CN102324303B - Gel electrolyte of hybrid polymer and preparation method thereof - Google Patents

Gel electrolyte of hybrid polymer and preparation method thereof Download PDF

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CN102324303B
CN102324303B CN 201110165031 CN201110165031A CN102324303B CN 102324303 B CN102324303 B CN 102324303B CN 201110165031 CN201110165031 CN 201110165031 CN 201110165031 A CN201110165031 A CN 201110165031A CN 102324303 B CN102324303 B CN 102324303B
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solvent
electrolyte
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gel electrolyte
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CN102324303A (en
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宋春梅
张亮
王永光
赵丹
唐妙根
常飞
梁晟斌
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SHANGHAI REALVISION ELECTRONIC TECHNOLOGY Co Ltd
East China Normal University
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SHANGHAI REALVISION ELECTRONIC TECHNOLOGY Co Ltd
East China Normal University
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Abstract

The invention relates to gel electrolyte of a hybrid polymer and a preparation method thereof, belonging to the technical field of chemicals and energy source cells thereof. The gel electrolyte of the hybrid polymer in the invention is shown as a chemical formula (I). The preparation method provided by the invention comprises the following step of reacting through mixing a hybrid polyacrylate/polyethylene glycol (PA/PEG) polymer and a redox couple iodide/I2 to obtain the gel electrolyte of the hybrid polymer. The gel electrolyte of the hybrid polymer in the invention is easy to package, favorable in electrochemical stability and the like and is expected to be widely applied to the preparation of solar cells. The preparation method provided by the invention has the characteristics of simple route, mild operation condition, simple product extraction step, high yield and the like.

Description

A kind of hybridized polymer gel electrolyte and preparation method thereof
Technical field
The invention belongs to chemistry and energy battery technical field thereof, relate to a kind of hybridized polymer gel electrolyte and preparation method thereof particularly.
Background technology
DSSC (DSSC) is a kind of efficient, cheap, free of contamination novel solar battery.1991, Gr tzel utilized bipyridyl ruthenium (II) complex dye and nanoporous TiO first 2The DSSC of film preparation has obtained 7.1% photoelectric conversion efficiency.DSSC has received numerous researchers' lasting research and has obtained significant progress since then.The liquid electrolyte component is 0.5 mol/L KI, 0.05 mol/L I in the U.S. Pat 6 479 745 2, solvent is a propene carbonate, the conductivity that records room temperature is 7.2 mS.cm -1But; There are shortcomings such as cell package difficulty, solvent evaporates, dyestuff desorption, corrosion counterelectrode and life-span weak point based on liquid electrolyte and DSSC; Encapsulation is simple, cheap, steady performance and polymer dielectric has, and has caused researcher's keen interest.
The DSSC polymer dielectric should meet the following conditions as the polymer dielectric with practical value: (1) conductivity at room temperature reaches 10 -3S.cm -1The order of magnitude; (2) good with the electrode interface contact performance, interface resistance is little, and the interface charge transmission speed is fast; (3) good electrochemical stability; (4) good processing properties.
Polyethylene glycol PEG and polyacrylate PA are the materials of solid electrolyte, and the present invention combines both, preparation PA/PEG polymer/iodide/I 2Gel electrolyte can make this polyelectrolyte have the advantage of two kinds of polymer.
The present invention has overcome electrolyte solution and DSSC exist in the prior art cell package difficulty, solvent evaporates, dyestuff desorption, corrosion counterelectrode and life-span and defectives such as has lacked, and has proposed a kind of hybridized polymer gel electrolyte and preparation method thereof.Beneficial effects such as hybridized polymer gel electrolyte of the present invention has the encapsulation of being easy to, electrochemical stability is good; It is simple that hybridized polymer gel electrolyte preparation method of the present invention has a route; Operating condition is gentle, the simple and productive rate advantages of higher of purification of products step.
