method for block polymerization to synthesize the amorphous polymer required for a kind of solid electrolyte, compare with other polymer phase, this solid electrolyte fully utilizes the cyberspace structure of polymkeric substance, thus obtain conducting electrolyte and the cell container of corresponding effect, but, the side chain of polymkeric substance too much can hinder again the motion after ionogen dissociation.
A kind of NEW TYPE OF COMPOSITE molecule ionogen being made up of the closed pore porous polymer foam that impregnated of nonaqueous electrolytic solution is disclosed at Chinese patent application 96197348.X, it comprises multiple closed pore limited by hole wall, hole wall constitutes the continuous solid phase parent with nonaqueous electrolytic solution dipping, form the micro-district of continuous solid phase, wherein multiple closed pore is filled with nonaqueous electrolytic solution substantially to form multiple liquid phase micro-area, and they are dispersed in the micro-district of above-mentioned continuous solid phase. This invention compound molecule ionogen not only has ionic conductance string very and very high physical strength, and can prevent nonaqueous electrolytic solution from leaking, and therefore the ionogen of this invention can be advantageously used in various non-aqueous electrochemical device. That is, the non-aqueous electrochemical device comprising compound molecule ionogen of the present invention is not
Only having excellent electrochemistry, and can maintain electrolytic solution wherein, 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 phase capacitive, its objective is to improve the dispersion in the polymer of lithium salt, and then improve electrical capacity and the charge-discharge velocity of solid electrolyte, adopt the polymkeric substance that polymethylmethacrylate this kind of side chain is relatively less and side chain is short simultaneously, it is the obstruction in order to reduce lithium ion and negatively charged ion movement under the effect of voltage after lithium salt dissociation, thus improves the electric conductivity of this solid electrolyte and be made up the capacity of battery of this ionogen.
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 lithium content in the polymer is 6��8%wt, should comprise containing the manufacturing process of the copolymer solid electrolyte of organolithium:
A: prepared by high reactivity methylamino-butyric acid lithium:
1) under the protection of nitrogen, the NaOH aqueous solution of 38%wt is added slowly in the N-Methyl pyrrolidone nmp solvent that temperature is 60��80 DEG C, then with the heat-up rate of 0.6��0.8 DEG C/min, temperature is raised to 100��120 DEG C, and under this temperature condition, after backflow insulation 3��4.5h, then temperature is raised to 180��200 DEG C by 1.6��1.8 DEG C/min heat-up rate, and under this temperature condition, backflow insulation 30��45min, then, the cooling rate of reaction mixture 0.6��0.8 DEG C/min is reduced the temperature to 150��160 DEG C, solid lithium chloride is added under this temperature condition, the mol ratio of NaOH:LiCl:NMP is 1:1.003:3, after insulation 2��3h, stop backflow, start the moisture content evaporated in back mixing compound, the liquid component being evaporated is detected every 5min, when the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%, stop after having a large amount of white crystal to precipitate out stirring and heating simultaneously, and under this temperature condition, it is incubated filtration while hot, during filtration, reaction system same amount and temperature are that the N-Methyl pyrrolidone solvent of 30 DEG C constantly rinses white crystal,
2). by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanolic soln containing white crystal 20��30%wt, then heating in water bath, is raised to 60��70 DEG C by temperature, and insulation backflow 45min, then, after reducing the temperature to 20��30 DEG C, filters;
3). to 2) after the filter cake repetitive scrubbing that obtains 6��8 times, filter cake is inserted in the vacuum drying oven of 100��110 DEG C after dry 2��3h, it is stand-by that white crystal becomes the white powder containing 30%��40%wt crystal water; Detecting gained white powder through Fourier infrared spectrograph analysis is methylamino-butyric acid lithium, and purity is 99��99.95%;
The acetone of B, organolithium, inorganic lithium and polymethylmethacrylate-methanol solution preparation
It is that powder and inorganic lithium powder are dissolved in the acetone of 5:1 mass ratio-methanol mixed solvent by the mol ratio of 3:1 by the white obtained in step A, and formed containing solid substance be the solution of 2��3%wt, when temperature is 50��65 DEG C, stirring and refluxing 2��3h, then, add the plexiglass powder in formula and 3��5% benzene polyacid ester compounds, thus make content in polymethylmethacrylate of organolithium and inorganic lithium be 6��8%wt, when temperature is 50��55 DEG C, stirring and refluxing 2��3h, polymethylmethacrylate wherein is made to be dissolved among acetone-methanol mixed solvent completely, stand-by,
Prepared by C, copolymer solid electrolyte containing organolithium
By B) step obtain containing organolithium, acetone-the methanol solution of inorganic lithium and polymethylmethacrylate is coated in polyvinylidene difluoride (PVDF) semi-permeable membranes surface, after acetone-methanol solvate wherein is evaporated completely, repeatedly apply again 16��18 times, then formed containing the solid electrolyte film of organolithium and the polymethylmethacrylate of inorganic lithium, finally this solid electrolyte film is placed in the dry 2��2.5h of vacuum drying oven that temperature is 50��55 DEG C, the obtained copolymer solid electrolyte target compound containing organolithium, the most high conductivity of resulting polymers solid electrolyte is 8.12��9.36x10-3S/cm, electrochemical stability window is 1.1��1.5V.
