CN1468909A - Gel-type solid polymer electrolyte and its prepn - Google Patents

Gel-type solid polymer electrolyte and its prepn Download PDF

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CN1468909A
CN1468909A CNA021261229A CN02126122A CN1468909A CN 1468909 A CN1468909 A CN 1468909A CN A021261229 A CNA021261229 A CN A021261229A CN 02126122 A CN02126122 A CN 02126122A CN 1468909 A CN1468909 A CN 1468909A
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gel
iodine
small molecules
polymer electrolyte
solid polymer
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CN1203130C (en
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康俊杰
方世壁
李永军
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Institute of Chemistry CAS
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Abstract

The gel-type solid polymer electrolyte consists of comb-shaped polysiloxane 3-59.3 wt%, crosslinking agent 0.7-12 wt%, polar small molecular weight plasticizer 40-85 wt% and inorganic iodine salt 0-15 wt%. The preparation process is also disclosed. The present invention has the advantages of simple preparation process, high ionic conductivity and high heat stability, and may be used in dye sensitized solar cell.

Description

A kind of gel-type solid polymer electrolyte and preparation method
Technical field the present invention relates to a kind of gel-type solid polymer electrolyte and preparation method, and it is simple that this ionogen has preparation technology, and the advantage of ionic conductance height and Heat stability is good can be used as the electrolyte in the dye sensitization solar battery.
Background technology is along with the continuous increase of the whole world to demand for energy, and people begin to pay attention to the development and utilization of sun power gradually in recent years.Nature, 1991,353:737 has reported a kind of novel dye sensitization solar battery.This battery has the photoelectric transformation efficiency height, makes advantages such as simple, that production cost is low.Dye sensitization solar battery uses the organic solution of iodine and iodide as ionogen usually.But use electrolytic solution can bring leakage and solvent evaporates problem.Solid solar battery or electrolytic solution solid state are the development trends of current dye sensitization solar battery in the world.Use copolymer solid electrolyte can not only overcome leakage and solvent evaporates problem, prolong the work-ing life of battery, can also reduce the sealing difficulty of battery greatly, therefore can fundamentally improve the stability and the practicality of battery.
Solar Energy Materials ﹠amp; Solar Cells, 2000,61:135 has reported a kind of solid electrolyte system based on oxyethane and epihalohydrin copolymer.But the room-temperature ion conductivity of this system only is 10 -5Cm -1, during as the electrolyte in the dye sensitization solar battery, can reduce the photoelectric transformation efficiency of battery.J.Phys.Chem., 1995,99:17071 has proposed a kind of gel-type solid polymer electrolyte that can be used for dye sensitization solar battery.This ionogen is body material with the polyacrylonitrile, improves ionic conductance by adding the carbonates softening agent, thereby has increased substantially the photoelectric transformation efficiency of battery.But because the employed polyacrylonitrile of this system is a simple linear polymer, therefore in use small molecules softening agent volatilization phenomenon is apparent in view, thereby reduces the ionic conductivity of electrolyte, and the battery performance that finally causes descends.
It is on the low side that summary of the invention the objective of the invention is to overcome in the above-mentioned prior art electrolyte ion conductivity, softening agent volatilization obvious defects, and a kind of gel-type solid polymer electrolyte has been proposed, the preparation method of gel-type solid polymer electrolyte is provided simultaneously.
