CN101792587B - Method for preparing composite solid electrolyte based on polyphosphazenes micron-sphere - Google Patents
Method for preparing composite solid electrolyte based on polyphosphazenes micron-sphere Download PDFInfo
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- CN101792587B CN101792587B CN2010101365334A CN201010136533A CN101792587B CN 101792587 B CN101792587 B CN 101792587B CN 2010101365334 A CN2010101365334 A CN 2010101365334A CN 201010136533 A CN201010136533 A CN 201010136533A CN 101792587 B CN101792587 B CN 101792587B
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Abstract
The invention discloses a method for preparing a composite solid electrolyte based on a polyphosphazenes micron-sphere, belonging to the technical field of lithium ion batteries. The method comprises the following steps of: preparing acetonitrile solution of the polyphosphazenes micron-sphere; and adding polyoxyethylene and lithium perchlorate and pouring the mixture to a polytetrafluoroethylene template to prepare the composite solid electrolyte. The polyphosphazenes micron-sphere prepared by the invention has uniform arrangement of the diameters, favorable dispersion degrees as well as smooth and uniform surfaces of the film, which proves that organic/inorganic hybrid polyphosphazenes micron-sphere and a PEO polymer electrolyte matrix have favorable compatibility and indicates that the composite polymer electrolyte has high room-temperature conductivity, a high electrochemical stable window and high lithium ion transference number. The composite solid electrolyte can be used as a lithium ion battery solid electrolyte material.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of lithium batteries, specifically be a kind of inorganic-organic hybrid based on the polyphosphazenes micron-sphere method for preparing composite solid electrolyte.
Background technology
Polymer dielectric because have light weight, visco-elasticity is good and advantage such as good film-forming property, especially is suitable as the electrolyte of lithium ion battery.Comparing with the ordinary liquid lithium ion battery, is that barrier film and electrolytical polymer Li-ion battery improve significantly at the aspects such as specific energy, security and structure design of battery with the polymer dielectric film.As the barrier film and the ionogen of polymer Li-ion battery, polymer dielectric film should possess characteristics such as the electrochemical window of higher conductivity at room temperature, good electrode interface stability, broad and favorable mechanical performance.Polyoxyethylene (PEO) is owing to the constitutional features with the ionic conduction of being easy to receives much concern, yet the polymer dielectric that is formed by PEO and an alkali metal salt has higher crystallization phases when room temperature, formed ionogen also can only at high temperature could use, thereby its practical application is restricted.The method that is commonly used to reduce PEO degree of crystallinity is to add the organic liquid softening agent, though the adding of liquid plasticizer has improved the ionic conductivity of polymer dielectric, but also destroyed electrolytical mechanical property and increased it and the reactive behavior of electrode materials simultaneously, reduced battery life.An important trend is the development all-solid-state composite polymer electrolyte, to replace the present polymer dielectric that contains liquid.
Solid composite polymeric thing ionogen (CPE) is to add SOLID ORGANIC or mineral filler in the polymer dielectric of plasticizer-containing not, forms composite polymer electrolyte.Compare when not filled, the specific conductivity of CPE obviously improves, and mechanical property improves, and strengthens with the interface stability of lithium electrode, and lithium ion transference number increases.That the composite polymer electrolyte that adds solid packing might become is all solid state, electrolyte of new generation in the high-performance chargeable lithium battery.Employed filler is mainly ceramic powder, stratified material (if you would take off soil) and ferroelectric material (as BaTiO in the composite polymer electrolyte
3, PbTiO
3) etc. inorganic materials.But have compatibility problem between mineral filler and the polymkeric substance, in polymeric matrix, easily form, thereby dispersion is inhomogeneous in polymer body, cause the ununiformity of dielectric film, limited the further raising of solid electrolyte chemical property from cluster.
The organic inorganic hybridization polyphosphazenes micron-sphere is except having the high surface area of conventional inorganic fillers, character such as high voidage, owing to have good thermostability and flame retardant properties, particularly its organic inorganic hybridization molecular structure makes it to compare traditional inorganic materials and can greatly improve consistency with the polymer dielectric matrix, improves electrochemical stability window; And the lone-pair electron on the N atom have complexing action to the Li ion, can increase specific conductivity and improve lithium ion transference number, are the very promising filler of a class in the polymerizable compound within thing ionogen, thereby quicken the industrialization process of full solid state polymer lithium cell.