The most 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 obtained battery work-ing life is 450Q��650Q, and discharge and recharge number of times is 1300��1800 times, and capacity is 180��220mAh/g.
Accompanying drawing explanation
Fig. 1: the process flow sheet of solid electrolyte of the present invention
Fig. 2: the correlated performance table of the solid electrolyte of the present invention.
Embodiment:
Embodiment 1
Under the protection of nitrogen, by 1.00:1.003:3.00 of the mol ratio of NaOH:LiCl:NMP, the NaOH aqueous solution of 50%wt is added in the N-Methyl pyrrolidone organic solvent that temperature is 60 DEG C slowly, then with the heat-up rate of 1.8 DEG C/min, temperature is raised to 100 DEG C, and under this temperature condition, after backflow insulation 4.5h, then temperature is raised to 180 DEG C by 2.8 DEG C/min heat-up rate, and under this temperature condition, backflow insulation 45min, then, the cooling rate of reaction mixture 0.8 DEG C/min is reduced the temperature to 150 DEG C, solid lithium chloride is added under this temperature condition, and after being incubated 3h, stop backflow, start the moisture content evaporated in back mixing compound, the liquid component being evaporated is detected every 5min, when the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%, stop after having a large amount of white crystal to precipitate out stirring and heating simultaneously, and under this temperature condition, it is incubated filtration while hot, during filtration, reaction system same amount and temperature are that the N-Methyl pyrrolidone solvent of 30 DEG C constantly rinses white crystal, the temperature of the colourless permeate obtained reduces the temperature to 60 DEG C with the cooling rate of 0.8 DEG C/min, filtrate precipitates out a large amount of white crystals again, then filter under this temperature condition, the white crystal obtained is dissolved in alcohol solvent, form the ethanolic soln containing white crystal 30%wt, then heating in water bath, temperature is raised to 70 DEG C, insulation backflow 45min, then, after reducing the temperature to 30 DEG C, filter, filter cake is stand-by, recycling filtrate, the filter cake repetitive scrubbing obtained 8 times, then inserts filter cake in the vacuum drying oven of 110 DEG C after dry 2h, and white crystal becomes the methylamino-butyric acid lithium that white powder is detected as purity 99.95% through Fourier infrared spectrograph analysis, the methylamino-butyric acid lithium white obtained is dissolved in the acetone-methanol mixed solvent of 5:1 mass ratio for the inorganic lithium powder such as powder and lithium iodide by the mol ratio of 3:1, and formed containing solid substance be the solution of 2%wt, when temperature is 65 DEG C, stirring and refluxing 3h, then, add the plexiglass powder in formula and 5% trioctyl trimellitate compound, thus make content in polymethylmethacrylate of methylamino-butyric acid lithium and lithium iodide be 6%wt, when temperature is 50 DEG C, stirring and refluxing 3h, polymethylmethacrylate wherein is made to be dissolved among acetone-methanol mixed solvent completely, obtain the acetone-methanol solution coating containing organolithium and the polymethylmethacrylate of inorganic lithium surperficial with polyvinylidene difluoride (PVDF) semi-permeable membranes, after acetone-methanol solvate wherein is evaporated completely, again apply the acetone-methanol solution of the polymethylmethacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 18 times, then formed containing the solid electrolyte film of organolithium and the polymethylmethacrylate of inorganic lithium, finally this solid electrolyte film is placed in the dry 2h of vacuum drying oven that temperature is 55 DEG C, so just obtain the polymer solid electrolyte film containing organolithium. the most high conductivity of this copolymer solid electrolyte is 8.12x10-3S/cm, electrochemical stability window is 1.1V, it may also be useful to the life-span is 650Q, and discharge and recharge number of times is 1800 times, and capacity is 180mAh/g.