Summary of the invention
The present invention proposes a kind of hybridized polymer gel electrolyte, it has the structure of following chemical formula (I):
Figure 2011101650319100002DEST_PATH_IMAGE002
Wherein, M +Represent Na +, K +Or Li +R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15R 4Represent CH 3Perhaps H.
The invention allows for the preparation method of said hybridized polymer gel electrolyte, through hydridization polyacrylate/polyethylene glycol PA/PEG polymer and redox couple iodide/I 2Mix, reaction obtains said hybridized polymer gel electrolyte.
The preparation method of hybridized polymer gel electrolyte of the present invention may further comprise the steps successively:
(1) acrylic ester monomer is dissolved in the solvent, initator is dissolved in the solvent; Feed nitrogen and heat up 50 ~ 90 ℃ to the mixture of polyethylene glycol and solvent, add said acrylic ester monomer and initator again, in the hydridization PA/PEG polymer that reaction obtains the PA structure shown in chemical formula (II),
Figure 2011101650319100002DEST_PATH_IMAGE003
Wherein, the number of x:y:z is than being (128 ~ 572): 10: (53 ~ 307); R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15R 4Represent CH 3Perhaps H;
(2) will pass through the PA/PEG polymer that step (1) handles and join iodide/I 2In the electrolyte solution, add additive agent electrolyte again, in sealed environment,, be cooled to room temperature again and obtain hybridized polymer gel electrolyte as claimed in claim 1 in 60-90 ℃ of heating, stirring; Wherein, said iodide/I 2Electrolyte solution is with iodide, I 2Obtain with solvent, after stirring.
Wherein, PA/PEG polymer: iodide/I in the said step (2) 2Electrolyte solution: the weight ratio of additive agent electrolyte is 1: (2.34 ~ 9): (0 ~ 0.25).
Wherein, acrylic ester monomer described in the said step (1) is methyl methacrylate MMA, methyl acrylate, butyl acrylate BA, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid fluoro heptyl ester, methacrylic acid fluoro heptyl ester, methacrylic acid MAA, acrylic acid; Said solvent is tetrahydrofuran THF, toluene, ethyl acetate; Said initator is azodiisobutyronitrile, dibenzoyl peroxide.
Wherein, the said methyl methacrylate MMA of step (1) (or methyl acrylate): butyl acrylate BA (or hydroxyethyl methacrylate or hydroxypropyl acrylate or acrylic acid fluoro heptyl ester or methacrylic acid fluoro heptyl ester): methacrylic acid MAA (or acrylic acid): initator: polyethylene glycol: the mass ratio of solvent is 1: (0.062 ~ 0.1): (0.18 ~ 0.9): (0.012 ~ 0.031): (0.54 ~ 0.86): (1.53 ~ 6.2).
Wherein, iodide/I in the said step (2) 2Iodide in the electrolyte solution: I 2: the mass ratio of solvent is 1:0.169: (10.7 ~ 25); Said iodide are NaI, KI or LiI, and said solvent is gamma-butyrolacton, N, dinethylformamide, N-methyl pyrrolidone.
Wherein, additive agent electrolyte is pyridine PY, tert .-butylpyridine TBP, guanidinium isothiocyanate GuSCN in the said step (2).
Wherein, said step (1) can be carried out purification step after accomplishing, and said PA/PEG polymer is dried to constant weight through revolving dried solvent final vacuum.Through purification step, can remove solvent and unreacted small amounts of monomer.
