CN101794908B - Method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope - Google Patents

Method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope Download PDF

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CN101794908B
CN101794908B CN201010136532XA CN201010136532A CN101794908B CN 101794908 B CN101794908 B CN 101794908B CN 201010136532X A CN201010136532X A CN 201010136532XA CN 201010136532 A CN201010136532 A CN 201010136532A CN 101794908 B CN101794908 B CN 101794908B
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polyphosphazenes
solid electrolyte
nanometer tube
solution
electrolyte based
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CN101794908A (en
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黄小彬
张家维
唐小真
刘凤凤
刘维
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Shanghai Jiaotong University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a method for preparing a solid electrolyte based on polyphosphazenes nanometer tube dope, belonging to the technical field of lithium ion batteries. The method comprises the following steps of: respectively and sequentially dissolving polyoxyethylene, lithium perchlorate and polyphosphazenes nanometer tubes into an organic solvent; dispersing and mixing the mixture; pouring the mixture on a polytetrafluoroethylene template to prepare a composite solid polymer electrolyte. An electrolyte film prepared by the invention has smooth and uniform surfaces, higher room-temperature conductivity, a high electrochemical stable window and high lithium ion transference number, and can be used as a lithium ion battery solid electrolyte material.

Description

Method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope
Technical field
That the present invention relates to is a kind of preparation method of technical field of lithium batteries, specifically is a kind of method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope of inorganic-organic hybrid.
Background technology
Lithium rechargeable battery because have that specific energy is big, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, pollution-free, special advantages such as security performance is good, become one of optimal environmental protection power supply of 21 century.But the easy leakage of liquid electrolyte is difficult for installing.Lithium ion polymer battery is except that the advantage with liquid lithium ionic cell, because adopt immobilising polymer dielectric, security performance is better, and can make the ultra-thin battery of arbitrary shape and size, thereby be more suitable for power supply as miniature electrical equipment, be with a wide range of applications.In numerous conducting polymer matrixes, polyethylene glycol oxide (PEO) also is the good solvent of lithium salts as fast-ionic conductor simultaneously, has advantages such as chemical stability is good, raw material is easy to get, synthetic method is simple.But because the higher ionic conductivity that causes of degree of crystallinity is lower, its thermal stability and mechanical performance are still waiting further raising to the pure PEO of non-modified simultaneously as solid polymer electrolyte.
Solid composite polymeric thing electrolyte (CPE) is to add SOLID ORGANIC or inorganic filler in the polymer dielectric of plasticizer-containing not, forms composite polymer electrolyte.Compare when not filled, the conductivity of CPE obviously improves, and mechanical performance 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 powders, stratified material (if you would take off soil) and ferroelectric material (as BaTiO in the composite polymer electrolyte 3, PbTiO 3) etc. inorganic material.But there is consistency problem between inorganic filler and the polymer, in polymeric matrix, easily form cluster, thereby dispersion is inhomogeneous in polymer body, has limited the further raising of solid electrolyte chemical property.
Organic inorganic hybridization poly phosphazene nano material is except character such as high surface with traditional inorganic nano material, high voidages, the inner simultaneously passage that complexity is arranged, have various different shapes and good thermal stability and fire resistance in addition, particularly its organic inorganic hybridization molecular structure makes it to compare traditional inorganic nano material and can greatly improve compatibility with the polymer dielectric matrix, improves electrochemical stability window; And the lone pair electrons on the N atom have complexing to the Li ion, can increase conductivity, improve lithium ion transference number, are the very promising filler of a class in the polymerizable compound within thing electrolyte, thereby quicken the industrialization process of full solid state polymer lithium battery.
Find that through literature search seat Jingyu, Ma Xiaomei, Cui Mengzhong, Huang Xiaobin etc. rolled up the 217th～220 page of the third phase in 2004 the 49th in " Science Bulletin " and delivered " PEO-LiClO to prior art 4The electrochemical research of-ZSM5 composite polymer electrolyte "; 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 AC impedance experiment shows that the introducing of ZSM5 has improved the ionic conductivity of CPE.With the method that AC 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 inorganic filler, relatively poor with the compatibility 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 compatibility polymer 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 solid electrolyte based on polyphosphazenes nanometer tube dope is provided, the surface smoothing homogeneous of the dielectric film for preparing, have higher 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 polyethylene glycol oxide (PEO) and lithium perchlorate (LiClO 4), join in the organic solvent, stir, get solution A;
The weight ratio of described polyethylene glycol oxide and lithium perchlorate is (4～12): 1.
Described stirring is specially uses magnetic stirrer dissolving 8～12 hours.
Step 2 takes by weighing polyphosphazene nanotube (PZSNT), joins in the organic solvent, and ultrasonic dispersion gets solution B;