Embodiment 2
Under the protection of nitrogen, by 1.00:1.003:3.00 of the mol ratio of NaOH:LiCl:NMP, the NaOH aqueous solution of 50%wt is added in the N-Methyl pyrrolidone organic solvent that temperature is 80 DEG C slowly, then with the heat-up rate of 1.6 DEG C/min, temperature is raised to 120 DEG C, and under this temperature condition, after backflow insulation 3h, then temperature is raised to 200 DEG C by 2.6 DEG C/min heat-up rate, and under this temperature condition, backflow insulation 30min, then, the cooling rate of reaction mixture 0.6 DEG C/min is reduced the temperature to 160 DEG C, solid lithium chloride is added under this temperature condition, and after being incubated 2h, stop backflow, start the moisture content evaporated in back mixing compound, the liquid component being evaporated is detected every 5min, when the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%, stop after having a large amount of white crystal to precipitate out stirring and heating simultaneously, and under this temperature condition, it is incubated filtration while hot, during filtration, reaction system same amount and temperature are that the N-Methyl pyrrolidone solvent of 30 DEG C constantly rinses white crystal, the temperature of the colourless permeate obtained reduces the temperature to 50 DEG C with the cooling rate of 0.6 DEG C/min, filtrate precipitates out a large amount of white crystals again, then filter under this temperature condition, the white crystal obtained is dissolved in alcohol solvent, form the ethanolic soln containing white crystal 20%wt, then heating in water bath, temperature is raised to 60 DEG C, insulation backflow 45min, then, after reducing the temperature to 20 DEG C, filter, filter cake is stand-by, recycling filtrate, the filter cake repetitive scrubbing obtained 6 times, then inserts filter cake in the vacuum drying oven of 100 DEG C after dry 3h, and white crystal becomes the methylamino-butyric acid lithium that white powder is detected as purity 99��% through Fourier infrared spectrograph analysis, the methylamino-butyric acid lithium white obtained is dissolved in the acetone-methanol mixed solvent of 5:1 mass ratio for the inorganic lithium powder such as powder and lithium iodate by the mol ratio of 3:1, and formed containing solid substance be the solution of 3%wt, when temperature is 50 DEG C, stirring and refluxing 3h, then, add the plexiglass powder in formula and the own ester cpds of 3% tri trimellitate, thus make content in polymethylmethacrylate of methylamino-butyric acid lithium and lithium iodide or lithium iodate be 8%wt, when temperature is 55 DEG C, stirring and refluxing 2h, polymethylmethacrylate wherein is made to be dissolved among acetone-methanol mixed solvent completely, obtain the acetone-methanol solution coating containing organolithium and the polymethylmethacrylate of inorganic lithium surperficial with polyvinylidene difluoride (PVDF) semi-permeable membranes, after acetone-methanol solvate wherein is evaporated completely, again apply the acetone-methanol solution of the polymethylmethacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 16 times, then formed containing the solid electrolyte film of organolithium and the polymethylmethacrylate of inorganic lithium, finally this solid electrolyte film is placed in the dry 2.5h of vacuum drying oven that temperature is 55 DEG C, so just obtain the polymer solid electrolyte film containing organolithium. the most high conductivity of this copolymer solid electrolyte is 9.36x10-3S/cm, electrochemical stability window is 1.5V, it may also be useful to the life-span is 450Q, and discharge and recharge number of times is 1300 times, and capacity is 180mAh/g.
