CN101872873B - Composite solid electrolyte based on surface modified Polyphosphazenes polyphosphazenes microsphere and preparation method thereof - Google Patents

Composite solid electrolyte based on surface modified Polyphosphazenes polyphosphazenes microsphere and preparation method thereof Download PDF

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CN101872873B
CN101872873B CN2010102143800A CN201010214380A CN101872873B CN 101872873 B CN101872873 B CN 101872873B CN 2010102143800 A CN2010102143800 A CN 2010102143800A CN 201010214380 A CN201010214380 A CN 201010214380A CN 101872873 B CN101872873 B CN 101872873B
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polyphosphazenes
sphere
solid electrolyte
polyethylene glycol
microsphere
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CN101872873A (en
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张家维
黄小彬
唐小真
陈奎永
顾晓俊
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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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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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 composite solid electrolyte based on a surface modified Polyphosphazenes polyphosphazenes microsphere and a preparation method thereof in the technical field of lithium batteries. The composite solid electrolyte comprises the following components in percentage by mass: the mass percent of polyoxyethylene and Polyphosphazenes polyphosphazenes microspheres is 1-30 and the mass of the polyoxyethylene and dissociable lithium salt is defined according to the 8-20 mole percent of oxygen atoms and lithium atoms. The preparation method comprises the following steps of: carrying out ultrasonic dispersion in a solvent; then adding the corresponding polyoxyethylene and dissociable lithium salt for magnetically and uniformly mixing; further casting the mixed solution on a polytetrafluoroethylene template to volatize the solvent in the mixed solution; and finally drying in a vacuum drying oven to obtain the composite solid electrolyte. The invention not only has high room-temperature conductivity, favorable mechanical capacity, no any liquid component, smooth and level surface, uniform inside components as well as high migration number of lithium ions and electrochemistry stable window.

Description

Based on composite solid electrolyte of surface modified Polyphosphazenes polyphosphazenes microsphere and preparation method thereof
Technical field
What the present invention relates to is electrolyte of a kind of technical field of lithium batteries and preparation method thereof, especially a kind of composite solid electrolyte based on surface modified Polyphosphazenes polyphosphazenes microsphere and preparation method thereof.
Technical background
Lithium ion battery because of its have that specific power is big, energy density is high, operating voltage is high, in light weight, volume is little, advantage such as nontoxic, pollution-free, on portable electric appts such as notebook computer, mobile phone, obtained using widely.The employed electrolyte of lithium ion battery is the nonaqueous electrolytic solution that contains lithium salts basically at present, has existed shortcomings such as the phenomenon of leakage, fail safe is not good enough.So people are devoted to replace with polymer dielectric the research work of liquid electrolyte.Polymer dielectric is electrolyte in battery, plays a part barrier film simultaneously again.Polymer dielectric is applied to lithium ion battery and helps preparing safety, light weight, high-energy-density and different battery.
The polymer dielectric of research is broadly divided into full solid state polymer electrolyte and gel polymer electrolyte at present.Though the gel polymer electrolyte conductivity is higher,, cause shortcomings such as bag liquid instability, bad mechanical property owing to contain a large amount of liquid plasticizers in the polymer.An important trend is the development all-solid-state composite polymer electrolyte, to replace the present polymer dielectric that contains liquid.Polyethylene glycol oxide (PEO) is owing to the architectural feature with the ionic conduction of being easy to receives much concern; Yet the polymer dielectric that is formed by PEO and alkali metal salt has higher crystalline phase when room temperature; Formed electrolyte also can only at high temperature could use, thereby its practical application is restricted.
In order to obtain the solid polymer electrolyte of high conductivity, in the polymer dielectric of plasticizer-containing not, add the composite polymer electrolyte (CPE) that the solid inorganic filler forms and be developed.Compare when not filled, the conductivity of CPE is significantly improved, and mechanical performance improves, and strengthens with the interface stability of lithium electrode, and lithium ion transference number increases.This shows the composite polymer electrolyte that has added solid packing, might become electrolyte of new generation in all solid state, the high-performance chargeable lithium battery.
Inorganic filler is divided into ceramic powders, stratified material, ferroelectric material (like BaTiO 3, PbTiO 3) etc.But the problem that has a compatibility between inorganic filler and the polymer; In polymeric matrix, form easily from group bunch; Inorganic particulate is assembled formed bigger grain, thereby dispersion is inhomogeneous in polymer body, has limited the further raising of solid polymer electrolyte electrical property.