The weight ratio of the polyethylene glycol oxide in described polyphosphazene nanotube and the step 1 is (0.01～0.55): 1.
Step 3 joins solution B in the solution A, and ultrasonic dispersion gets mixed solution;
Step 4 is cast to the mixed solution of step 3 gained on the polytetrafluoroethylene template, and vacuumize promptly gets the complex solid polymer dielectric.
Drying was 24～48 hours under described vacuumize was specially 50 ℃.
Described organic solvent is oxolane, acetone or acetonitrile.
The time of described ultrasonic dispersion is 15～30 minutes.
The complex solid polymer dielectric that method for preparing obtains, its component and percentage by weight are: polyethylene glycol oxide (PEO) 54～91%, lithium perchlorate (LiClO 4) 7～16% and polyphosphazene nanotube (PZSNT) 1～30%, its chemical composition general formula is: PEO/LiClO 4/ PZSNT.
Compared with prior art, the present invention has following beneficial effect: the polyphosphazene nanotube among the present invention is good dispersion in PEO based polyalcohol system, and inorganic-organic hybrid polyphosphazenes nanometer tube dope solid polymer electrolyte has high room-temperature conductivity and lithium ion transference number and electrochemical stability window.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) photo of the complex solid polymer dielectric of gained polyphosphazenes nanometer tube dope among the embodiment 1.
Fig. 2 is the complex solid polymer dielectric room temperature AC impedance spectrogram of gained polyphosphazenes nanometer tube dope among the embodiment 1.
Fig. 3 is the linear potential scanning curve of the complex solid polymer dielectric of gained polyphosphazenes nanometer tube dope among the embodiment 1.
Fig. 4 is the time current curve of the complex solid polymer dielectric of gained polyphosphazenes nanometer tube dope 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 execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Step 1 takes by weighing 1.0g polyethylene glycol oxide (PEO) and 0.125g lithium perchlorate (LiClO 4) (PEO and LiClO 4Weight ratio be 8: 1), join in the 30ml acetonitrile, magnetic stirrer 8 hours, solution A;
Step 2 takes by weighing 0.1g polyphosphazene nanotube (PZSNT) (weight ratio of PZSNT and PEO is 0.1: 1), joins in the acetonitrile, and ultrasonic dispersion 15 minutes gets solution B;
Step 3 joins solution B in the solution A, and ultrasonic dispersion 15 minutes gets mixed solution;
Step 4 is cast to the mixed solution of step 3 gained on the polytetrafluoroethylene template, in the vacuum drying chamber 50 ℃ dry 24 hours down, promptly get the complex solid polymer dielectric.
The implementation result of present embodiment: Fig. 1 is scanning electron microscopy (SEM) photo of the complex solid polymer dielectric of the polyphosphazene nanotube PZSNT doping of preparation.As can be seen from the figure, the surface smoothing homogeneous of film proves that organic inorganic hybridization polyphosphazene nanotube and PEO polymer dielectric matrix have good compatibility.Fig. 2 is the complex solid polymer dielectric room temperature AC impedance spectrogram of polyphosphazene nanotube (PZSNT) doping of preparation.The room-temperature conductivity that calculates is 1.5 * 10 -5S/cm is than two orders of magnitude of room-temperature conductivity raising of pure PEO.Fig. 3 is the linear potential scanning curve of the complex solid polymer dielectric that mixes of the polyphosphazene nanotube (PZSNT) of preparation.The electrochemical stability window of reading the complex solid polymer dielectric that polyphosphazene nanotube (PZSNT) mixes from figure is 5.0V, than pure PEO height 0.5V.Fig. 4 is the time current curve of the complex solid polymer dielectric that gained polyphosphazene nanotube PZSNT mixes among the embodiment 1.From figure, read initial current value and steady-state current value, by calculating lithium ion transference number is that the above characterization result of 0.38. 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 use.
Embodiment 2
Step 1 takes by weighing 1.0g polyethylene glycol oxide (PEO) and 0.1g lithium perchlorate (LiClO 4) (PEO and LiClO 4Weight ratio be 10: 1), join in the 40ml acetonitrile, magnetic stirrer 9 hours, solution A;
Step 2 takes by weighing 0.05g polyphosphazene nanotube (PZSNT) (weight ratio of PZSNT and PEO is 0.05: 1), joins in the acetonitrile, and ultrasonic dispersion 20 minutes gets solution B;
Step 3 joins solution B in the solution A, and ultrasonic dispersion 20 minutes gets mixed solution;
Step 4 is cast to the mixed solution of step 3 gained on the polytetrafluoroethylene template, in the vacuum drying chamber 50 ℃ dry 30 hours down, promptly get the complex solid polymer dielectric.
The implementation result of present embodiment: the sign of complex solid polymer dielectric such as embodiment 1.This composite polymer electrolyte room-temperature conductivity is 1.3 * 10 -5S/cm, electrochemical stability window is 4.9V, lithium ion transference number is that this composite polymer electrolyte of 0.36. 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.
Embodiment 3
Step 1 takes by weighing 1.0g polyethylene glycol oxide (PEO) and 0.2g lithium perchlorate (LiClO 4) (PEO and LiClO 4Weight ratio be 5: 1), join in the 50ml acetonitrile, magnetic stirrer 10 hours, solution A;
Step 2 takes by weighing 0.1g polyphosphazene nanotube (PZSNT) (weight ratio of PZSNT and PEO is 0.1: 1), joins in the acetonitrile, and ultrasonic dispersion 25 minutes gets solution B;
Step 3 joins solution B in the solution A, and ultrasonic dispersion 25 minutes gets mixed solution;
Step 4 is cast to the mixed solution of step 3 gained on the polytetrafluoroethylene template, in the vacuum drying chamber 50 ℃ dry 35 hours down, promptly get the complex solid polymer dielectric.、
The implementation result of present embodiment: the sign of complex solid polymer dielectric such as embodiment 1.This composite polymer electrolyte room-temperature conductivity is 1.2 * 10 -5S/cm, electrochemical stability window is 5.0V, this composite polymer electrolyte of lithium ion transference number 0.35. 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 (5)