Existing shown in the following chemical formula of intermolecular hydrogen bonding (III) in the PA/PEG polymer that above-mentioned steps (1) obtains:
Figure 2011101650319100002DEST_PATH_IMAGE004
Hybridized polymer gel electrolyte of the present invention is polyacrylate/polyethylene glycol PA/PEG polymer and redox couple iodide/I 2Hybrid reaction forms, and this hybrid gel electrolyte is the thermoplastic gel electrolyte, is immobilising gel state during room temperature, when heating, is flowable thick liquid, so help assembled battery; Conductivity at room temperature reaches 10 -3S.cm -1The order of magnitude; Good with the electrode interface contact performance, interface resistance is little, and the interface charge transmission speed is fast; Good electrochemical stability and good processing properties; After being assembled into DSSC DSSC, the photoelectric conversion efficiency of battery ηReach 3.6%, with corresponding electrolyte solution (0.6 mol/L iodide such as NaI, 0.06 mol/L I 2, solvent is gamma-butyrolacton GBL) photoelectric conversion efficiency η=3.83% is close.
The present invention combines polyethylene glycol PEG and polyacrylate, obtains having the hydridization PA/PEG polymer/iodide/I like following chemical formula (I) structure 2Gel electrolyte,
Figure 2011101650319100002DEST_PATH_IMAGE005
M in the formula +Represent Na +, K +Or Li +R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15Deng fluoro-alkyl; R 4Represent CH 3Perhaps H.
Compare beneficial effect such as hybridized polymer gel electrolyte of the present invention has the encapsulation of being easy to, electrochemical stability is good with electrolyte solution.The hybridized polymer gel electrolyte preparation method route that the present invention proposes is simple, and operating condition is gentle, and the purification of products step is simple, and productive rate is high; Carboxyl in the PA/PEG polymer of the present invention can with Na +, K +Or Li +In conjunction with, help to reduce dark current, improve conductivity.
Description of drawings
Fig. 1 is the Fourier transform infrared spectroscopy IR figure of PA/PEG polymer among the embodiment 3.
Fig. 2 is density of photocurrent-voltage (J-V) test result curve chart with the prepared DSSC DSSC of gel-form solid polymer electrolyte of the present invention of preparation among the embodiment 3.
Embodiment
In conjunction with following specific embodiment and accompanying drawing, the present invention is done further detailed description, protection content of the present invention is not limited to following examples.Under spirit that does not deviate from inventive concept and scope, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection range with the appending claims.
Hybridized polymer gel electrolyte of the present invention has the structure of following chemical formula (I):
Figure 2011101650319100002DEST_PATH_IMAGE006
Wherein, M +Represent Na +, K +Or Li +R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15Deng fluoro-alkyl; R 4Represent CH 3Perhaps H.
The preparation method of hybridized polymer gel electrolyte is through PA/PEG polymer and redox couple iodide/I 2Hybrid reaction forms hybridized polymer gel electrolyte of the present invention.Preparation method of the present invention specifically may further comprise the steps:
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively; At first in reaction bulb, add polyethylene glycol (PEG) and solvent, be dissolved in acrylic ester monomer such as methyl methacrylate MMA, methyl acrylate, butyl acrylate BA, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid fluoro heptyl ester, methacrylic acid fluoro heptyl ester, methacrylic acid MAA, acrylic acid in the solvent; Be dissolved in initator in the solvent, through-flow moving nitrogen heats up 50 ~ 90 ℃, acrylate monomer solution and initator solvent slowly is added dropwise in the reaction bulb reaction 6-24 h simultaneously;
Monomers methyl methacrylate MMA (or methyl acrylate): butyl acrylate BA (or hydroxyethyl methacrylate or hydroxypropyl acrylate or acrylic acid fluoro heptyl ester or methacrylic acid fluoro heptyl ester): methacrylic acid MAA (or acrylic acid): initator: PEG: the mass ratio of solvent is 1: (0.062 ~ 0.1): (0.18 ~ 0.9): (0.012 ~ 0.031): (0.54 ~ 0.86): (1.53 ~ 6.2).
Initator is azodiisobutyronitrile, dibenzoyl peroxide, and solvent is tetrahydrofuran THF, toluene, ethyl acetate etc.