A kind of gel-type solid polymer electrolyte of the present invention is made up of the three-dimensional network type polymer backbone, polarity small molecules softening agent and the inorganic salt compounded of iodine that are hung with quaternary ammonium group.The described three-dimensional network type polymer backbone that is hung with quaternary ammonium group is to be made by crosslinking reaction by comb shaped polysiloxane and linking agent.
A kind of gel-type solid polymer electrolyte, percentage ratio meter by weight, form by following component and content:
Comb shaped polysiloxane 3～59.3%
Linking agent 0.7～12%
Polarity small molecules softening agent 40～85%
Inorganic salt compounded of iodine 0～15%
The structural formula of described comb shaped polysiloxane is as follows:
Figure A0212612200051
In above-mentioned chemical structural formula, R 1For molecular weight is that 400～3500 polyether lateral chain (also is (CH 2) 3O (CH 2CH 2O) n(CH 2CH (CH 3) O) nH); R 2For end has the anionic quaternary ammonium salt side chain of iodine (also is (CH 2) 3N +(CH 3) 3I -); X+y+z=25～150; (y+z)/(x+y+z) * 100=10%; Z/ (y+z) * 100%=10～90%.
Comb shaped polysiloxane of the present invention is by the containing hydrogen silicone oil (M that contains 1 molar part SiH repeating unit n=2000～11000, the SiH repeating unit account for total repetition unit number 10%) and the allyl polyether alcohol of 0.1～0.9 molar part (also be CH 2=CHCH 2O (CH 2CH 2O) n(CH 2CH (CH 3) nO) H, M n=400～3500), the N of 0.15～1.35 molar part, the N-DMAA carries out quaterisation with the methyl iodide of 1～9 molar part and obtains after the addition of silicon hydrogen.
Described polarity small molecules softening agent is NSC 11801 (EC), propylene carbonate (PC), gamma-butyrolactone (γ-BL), N, dinethylformamide (DMF) or their arbitrary proportion mixture.Preferred NSC 11801 (EC), propylene carbonate (PC) or their arbitrary proportion mixture.
Described inorganic salt compounded of iodine is potassiumiodide, sodium iodide.Described linking agent is the isocyanic ester of trifunctional, and structural formula is as follows:
Figure A0212612200061
A kind of gel-type solid polymer electrolyte of the present invention is made up of said components, makes through thermal curing method.Described three-dimensional network type polymer backbone can be given the ionogen excellent mechanical property; By polarity small molecules softening agent is trapped in the three-dimensional network type polymer backbone, can reduce the volatilization of small molecules softening agent significantly.Be suspended on the quaternary ammonium group on the three-dimensional network type polymer backbone, can be used as ion source, the iodine negatively charged ion is provided.Polarity small molecules softening agent can promote quaternary ammonium group and inorganic salt compounded of iodine to dissociate, and the ion transport passage is provided.The inorganic salt compounded of iodine that adds can provide extra iodine negatively charged ion, and can interact with the quaternary ammonium group that is suspended on the three-dimensional network type polymer backbone, further promotes dissociating of salt, thereby improves the room-temperature ion conductivity.The room-temperature ion conductivity of gel-type solid polymer electrolyte of the present invention is up to 10 -3S/cm.
The preparation method of a kind of gel-type solid polymer electrolyte of the present invention adopts the thermal curing method film forming, by weight percentage, carries out as follows:
A. with comb shaped polysiloxane 3%～59.3%, linking agent 0.7～12%, polarity small molecules softening agent 40～85%, inorganic salt compounded of iodine 0～15% mixes, and stirs and makes it dissolving, generates homogeneous liquid;
B. homogeneous liquid is placed encloses container, heated 2～8 hours down, obtain electrolytic thin-membrane at 60～90 ℃.