The surface group of filler has very big influence to the electrical property of polymer dielectric.At polymer/filler boundary is the fast zone of transmission of ion, thereby the chemical property of filling surface group can pass through its influence to interfacial property, and then influences the migration velocity of ion.Therefore, in order to improve other electrochemical properties such as ionic conductivity of composite polymer electrolyte, it is necessary that filler is carried out surface modification.And inorganic filler is existing significant limitation aspect the modification of surface group.
Literature search through to prior art is found, Du Hongyan, and the journey amber, Yang Yongs etc. rolled up the 215th～221 page of the 2nd phase in 2004 the 10th in " electrochemistry " and have delivered " PEO base nano composite polymer electrolyte electrochemical Study on Properties ", mentioned with PEO in the literary composition 8-LiClO 4Make parent, nanometer SiO 2Be filler, process PEO 8-LiClO 4-SiO 2(x%) serial composite polymer electrolyte is measured this electrolytical conductivity, lithium ion transference number and electrochemical stability window, and its crystalline structure is made the differential thermal analysis sign.The result shows, nanometer SiO 2Introducing, significantly improved electrolytical conductivity, in the time of 22 ℃, reach 4.3 * 10 -5S cm -1In addition, also inquired into the influence mechanism of filler to the raising of composite polymer electrolyte conductivity.But because SiO 2Be 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 good with compatibility polymer, and the exploitation of the high new organic inorganic hybridization filler of ionic conductivity and lithium ion transference number becomes problem demanding prompt solution.
The organic inorganic hybridization polyphosphazenes micron-sphere not only has the high surface of conventional inorganic fillers; Character such as high voidage; Good hot property and fire resistance are also arranged, and the lone pair electrons on the N atom can have complexing to the Li ion simultaneously, can increase conductivity and improve lithium ion transference number.Particularly its organic inorganic hybridization molecular structure makes it to have the organic easy modification property that traditional inorganic material is short of most, and making in its polymerizable compound within thing electrolyte to become one type of very promising filler.
Organic inorganic hybridization polyphosphazenes micron-sphere behind the surface functional group modification is mixed in the polymeric system; Under the effect of organo-functional group, except can be, outside advantages such as electrode stability further improve with the enhancing of conventional inorganic fillers to electrolyte mechanical performance, hot property; Can also increase the compatibility of filler and polymeric matrix; Thereby further improve conductivity, improve lithium ion transference number, convenient and simple develop various new type of polymer electrolyte.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, purpose is to provide a kind of composite solid electrolyte based on surface modified Polyphosphazenes polyphosphazenes microsphere and preparation method thereof.Conductivity of the present invention is high, and satisfactory mechanical property has complex solid polymer dielectric that the surface-functionalized group modified organic inorganic hybridization polyphosphazenes micron-sphere of good electrochemical stability mixes and preparation method thereof.
The present invention realizes through following technical scheme:
The composite solid electrolyte that the present invention relates to based on surface modified Polyphosphazenes polyphosphazenes microsphere; Its constituent mass percentage is: polyethylene glycol oxide and polyphosphazenes micron-sphere mass percent are 1%～30%, and polyethylene glycol oxide and dissociable lithium salts quality are 8%～20% to confirm according to O/Li (molar percentage of oxygen atom and lithium atom).
Described polyethylene glycol oxide molecular weight Mw is 100,000～1000,000;
Described dissociable lithium salts molecular weight Mw is 106.5;
Described surface modified Polyphosphazenes polyphosphazenes microsphere filler molecular weight Mw is 1380;
Described dissociable lithium salts is LiClO 4
Described surface modified Polyphosphazenes polyphosphazenes microsphere filler be the surface through chemical group modify-OH ,-COC perhaps-the COOC polyphosphazenes micron-sphere, surface attachment difference in functionality group.
The invention still further relates to like above-mentioned method for preparing composite solid electrolyte, comprise the steps: based on surface modified Polyphosphazenes polyphosphazenes microsphere
1. according to polyethylene glycol oxide and polyphosphazenes micron-sphere mass percent: 1%～30% takes by weighing surface modified Polyphosphazenes polyphosphazenes microsphere, ultrasonic dispersion in solvent;
Step described ultrasonic in 1. is separated into 10～60 minutes;
The described solvent of step in 1. is acetonitrile.
2. be that the molar percentage of O/Li is according to polyethylene glycol oxide and dissociable lithium salts then: 8%～20% ratio adds corresponding polyethylene glycol oxide and dissociable lithium salts, and magnetic agitation is even;
The described magnetic agitation of step in 2. is 5～25 hours.