The molecular formula of the polyethylene glycol PEG that is adopted among the preparation method of the present invention is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 4 ~ 45 integer, is commercially available SILVER REAGENT product;
The PA structure is shown in chemical formula (II) in the hydridization PA/PEG polymer:
Figure 2011101650319100002DEST_PATH_IMAGE007
The number of x:y:z is than being (128 ~ 572) in the formula: 10: (53 ~ 307); R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15Deng fluoro-alkyl; R 4Represent CH 3Perhaps H.
Existing shown in the following chemical formula of intermolecular hydrogen bonding (III) in the PA/PEG polymer:
Figure 2011101650319100002DEST_PATH_IMAGE008
Second step: the preparation of hybridized polymer gel electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing iodide, I 2And solvent, join in the flask, stir the preparation electrolyte solution.Wherein, iodide, I 2With the mass ratio of solvent be 1:0.169: (10.7 ~ 25).Above-mentioned iodide can be respectively NaI, KI or LiI.Solvent is gamma-butyrolacton, N, dinethylformamide, N-methyl pyrrolidone etc.
The PA/PEG polymer that the first step of learning from else's experience is handled joins in the electrolyte solution of above-mentioned preparation; Add additive agent electrolyte (also can not adding) again; Be sealed in the flask; At the viscous solution of 60-90 ℃ of following heated and stirred formation homogeneous phase, cool to room temperature promptly gets hybridized polymer gel electrolyte of the present invention then.
Wherein, PA/PEG polymer: electrolyte solution: the additive agent electrolyte weight ratio is 1: (2.34 ~ 9): (0 ~ 0.25).Additive agent electrolyte is pyridine PY, tert .-butylpyridine TBP, guanidinium isothiocyanate GuSCN.
Among the present invention, after first step reaction finishes, can also make with extra care, revolve dried solvent, put into vacuum drying chamber then and be dried to constant weight, get the white solid powder the PA/PEG polymer.
PA/PEG polymer/iodide of the present invention/the I that adopts preparation method of the present invention to obtain 2The hybrid gel electrolyte has following structure,
Figure 2011101650319100002DEST_PATH_IMAGE009
M in the formula +Represent Na +, K +Or Li +R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15Deng fluoro-alkyl; R 4Represent CH 3Perhaps H.
Use the conductivity of the close scientific instrument of the Nereid DDS-307A of Co., Ltd type electric conductivity appearance test gel-form solid polymer electrolyte of the present invention hybridized polymer gel electrolyte in the time of 30 ℃.
Hybridized polymer gel electrolyte of the present invention is prepared into DSSC DSSC, and method is following: at first, and with TiO 2Electrode keeps flat, and fixes with 3M magic adhesive tape; With the gel electrolyte heat fused, drop in TiO 2On the electrode, the blade blade coating tears adhesive tape off, on electrode, puts the Surlyn zona; The Pt electrode is installed, is clamped, put into 120 ℃ of baking oven heating 1min heat-sealing; Again battery is put into 65 ℃ of baking ovens and be incubated 0.5h.Use Keithley model 2440 digital source tables and U.S. Newport company solar simulator then, at 1 sunlight sun (AM 1.5,100 mW.cm -2) record DSSC DSSC photovoltaic conversion efficiency under the condition η
Embodiment 1
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 8.58 g and oxolane 10 g, is dissolved in acrylic ester monomer MMA 13g, BA 1g, MAA 6g among solvent 25 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the solvent 5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:3.077.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The PA structure is shown in chemical formula (II) in the hydridization PA/PEG polymer that reaction obtains:
Figure 2011101650319100002DEST_PATH_IMAGE010
The number of x:y:z is than being 166:10:89 in the formula; R 1Represent CH 3R 2Represent H; R 3Represent C 4H 9R 4Represent CH 3
The intermolecular hydrogen bonding that exists in the PA/PEG polymer is shown below:
Figure DEST_PATH_IMAGE011
Above-mentioned initator azodiisobutyronitrile is replaceable to be dibenzoyl peroxide, and tetrahydrofuran THF is replaceable to be toluene, ethyl acetate etc.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing iodide NaI 9 g, I 21.524 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 123 g, iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:12.5.