The gel-type solid polymer electrolyte of the present invention's preparation has been obtained following invention effect: 1. preparation technology is simple, and curing speed is fast, is easy to realize suitability for industrialized production; 2. ionic conductance height; 3. thermostability, film-forming properties and mechanical property are good.Gel-type solid polymer electrolyte of the present invention can be as the electrolyte in the dye sensitization solar battery.
Embodiment:
Embodiment 1
Containing hydrogen silicone oil (the M that will contain 0.01mol SiH repeating unit n=7400; The SiH repeating unit account for total repetition unit number 10%) and 0.005mol allyl polyether alcohol (M n=2300) be dissolved in the 50mL toluene.Under nitrogen protection, be warming up to 60 ℃, add the dichloromethane solution (1mg/mL) of 0.5mL dicyclopentadiene platinum chloride.Be warming up to 90 ℃, reaction 24h.Add 0.0075mol N then, the dichloromethane solution (1mg/mL) of N-DMAA and 4.8mL dicyclopentadiene platinum chloride continues reaction 24h.Rotary evaporation is removed toluene and excessive N, and the N-DMAA obtains thick liquid.Above-mentioned thick liquid is dissolved in the 25mL ethanol, adds the methyl iodide of 0.05mol, react 24h down at 40 ℃.Rotary evaporation is removed ethanol and excessive methyl iodide, obtains comb type polysiloxane (z/ (y+z) * 100%=50%).
Embodiment 2
Containing hydrogen silicone oil (the M that will contain 0.01mol SiH repeating unit n=7400; The SiH repeating unit account for total repetition unit number 10%) and 0.001mol allyl polyether alcohol (M n=2300) be dissolved in the 50mL toluene.Under nitrogen protection, be warming up to 60 ℃, add the dichloromethane solution (1mg/mL) of 0.1mL dicyclopentadiene platinum chloride.Be warming up to 90 ℃, reaction 24h.Add 0.0135mol N then, the dichloromethane solution (1mg/mL) of N-DMAA and 5.2mL dicyclopentadiene platinum chloride continues reaction 24h.Rotary evaporation is removed toluene and excessive N, and the N-DMAA obtains thick liquid.Above-mentioned thick liquid is dissolved in the 25mL ethanol, adds the methyl iodide of 0.09mol, react 24h down at 40 ℃.Rotary evaporation is removed ethanol and excessive methyl iodide, obtains comb type polysiloxane (z/ (y+z) * 100%=90%).
Embodiment 3
With the comb type polysiloxane among the 2.75g embodiment 1,0.45g linking agent, 2.88g EC, 1.92gPC join in the 50mL single port flask; Induction stirring made it to dissolve fully in 4 hours, generated homogeneous liquid; Place the container of sealing then, heated 4 hours down, obtain electrolytic thin-membrane at 80 ℃.
This system room-temperature ion conductivity is 7.7 * 10 -4S/cm.
Embodiment 4
With the comb type polysiloxane among the 1.72g embodiment 1,0.28g linking agent, 6g DMF join in the 50mL single port flask; Induction stirring made it to dissolve fully in 4 hours, generated homogeneous liquid; Place the container of sealing then, heated 4 hours down, obtain electrolytic thin-membrane at 80 ℃.
This system room-temperature ion conductivity is 1.1 * 10 -3S/cm.
Embodiment 5
With the comb type polysiloxane among the 2.48g embodiment 1,0.4g linking agent, 2.59g EC, 1.73gPC, 0.8gKI join in the 50mL single port flask; Induction stirring made it to dissolve fully in 4 hours, generated homogeneous liquid; Place the container of sealing then, heated 4 hours down, obtain electrolytic thin-membrane at 80 ℃.
This system room-temperature ion conductivity is 1.67 * 10 -3S/cm.
Embodiment 6
With the comb type polysiloxane among the 1.89g embodiment 2,0.11g linking agent, 3g γ-BL join in the 50mL single port flask; Induction stirring made it to dissolve fully in 4 hours, generated homogeneous liquid; Place the container of sealing then, heated 4 hours down, obtain electrolytic thin-membrane at 80 ℃.
This system room-temperature ion conductivity is 9.7 * 10 -4S/cm.