3. further mixed solution is cast on the polytetrafluoroethylene template volatilization solvent wherein.
4. dry in vacuum drying chamber at last, can obtain the complex solid polymer dielectric.
The drying of step in 4. is meant under 50 ℃, dry 24～48 hours.
The present invention has stressed the improved action of the polyphosphazenes micron-sphere of different surfaces chemical state to CPE.The functional group component of polyphosphazenes micron-sphere finishing and content have fundamental influence to conductivity, lithium ion transference number and the electrochemical stability window of composite polymer electrolyte.
CPE prepared in accordance with the present invention especially uses the CPE of the polyphosphazenes micron-sphere of modification as filler, and not only room-temperature conductivity is high; And satisfactory mechanical property, not containing any liquid component, smooth surface is smooth; Internal composition is even, and high lithium ion transference number and electrochemical stability window are arranged.
Description of drawings
Fig. 1 is the scanning electron microscopy SEM photo of polyphosphazenes micron-sphere (surface-OH is group modified).
Fig. 2 is the scanning electron microscopy SEM photo of the complex solid polymer dielectric that gained polyphosphazenes micron-sphere (surface-OH is group modified) mixes among the embodiment 1.
Fig. 3 is at PEO 10-LiClO 4Conductivity-the temperature curve that adds different amount modification polyphosphazenes micron-spheres (surface-OH is group modified) in the system.X=5 representes that the modification polyphosphazenes micron-sphere (surface-OH is group modified) that adds is 5%, and X=10 representes that the modification polyphosphazenes micron-sphere (surface-OH is group modified) that adds is 10%, by that analogy.
Fig. 4 is at PEO 10-LiClO 4Conductivity-the temperature curve that adds different amount modification polyphosphazenes micron-spheres (surface-COC is group modified) in the system.X=5 representes that the modification polyphosphazenes micron-sphere (surface-COC is group modified) that adds is 5%, and X=10 representes that the modification polyphosphazenes micron-sphere (surface-COC is group modified) that adds is 10%, by that analogy.
Fig. 5 is at PEO 10-LiClO 4Conductivity-the temperature curve that adds different amount modification polyphosphazenes micron-spheres (surface-COOC is group modified) in the system.X=5 representes that the modification polyphosphazenes micron-sphere (surface-COOC is group modified) that adds is 5%, and X=10 representes that the modification polyphosphazenes micron-sphere (surface-COOC is group modified) that adds is 10%, by that analogy.
Embodiment
Present embodiment provided detailed execution mode and process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1.
Step 1 takes by weighing 0.1g polyphosphazenes micron-sphere (surface-OH is group modified) (polyphosphazenes micron-sphere quality be PEO quality 10%) and joins in the 30ml acetonitrile ultrasonic dispersion 15 minutes;
Step 2 takes by weighing the PEO (Mw～300,000) of 1.0g and the LiClO of 0.242g respectively 4(PEO and LiClO 4The O/Li mol ratio be 10: 1) add in the acetonitrile dispersion liquid of polyphosphazenes micron-sphere magnetic stirrer dissolving 8 hours;
Step 3 is cast to the mixed solution that obtains on the polytetrafluoroethylene template, solvent flashing 6 hours,
Step 4 is transferred to the polymer dielectric film that obtains in the step 3 in the vacuum drying chamber, and 50 ℃ were continued down dry 24 hours, and can obtain the complex solid polymer dielectric.
The implementation result of present embodiment: Fig. 1 is the scanning electron microscopy SEM photo of the polyphosphazenes micron-sphere (surface-OH is group modified) of preparation.As can be seen from the figure, polyphosphazenes micron-sphere diameter Distribution homogeneous, decentralization is fine; Fig. 2 is the scanning electron microscopy SEM photo of the complex solid polymer dielectric of polyphosphazenes micron-sphere (surface-OH the is group modified) doping of preparation.As can be seen from the figure, the surface smoothing homogeneous of film proves that organic inorganic hybridization polyphosphazenes micron-sphere (surface-OH is group modified) and PEO polymer dielectric matrix have good compatibility.Fig. 3 is at PEO 10-LiClO 4Conductivity-the temperature curve that adds different amount modification polyphosphazenes micron-spheres (surface-OH is group modified) in the system.The room-temperature conductivity that sign through composite polymer electrolyte calculates is 1.45 * 10 -5S/cm improves two one magnitude than the room-temperature conductivity of pure PEO, and lithium ion transference number is 0.32, and electrochemical stability window is 5.0V.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 0.2g polyphosphazenes micron-sphere (surface-COC modification) (polyphosphazenes micron-sphere quality be PEO quality 20%) and joins in the 40ml acetonitrile ultrasonic dispersion 20 minutes;
Step 2 takes by weighing the PEO (Mw～400,000) of 1.0g and the LiClO of 0.3025g respectively 4(PEO and LiClO 4The O/Li mol ratio be 8: 1) add in the acetonitrile dispersion liquid of polyphosphazenes micron-sphere magnetic stirrer dissolving 9 hours;
Step 3 is cast to the mixed solution that obtains on the polytetrafluoroethylene template, solvent flashing 7 hours,
Step 4 is transferred to the polymer dielectric film that obtains in the step 3 in the vacuum drying chamber, and 50 ℃ were continued down dry 28 hours, and can obtain the complex solid polymer dielectric.