Above-mentioned NaI can replace with KI or LiI, the replaceable one-tenth of solvent gamma-butyrolacton N, dinethylformamide.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g; Add additive agent electrolyte pyridine 0.735 g again; Be sealed in the flask; At the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25.73 g then.
Wherein, PA/PEG polymer: electrolyte solution: the additive agent electrolyte weight ratio is 1:4:0.1471.
Above-mentioned additive agent electrolyte pyridine PY can replace with tert .-butylpyridine TBP, guanidinium isothiocyanate GuSCN.
After first step reaction finishes, can also increase purification step, promptly the PA/PEG polymer further handled, revolve dried solvent, put into vacuum drying chamber then and be dried to constant weight for 80 ℃, get white solid powder 27.1 g, yield 95%.
PA/PEG polymer that present embodiment obtains and electrolyte solution form ionic bond, and structural formula is following:
Figure 2011101650319100002DEST_PATH_IMAGE012
In the formula, M +Represent Na +R 1Represent CH 3R 2Represent H; R 3Represent C 4H 9R 4Represent CH 3When iodide are KI, M +Represent K +When iodide are LiI, M +Represent Li +
The hybrid gel electrolyte that obtains is used the close scientific instrument of the Nereid DDS-307A of Co., Ltd type electric conductivity appearance, and the conductivity of hybridized polymer gel electrolyte is 2.91 mS.cm when recording 30 ℃ -1
With hybridized polymer gel electrolyte sample preparation DSSC DSSC.At first, with TiO 2Electrode keeps flat, and fixes with 3M magic adhesive tape; With the gel electrolyte heat fused, drop in TiO 2On the electrode, the blade blade coating tears adhesive tape off, on electrode, puts the Surlyn zona; The Pt electrode is installed, is clamped, put into 120 ℃ of baking oven heating 1min heat-sealing; Again battery is put into 65 ℃ of baking ovens and be incubated 0.5h.
With Keithley model 2440 digital source tables and U.S. Newport company solar simulator, at 1 sunlight sun (AM 1.5,100 mW.cm -2) under the condition, cell area 0.16cm 2The time, record the photovoltaic conversion efficiency of DSSC DSSC ηBe 3.6%.
Embodiment 2
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 8.58 g and solvent 5 g oxolanes, is dissolved in acrylic ester monomer MMA 13g, BA 1g, MAA 6g among solvent 12.5 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the 2.5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:1.538.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The molecular structural formula that obtains PA/PEG polymer of the present invention is identical with embodiment 1, and the number of x:y:z is than being 166:10:89 in this formula of present embodiment.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 7.5 g, I 21.27 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 121.2 g; Iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:15.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g; Add additive agent electrolyte tert .-butylpyridine 1.25 g again; Be sealed in the flask; At the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 26.25 g then.
Wherein, PA/PEG polymer: electrolyte solution: the additive agent electrolyte weight ratio is 1:4:0.25.
Above-mentioned additive agent electrolyte tert .-butylpyridine can replace to guanidinium isothiocyanate GuSCN.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 27.4 g, yield 96%.
The gel-form solid polymer electrolyte that obtains, preparation DSSC DSSC.Record its photovoltaic conversion efficiency ηBe 2.99%.
Embodiment 3
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 8.58 g and oxolane 10 g, is dissolved in acrylic ester monomer MMA 13g, BA 1g, MAA 6g among solvent 25 g; Be dissolved in initator azodiisobutyronitrile 0.4 g among oxolane 45 g, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 6 h.
In the present embodiment, monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.03076:0.66:6.154.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The PA/PEG polymer molecular structure formula that present embodiment obtains is identical with embodiment 1; The number of x:y:z is than being 166:10:89 in the present embodiment formula.