Find that through literature search seat Jingyu, Ma Xiaomei, Cui Mengzhong etc. rolled up the 401st～406 page of the fifth phase in 2005 the 63rd at " chemical journal " and delivered " PEO-LiClO to prior art
4-ZSM5 composite polymer electrolyte I. electrochemical research "; mention in the literary composition that with a kind of molecular sieve ZSM5 be filler; make PEO-LiClO4-ZSM5 all-solid-state composite polymer electrolyte (CPE) film by solution casting method, the alternating-current impedance experiment shows that the introducing of ZSM5 has improved the ionic conductivity of CPE.With the method that alternating-current impedance-steady state current combines the lithium ion transference number of CPE is measured, the result shows and mixes that lithium ion transference number obtains raising behind the ZSM5.But because ZSM5 is a kind of mineral filler, relatively poor with the consistency of PEO, than high filler loading capacity the time, can cause reunion, ionic conductivity and lithium ion transference number are reduced.Therefore a kind of and consistency polymkeric substance is good, and the exploitation of the high new organic inorganic hybridization filler of ionic conductivity and lithium ion transference number becomes problem demanding prompt solution.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of method for preparing composite solid electrolyte based on polyphosphazenes micron-sphere is provided, the polyphosphazenes micron-sphere diameter Distribution homogeneous for preparing, dispersity is fine; The surface smoothing homogeneous of film, proof organic inorganic hybridization polyphosphazenes micron-sphere and PEO polymer dielectric matrix have good consistency, show that this composite polymer electrolyte has high room-temperature conductivity and high electrochemical stability window, and high lithium ion transference number, can be used as the lithium ion battery solid electrolyte material and use.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
Step 1 takes by weighing polyphosphazenes micron-sphere, ultra-sonic dispersion in acetonitrile afterwards, the acetonitrile solution of polyphosphazenes micron-sphere;
The quality of described polyphosphazenes micron-sphere be the polyoxyethylene quality 1%～30%.
The time of described ultra-sonic dispersion is 10～60 minutes.
Step 2 is got polyoxyethylene and lithium perchlorate, joins in the step 1 gained solution, and mixing gets mixing solutions;
Describedly get polyoxyethylene and lithium perchlorate is specially: according to the mol ratio of Sauerstoffatom and lithium atom is that 8～20 ratio is got polyoxyethylene and lithium perchlorate.
Drying was 24～48 hours under described vacuum-drying was specially 50 ℃.
Compared with prior art, the present invention has following beneficial effect: composite solid polymer dielectric of the present invention has higher room-temperature conductivity and bigger lithium ion transference number and electrochemical stability window, mechanical property and Heat stability is good can be as the ionogen of solid lithium ion battery.
Description of drawings
Fig. 1 is the scanning electronic microscope SEM photo of polyphosphazenes micron-sphere (PZSMS).
Fig. 2 is the surface scan electron microscope SEM photo of the adulterated composite solid polymer dielectric of gained polyphosphazenes micron-sphere (PZSMS) among the embodiment 1.
Fig. 3 is the alternating-current impedance spectrogram of 25 ℃ of the adulterated composite solid polymer dielectric of gained polyphosphazenes micron-sphere (PZSMS) room temperatures among the embodiment 1.
Fig. 4 is the linear potential scanning curve of the adulterated composite solid polymer dielectric of gained polyphosphazenes micron-sphere (PZSMS) among the embodiment 1.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Step 1 takes by weighing the 0.1g polyphosphazenes micron-sphere, join in the 30ml acetonitrile, ultra-sonic dispersion 15 minutes, the acetonitrile solution of polyphosphazenes micron-sphere;
Step 2 takes by weighing the LiClO of 1.0g polyoxyethylene and 0.242g respectively
4(PEO and LiClO
4The O/Li mol ratio be 10: 1), join in the acetonitrile solution of polyphosphazenes micron-sphere, magnetic stirrer 8 hours, mixing solutions;
The implementation result of present embodiment: Fig. 1 is scanning electronic microscope (SEM) photo of polyphosphazenes micron-sphere (PZSMS).As can be seen from the figure, polyphosphazenes micron-sphere diameter Distribution homogeneous, dispersity is fine; Fig. 2 is scanning electronic microscope (SEM) photo of the adulterated composite solid polymer dielectric of polyphosphazenes micron-sphere (PZSMS) of preparation.As can be seen from the figure, the surface smoothing homogeneous of film proves that organic inorganic hybridization polyphosphazenes micron-sphere and PEO polymer dielectric matrix have good consistency.Fig. 3 is the alternating-current impedance spectrogram of 25 ℃ of the adulterated composite solid polymer dielectric of polyphosphazenes micron-sphere (PZSMS) room temperatures of preparation.The room-temperature conductivity that calculates is 1.25 * 10
-5S/cm is than two orders of magnitude of room-temperature conductivity raising of pure PEO.Fig. 4 is the linear potential scanning curve of the adulterated composite solid polymer dielectric of polyphosphazenes micron-sphere (PZSMS) of preparation.The electrochemical stability window of reading the adulterated composite solid polymer dielectric of polyphosphazenes micron-sphere (PZSMS) from figure is 5.0V, than pure PEO height 0.5V.Can obtain lithium ion transference number by calculating is 0.31.Above characterization result shows that this composite polymer electrolyte has high room-temperature conductivity and high electrochemical stability window, and high lithium ion transference number, can be used as the lithium ion battery solid electrolyte material and uses.