Embodiment 3
Under the protection of nitrogen, by 1.00:1.003:3.00 of the mol ratio of NaOH:LiCl:NMP, the NaOH aqueous solution of 50%wt is added in the N-Methyl pyrrolidone organic solvent that temperature is 7080 DEG C slowly, then with the heat-up rate of 1.7 DEG C/min, temperature is raised to 110 DEG C, and under this temperature condition, after backflow insulation 4.0h, then temperature is raised to 190 DEG C by 2.7 DEG C/min heat-up rate, and under this temperature condition, backflow insulation 40min, then, the cooling rate of reaction mixture 0.7 DEG C/min is reduced the temperature to 155 DEG C, solid lithium chloride is added under this temperature condition, and after being incubated 2.5h, stop backflow, start the moisture content evaporated in back mixing compound, the liquid component being evaporated is detected every 5min, when the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%, stop after having a large amount of white crystal to precipitate out stirring and heating simultaneously, and under this temperature condition, it is incubated filtration while hot, during filtration, reaction system same amount and temperature are that the N-Methyl pyrrolidone solvent of 30 DEG C constantly rinses white crystal, the temperature of the colourless permeate obtained reduces the temperature to 555 DEG C with the cooling rate of 0.7 DEG C/min, filtrate precipitates out a large amount of white crystals again, then in this temperature
Filtering under 15 conditions, the white crystal obtained is dissolved in alcohol solvent, forms the ethanolic soln containing white crystal 26%wt, then heating in water bath, temperature is raised to 650 DEG C, and insulation backflow 45min, then, after reducing the temperature to 28 DEG C, filtering, filter cake is stand-by, recycling filtrate; The filter cake repetitive scrubbing obtained 7 times, then inserts filter cake in the vacuum drying oven of 108 DEG C after dry 2.6h, and white crystal becomes the methylamino-butyric acid lithium that white powder is detected as purity 99.91% through Fourier infrared spectrograph analysis; The methylamino-butyric acid lithium white obtained is dissolved in the acetone-methanol mixed solvent of 5:1 mass ratio for powder and the inorganic lithium powder such as lithium iodide and lithium iodate (each 50%) by the mol ratio of 3:1, and formed containing solid substance be the solution of 2.5%wt, be 60 DEG C in temperature
When, stirring and refluxing 2.8h, then, add the plexiglass powder and 4%1 in formula, 2, 4-triisooctyl trimellitate compound, thus make content in polymethylmethacrylate of methylamino-butyric acid lithium and lithium iodide and lithium iodate (each 50%) be 6.8%wt, when temperature is 53 DEG C, stirring and refluxing 2.6h, polymethylmethacrylate wherein is made to be dissolved among acetone-methanol mixed solvent completely, obtain the acetone-methanol solution coating containing organolithium and the polymethylmethacrylate of inorganic lithium surperficial with polyvinylidene difluoride (PVDF) semi-permeable membranes, after acetone-methanol solvate wherein is evaporated completely, again apply the acetone-methanol solution of the polymethylmethacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply
17 times, then formed containing the solid electrolyte film of organolithium and the polymethylmethacrylate of inorganic lithium, finally this solid electrolyte film is placed in the dry 2.3h of vacuum drying oven that temperature is 3 DEG C, has so just obtained the polymer solid electrolyte film containing organolithium. The most high conductivity of this copolymer solid electrolyte is 8.83x10-3S/cm, electrochemical stability window is 1.3V, it may also be useful to the life-span is 584Q, and discharge and recharge number of times is 1531 times, capacity 200mAh/g.
Comparative example 1
The inorganic lithium powder such as commercially available chemical pure methylamino-Sodium propanecarboxylate white powder and lithium iodate are dissolved in the acetone-methanol mixed solvent of 5:1 mass ratio by the mol ratio of 3:1, and formed containing solid substance be the solution of 3%wt, when temperature is 65 DEG C, stir back 2.3h, then, add the plexiglass powder and 4%1 in formula, 2, 4-triisooctyl trimellitate compound, thus make methylamino-Sodium propanecarboxylate and lithium iodide or the lithium iodate content 8%wt in polymethylmethacrylate, when temperature is 50��55 DEG C, stirring and refluxing 2��3h, polymethylmethacrylate wherein is made to be dissolved among acetone-methanol mixed solvent completely, obtain the acetone-methanol solution coating containing organolithium and the polymethylmethacrylate of inorganic lithium surperficial with polyvinylidene difluoride (PVDF) semi-permeable membranes, after acetone-methanol solvate wherein is evaporated completely, again apply the acetone-methanol solution of the polymethylmethacrylate of organolithium and inorganic lithium, after being evaporated completely Deng acetone-methanol solvate, send out and repeatedly apply 18 times, then formed containing the solid electrolyte film of organolithium and the polymethylmethacrylate of inorganic lithium, finally this solid electrolyte film is placed in the dry 2.5h of vacuum drying oven that temperature is 55 DEG C, so just obtain the polymer solid electrolyte film containing organic sodium. the most high conductivity of this copolymer solid electrolyte is 9.10x10-6S/cm, electrochemical stability window is 1.0V, and obtained battery work-ing life is 80Q, and discharge and recharge number of times is 302 times, and capacity is 1.3mAh/g.