Subtractive process is identical with embodiment 1.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 9 g, I 21.524 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 123 g, iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:12.5.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g, are sealed in the flask, and at the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25 g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:4.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 22.8 g, yield 80 %.Shown in Figure 1 is the Fourier transform infrared spectroscopy IR figure of present embodiment PA/PEG polymer.
Recording the conductivity of gel-form solid polymer electrolyte in the time of 30 ℃ is 2.8 mS.cm -1
With the gel-form solid polymer electrolyte of preparation, preparation DSSC DSSC.Record its photovoltaic conversion efficiency ηBe 3.3%.Shown in Figure 2 is density of photocurrent-voltage (J-V) test result curve chart of the prepared DSSC DSSC of present embodiment gel-form solid polymer electrolyte.
Embodiment 4
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 4.35 g and oxolane 5 g, is dissolved in acrylic ester monomer MMA 8 g, BA 0.5 g, MAA 1.5 g among solvent 10 g; Be dissolved in initator azodiisobutyronitrile 0.1 g among oxolane 5 g, through-flow moving nitrogen heats up 50 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.0625:0.1875:0.0125:0.5438:2.5.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The number of x:y:z is than being 204:10:53 in the PA/PEG polymer molecular structure formula that present embodiment obtains.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 9 g, I 21.524 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 123 g, iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:12.5.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 11.7 g, are sealed in the flask, and at the viscous solution of 60 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 16.7g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:2.34.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 12.7 g, yield 89 %.
Recording the conductivity of gel-form solid polymer electrolyte in the time of 30 ℃ that embodiment 4 obtains is 2.0 mS.cm -1
Embodiment 5
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 21.5 g and toluene 30 g, is dissolved in acrylic ester monomer MMA 25 g, BA 2.5 g, MAA 22.5 g among solvent 60 g; Be dissolved in initator azodiisobutyronitrile 0.5 g among toluene 10 g, through-flow moving nitrogen heats up 90 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 6 h.
Monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.1:0.9:0.02:0.86:4.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The PA/PEG polymer molecular structure formula that present embodiment obtains is identical with embodiment 2; The number of x:y:z is than being 128:10:160 in the present embodiment formula.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 9 g, I 21.524 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 123 g, iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:12.5.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 45 g, are sealed in the flask, and at the viscous solution of 90 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 50 g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:9.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 64.3 g, yield 90 %.
Recording the conductivity of gel-form solid polymer electrolyte in the time of 30 ℃ is 5.1 mS.cm -1
Embodiment 6
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 8.58 g and solvent 5 g oxolanes, is dissolved in acrylic ester monomer MMA 13g, BA 1g, MAA 6g among solvent 12.5 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the 2.5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:1.538.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 4 integer, is commercially available SILVER REAGENT product.
The molecular structural formula that obtains PA/PEG polymer of the present invention is identical with embodiment 1, and the number of x:y:z is than being 166:10:89 in the formula.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 4.5 g, I 20.76 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution, iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:25.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g, are sealed in the flask, and at the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25 g then.
Wherein, PA/PEG polymer: electrolyte solution: the additive agent electrolyte weight ratio is 1:4.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 26.9 g, yield 95%.
Recording the conductivity of gel-form solid polymer electrolyte in the time of 30 ℃ is 2.65 mS.cm -1
Embodiment 7
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol (PEG) 8.58 g and solvent 5 g oxolanes, is dissolved in acrylic ester monomer MMA 13g, BA 1g, MAA 6g among solvent 12.5 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the 2.5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA:BA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:1.538.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 45 integer, is commercially available SILVER REAGENT product.
The molecular structural formula that obtains PA/PEG polymer of the present invention is identical with embodiment 1, and the number of x:y:z is than being 166:10:89 in the formula.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 10.5 g, I 21.78 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution, iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:10.7.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g, are sealed in the flask, and at the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25 g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:4.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 27.6 g, yield 96.5%.