Embodiment 2
Step 1 takes by weighing the 0.2g polyphosphazenes micron-sphere, join in the 40ml acetonitrile, ultra-sonic dispersion 20 minutes, the acetonitrile solution of polyphosphazenes micron-sphere;
Step 2 takes by weighing the LiClO of 1.0g polyoxyethylene and 0.3025g respectively
4(PEO and LiClO
4The O/Li mol ratio be 8: 1), join in the acetonitrile solution of polyphosphazenes micron-sphere, magnetic stirrer 9 hours, mixing solutions;
The implementation result of present embodiment: the sign of composite solid polymer dielectric such as embodiment 1.This composite polymer electrolyte room-temperature conductivity is 1.1 * 10
-5S/cm, electrochemical stability window is 4.9V, lithium ion transference number is that this composite polymer electrolyte of 0.29. has high room-temperature conductivity and high electrochemical stability window equally, and high lithium ion transference number, can be used as the lithium ion battery solid electrolyte material and uses.
Step 1 takes by weighing the 0.3g polyphosphazenes micron-sphere, join in the 40ml acetonitrile, ultra-sonic dispersion 30 minutes, the acetonitrile solution of polyphosphazenes micron-sphere;
Step 2 takes by weighing the LiClO of 1.0g polyoxyethylene and 0.2017g respectively
4(PEO and LiClO
4The O/Li mol ratio be 12: 1), join in the acetonitrile solution of polyphosphazenes micron-sphere, magnetic stirrer 10 hours, mixing solutions;
The implementation result of present embodiment: the sign of composite solid polymer dielectric such as embodiment 1.This composite polymer electrolyte room-temperature conductivity is 1.02 * 10
-5S/cm, electrochemical stability window is 5.0V, this composite polymer electrolyte of lithium ion transference number 0.30. has high room-temperature conductivity and high electrochemical stability window equally, and high lithium ion transference number, can be used as the lithium ion battery solid electrolyte material and uses.
Claims (3)
1. the method for preparing composite solid electrolyte based on polyphosphazenes micron-sphere is characterized in that, comprises the steps:
Step 1 takes by weighing polyphosphazenes micron-sphere, ultra-sonic dispersion in acetonitrile afterwards, the acetonitrile solution of polyphosphazenes micron-sphere;
Step 2 is got polyoxyethylene and lithium perchlorate, joins in the step 1 gained solution, and mixing gets mixing solutions;
Step 3 is cast to mixing solutions on the tetrafluoroethylene template, solvent flashing, and vacuum-drying can obtain the composition polymer solid electrolyte;
The quality of described polyphosphazenes micron-sphere is 1%～30% of a polyoxyethylene quality;
Describedly get polyoxyethylene and lithium perchlorate is specially: according to the mol ratio of Sauerstoffatom and lithium atom is that 8～20 ratio is got polyoxyethylene and lithium perchlorate.
2. the method for preparing composite solid electrolyte based on polyphosphazenes micron-sphere according to claim 1 is characterized in that, the time of described ultra-sonic dispersion is 10～60 minutes.
3. the method for preparing composite solid electrolyte based on polyphosphazenes micron-sphere according to claim 1 is characterized in that, drying was 24～48 hours under described vacuum-drying was specially 50 ℃.
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| CN101924246A (en) * | 2010-09-07 | 2010-12-22 | 上海交通大学 | Preparation method of composite solid electrolyte based on polyphosphazene carbide micro-nanometer material |
| CN102618042B (en) * | 2012-03-09 | 2013-12-25 | 宁波长阳科技有限公司 | Polyphosphazene composition, solar cell back film with polyphosphazene coatings and preparation method of solar cell back film |
| CN106898811B (en) * | 2017-05-08 | 2019-07-23 | 北京化工大学 | A kind of solid electrolyte and preparation method thereof with dual diversion sub-network |
| CN110931844B (en) * | 2019-12-25 | 2022-12-23 | 西安大工迅驰材料科技有限公司 | All-solid-state composite polymer electrolyte containing modified molecular sieve |
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| US20020185627A1 (en) * | 2001-05-29 | 2002-12-12 | Chung Yuan Christian University | Solid composite polymer electrolyte |
| JP2002358823A (en) * | 2001-05-31 | 2002-12-13 | Nitto Denko Corp | Gel electrolyte and utilization of the same |
| CN1282710C (en) * | 2004-12-16 | 2006-11-01 | 上海交通大学 | Full-solid composite polymer electrolyte containing molecular sieve and preparation method therefor |
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