The implementation result of present embodiment: the sign of complex solid polymer dielectric such as embodiment 1.Fig. 4 is at PEO 10-LiClO 4Conductivity-the temperature curve that adds different amount modification polyphosphazenes micron-spheres (surface-COC is group modified) in the system.This composite polymer electrolyte room-temperature conductivity is 1.65 * 10 -5S/cm, lithium ion transference number are 0.34, and electrochemical stability window is 5.0V.This composite polymer electrolyte 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 0.3g polyphosphazenes micron-sphere (surface-COOC modification) (polyphosphazenes micron-sphere quality be PEO quality 30%) and joins in the 45ml acetonitrile ultrasonic dispersion 30 minutes;
Step 2 takes by weighing the PEO (Mw～500,000) of 1.0g and the LiClO of 0.2017g respectively 4(PEO and LiClO 4The O/Li mol ratio be 12: 1) add in the acetonitrile dispersion liquid of polyphosphazenes micron-sphere magnetic stirrer dissolving 10 hours;
Step 3 is cast to the mixed solution that obtains on the polytetrafluoroethylene template, solvent flashing 8 hours,
Step 4 is transferred to the polymer dielectric film that obtains in the step 3 in the vacuum drying chamber, transfers in the vacuum drying chamber, and 50 ℃ were continued down dry 32 hours, and can obtain the complex solid polymer dielectric.
The implementation result of present embodiment: the sign of complex solid polymer dielectric such as embodiment 1.Fig. 5 is at PEO 10-LiClO 4Conductivity-the temperature curve that adds different amount modification polyphosphazenes micron-spheres (surface-COOC is group modified) in the system.This composite polymer electrolyte room-temperature conductivity is 1.75 * 10 -5S/cm, lithium ion transference number are 0.35, and electrochemical stability window is 5.1V.This composite polymer electrolyte 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 (1)

1. method for preparing composite solid electrolyte based on surface modified Polyphosphazenes polyphosphazenes microsphere; This composite solid electrolyte constituent mass percentage is: the mass percent of polyphosphazenes micron-sphere and polyethylene glycol oxide is 1%-30%, and polyethylene glycol oxide and dissociable lithium salts quality are that 8%-20% confirms according to the molar percentage of oxygen atom and lithium atom;
Described component molecular weight is: polyethylene glycol oxide molecular weight Mw is 100,000-1000, and 000, dissociable lithium salts molecular weight Mw is 106.5, polyphosphazenes micron-sphere filler molecular weight Mw is 1380;
Described dissociable lithium salts is LiClO 4
Described surface modified Polyphosphazenes polyphosphazenes microsphere filler is that the surface is modified-the OH polyphosphazenes micron-sphere through chemical group, it is characterized in that said method comprises the steps:
1. according to polyethylene glycol oxide and polyphosphazenes micron-sphere mass percent: 1%-30% takes by weighing surface modified Polyphosphazenes polyphosphazenes microsphere, and ultrasonic dispersion is 10-60 minute in acetonitrile;
2. be that the molar percentage of oxygen atom and lithium atom is according to polyethylene glycol oxide and dissociable lithium salts then: the ratio of 8%-20% adds corresponding polyethylene glycol oxide and dissociable lithium salts, the even 5-25 of magnetic agitation hour;
3. further mixed solution is cast on the polytetrafluoroethylene template volatilization solvent wherein;
4. at last in vacuum drying chamber under 50 ℃, dry 24-48 hour, can obtain the complex solid polymer dielectric.
CN2010102143800A 2010-06-30 2010-06-30 Composite solid electrolyte based on surface modified Polyphosphazenes polyphosphazenes microsphere and preparation method thereof Expired - Fee Related CN101872873B (en)

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