1. the method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope is characterized in that, comprises the steps:
Step 1 takes by weighing polyethylene glycol oxide (PEO) and lithium perchlorate (LiClO 4), join in the organic solvent, stir, get solution A, the weight ratio of described polyethylene glycol oxide and lithium perchlorate is (4～12): 1;
Step 2 takes by weighing polyphosphazene nanotube (PZSNT), joins in the organic solvent, and ultrasonic dispersion gets solution B, and the weight ratio of the polyethylene glycol oxide in described polyphosphazene nanotube and the step 1 is (0.01～0.55): 1;
Step 3 joins solution B in the solution A, and ultrasonic dispersion gets mixed solution;
Step 4 is cast to the mixed solution of step 3 gained on the polytetrafluoroethylene template, and vacuumize promptly gets the complex solid polymer dielectric;
The component of described complex solid polymer dielectric and percentage by weight are: polyethylene glycol oxide 54～91%, lithium perchlorate 7～16% and polyphosphazene nanotube 1～30%.
2. the method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope according to claim 1 is characterized in that, described stirring is specially uses magnetic stirrer dissolving 8～12 hours.
3. the method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope according to claim 1 is characterized in that, drying was 24～48 hours under described vacuumize was specially 50 ℃.
4. the method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope according to claim 1 is characterized in that described organic solvent is oxolane, acetone or acetonitrile.
5. the method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope according to claim 1 is characterized in that the time of described ultrasonic dispersion is 15～30 minutes.
CN201010136532XA 2010-03-31 2010-03-31 Method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope Expired - Fee Related CN101794908B (en)

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