Claims (3)
1. the manufacturing process of a polymer solid electrolyte film, in its solid electrolyte, organolithium and inorganic lithium mol ratio are 3:1, described organolithium and inorganic lithium content in the polymer is 6��8%wt, should comprise containing the manufacturing process of the copolymer solid electrolyte of organolithium:
A: prepared by methylamino-butyric acid lithium:
1). under the protection of nitrogen, the NaOH aqueous solution of 38%wt slowly is added in the N-Methyl pyrrolidone nmp solvent of temperature 60��80 DEG C, then with the heat-up rate of 0.6��0.8 DEG C/min, temperature is raised to 100��120 DEG C, and under this temperature condition, backflow insulation 3��4.5h, then with the heat-up rate of 1.6��1.8 DEG C/min, temperature is raised to 180��200 DEG C, and under this temperature condition, backflow insulation 30��45min, then, reaction mixture is reduced the temperature to 150��160 DEG C with the cooling rate of 0.6��0.8 DEG C/min, solid lithium chloride is added under this temperature condition, the mol ratio of NaOH:LiCl:NMP is 1:1.003:3, after insulation 2��3h, stop backflow, start the moisture evaporating in reaction mixture, the liquid component being evaporated is detected every 5min, when the amount containing N-Methyl pyrrolidone solvent in the liquid component evaporated accounts for 90%, stop after having a large amount of white crystal to precipitate out stirring and heating simultaneously, and under this temperature condition, it is incubated filtration while hot, during filtration with reaction system same amount and temperature be 30 DEG C N-Methyl pyrrolidone solvent constantly rinse white crystal,
2). by 1) white crystal that obtains is dissolved in alcohol solvent, forms the ethanolic soln containing white crystal 20��30%wt, then heating in water bath, temperature is raised to 60��70 DEG C, insulation backflow 45min, then, after reducing the temperature to 20��30 DEG C, filter to obtain filter cake;
3). to 2) after the filter cake repetitive scrubbing that obtains 6��8 times, filter cake is inserted in the vacuum drying oven of 100��110 DEG C after dry 2��3h, it is stand-by that white crystal becomes the white powder containing 30%��40%wt crystal water; Detecting gained white powder through Fourier infrared spectrograph analysis is methylamino-butyric acid lithium, and purity is 99��99.95%;
B, acetone-methanol solution preparation containing organolithium, inorganic lithium and polymethylmethacrylate
The white powder obtained in step A and inorganic lithium powder are dissolved in the acetone that mass ratio is 5:1-methanol mixed solvent by the mol ratio of 3:1, and formed containing solid substance be the solution of 2��3%wt, when temperature is 50��65 DEG C, stirring and refluxing 2��3h, then, add the benzene polyacid ester compound of the plexiglass powder in formula and 3��5%, thus make content in polymethylmethacrylate of organolithium and inorganic lithium be 6��8%wt, when temperature is 50��55 DEG C, stirring and refluxing 2��3h, polymethylmethacrylate wherein is made to be dissolved among acetone-methanol mixed solvent completely, stand-by,
Prepared by C, copolymer solid electrolyte containing organolithium
By B) step obtains containing organolithium, acetone-the methanol solution of inorganic lithium and polymethylmethacrylate is coated in polyvinylidene difluoride (PVDF) semi-permeable membranes surface, after acetone-methanol solvate wherein is evaporated completely, repeatedly apply again 16��18 times, then formed containing the solid electrolyte film of organolithium and the polymethylmethacrylate of inorganic lithium, finally this solid electrolyte film is placed in the dry 2��2.5h of vacuum drying oven that temperature is 50��55 DEG C, the obtained copolymer solid electrolyte target compound containing organolithium, the electric conductivity of resulting polymers solid electrolyte is (8.12��9.36) �� 10-3S/cm, electrochemical stability window is 1.1��1.5V.
2. the manufacturing process of polymer solid electrolyte film according to claim 1, it is characterised in that, described inorganic lithium is 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 compound is the one of following material: the own ester of trioctyl trimellitate, tri trimellitate, pyromellitic acid four ester, 1,2,4-triisooctyl trimellitate.
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