Claims (7)

1. gel-type solid polymer electrolyte, percentage ratio meter by weight, form by following component and content:
Comb shaped polysiloxane 3～59.3%
Linking agent 0.7～12%
Polarity small molecules softening agent 40～85%
Inorganic salt compounded of iodine 0～15%
2. according to the solid electrolyte of claim 1, it is characterized in that: the structural formula of described comb shaped polysiloxane is as follows:
Figure A0212612200021
In above-mentioned chemical structural formula, R1 is that molecular weight is 400～3500 polyether lateral chain; R2 is that end has the anionic quaternary ammonium salt side chain of iodine; X+y+z=25～150; (y+z)/(x+y+z) * 100=10%; Z/ (y+z) * 100%=10～90%.
3. according to the solid electrolyte of claim 1, it is characterized in that: described linking agent is the isocyanic ester of trifunctional, and structural formula is as follows:
4. according to the solid electrolyte of claim 1, it is characterized in that: described polarity small molecules softening agent is NSC 11801, propylene carbonate, gamma-butyrolactone, N, dinethylformamide or their arbitrary proportion mixture.
5. according to the solid electrolyte of claim 4, it is characterized in that: described polarity small molecules softening agent is NSC 11801, propylene carbonate or their arbitrary proportion mixture.
6. according to the solid electrolyte of claim 4, it is characterized in that: described inorganic salt compounded of iodine is potassiumiodide, sodium iodide.
7. the preparation method of a gel-type solid polymer electrolyte adopts the thermal curing method film forming, by weight percentage, carries out as follows:
A. with comb shaped polysiloxane 3%～59.3%, linking agent 0.7～12%, polarity small molecules softening agent 40～85%, inorganic salt compounded of iodine 0～15% mixes, and stirs and makes it dissolving, generates homogeneous liquid;
B. homogeneous liquid is placed encloses container, heated 2～8 hours down, obtain electrolytic thin-membrane at 60～90 ℃.
CN 02126122 2002-07-16 2002-07-16 Gel-type solid polymer electrolyte and its prepn Expired - Fee Related CN1203130C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320664C (en) * 2004-04-22 2007-06-06 复旦大学 Solar cel adopting organic/inorganic nano doped quasi-solid state electrolyte, and its prepn. method
CN1320663C (en) * 2004-04-22 2007-06-06 复旦大学 Solar cell based on polymer doped quasi-solid state electrolyte material and its prepn. method
CN100470685C (en) * 2006-09-14 2009-03-18 中国科学院等离子体物理研究所 Quasi-solid nano-composite gel electrolyte, its production and use
CN1772806B (en) * 2005-10-29 2010-08-11 华侨大学 Prepn of AS resin/N-alkyl pyridine iodine salt polymer gel electrolyte
CN101950676A (en) * 2010-09-27 2011-01-19 彩虹集团公司 Preparation method of solid-state dye-sensitized solar cell
CN101604578B (en) * 2009-07-16 2011-11-16 长兴化学工业股份有限公司 Electrolyte composition
CN102290246A (en) * 2011-06-20 2011-12-21 华东师范大学 Polymer gel electrolyte and preparation method thereof
CN103208651A (en) * 2013-03-26 2013-07-17 中南大学 Siloxane-based solid electrolyte and preparation and application thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320664C (en) * 2004-04-22 2007-06-06 复旦大学 Solar cel adopting organic/inorganic nano doped quasi-solid state electrolyte, and its prepn. method
CN1320663C (en) * 2004-04-22 2007-06-06 复旦大学 Solar cell based on polymer doped quasi-solid state electrolyte material and its prepn. method
CN1772806B (en) * 2005-10-29 2010-08-11 华侨大学 Prepn of AS resin/N-alkyl pyridine iodine salt polymer gel electrolyte
CN100470685C (en) * 2006-09-14 2009-03-18 中国科学院等离子体物理研究所 Quasi-solid nano-composite gel electrolyte, its production and use
CN101604578B (en) * 2009-07-16 2011-11-16 长兴化学工业股份有限公司 Electrolyte composition
CN101950676A (en) * 2010-09-27 2011-01-19 彩虹集团公司 Preparation method of solid-state dye-sensitized solar cell
CN101950676B (en) * 2010-09-27 2012-01-04 彩虹集团公司 Preparation method of solid-state dye-sensitized solar cell
CN102290246A (en) * 2011-06-20 2011-12-21 华东师范大学 Polymer gel electrolyte and preparation method thereof
CN102290246B (en) * 2011-06-20 2012-10-17 华东师范大学 Polymer gel electrolyte and preparation method thereof
CN103208651A (en) * 2013-03-26 2013-07-17 中南大学 Siloxane-based solid electrolyte and preparation and application thereof
CN103208651B (en) * 2013-03-26 2015-07-29 中南大学 A kind of siloxy group solid electrolyte and Synthesis and applications thereof

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