Recording the conductivity of gel-form solid polymer electrolyte in the time of 30 ℃ is 5.0 mS.cm -1
Embodiment 8
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively; At first in reaction bulb, add polyethylene glycol 8.58 g and solvent 5 g oxolanes, be dissolved in acrylic ester monomer MMA 13g, hydroxyethyl methacrylate HEMA 1g, MAA 6g among solvent 12.5 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the 2.5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h,
In the present embodiment, monomer M MA:HEMA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:1.538.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The molecular structural formula that obtains PA in the PA/PEG polymer of the present invention is:
Figure DEST_PATH_IMAGE013
Wherein, the number of x:y:z is than being 169:10:90; R 1Represent CH 3R 2Represent CH 3R 3Represent CH 2CH 2OH; R 4Represent CH 3
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 7.5 g, I 21.27 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 121.2 g; Iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:15.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.Above-mentioned methyl methacrylate can replace with methyl acrylate, and methacrylic acid can replace with acrylic acid.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g, are sealed in the flask, and at the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25 g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:4.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 27 g, yield 94.5 %.
The conductivity of gel-form solid polymer electrolyte is 2 mS.cm when recording 30 ℃ -1
Embodiment 9
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol 8.58 g and solvent 5 g oxolanes, is dissolved in acrylic ester monomer MMA 13g, hydroxypropyl acrylate HPA 1g, MAA 6g among solvent 12.5 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the 2.5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA:HPA:MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:1.538.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The molecular structural formula that obtains PA in the PA/PEG polymer of the present invention is:
Figure 2011101650319100002DEST_PATH_IMAGE014
Wherein, the number of x:y:z is than being 169:10:90; R 1Represent CH 3R 2Represent H; R 3Represent CH 2CH 2CH 2OH; R 4Represent CH 3
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 7.5 g, I 21.27 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 121.2 g; Iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:15.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.Above-mentioned methyl methacrylate can replace with methyl acrylate, and methacrylic acid can replace with acrylic acid.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g, are sealed in the flask, and at the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25 g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:4.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 26.6 g, yield 93%.
The conductivity of gel-form solid polymer electrolyte is 2.05 mS.cm when recording 30 ℃ -1
Embodiment 10
The first step: the preparation of PA/PEG polymer
Reaction bulb connects condensed water, mechanical agitation and flowing nitrogen respectively, at first in reaction bulb, adds polyethylene glycol 8.58 g and solvent 5 g oxolanes, is dissolved in acrylic ester monomer MMA 13g, acrylic acid fluoro heptyl ester 1g, MAA 6g among solvent 12.5 g; Be dissolved in initator azodiisobutyronitrile 0.2 g in the 2.5 g oxolanes, through-flow moving nitrogen heats up 70 ℃, and acrylate monomer solution and initator solvent slowly are added dropwise in the reaction bulb simultaneously, reacts 24 h.
In the present embodiment, monomer M MA: acrylic acid fluoro heptyl ester: MAA: initiator A IBN:PEG: the mass ratio of solvent is 1:0.07692:0.4615:0.01538:0.66:1.538.The molecular formula of polyethylene glycol PEG is HO-(CH 2CH 2O) nH, n represents CH 2CH 2The mean value of the repetitive number of O is 9 integer, is commercially available SILVER REAGENT product.
The molecular structural formula that obtains PA in the PA/PEG polymer of the present invention is:
Figure 318981DEST_PATH_IMAGE014
Wherein, the number of x:y:z is than being 572:10:307; R 1Represent CH 3R 2Represent H; R 3Represent C 7F 15R 4Represent CH 3
Above-mentioned methyl methacrylate can replace with methyl acrylate, and methacrylic acid can replace with acrylic acid; Aforesaid propylene acid fluoro heptyl ester can replace with acrylate containing fluorine monomers such as methacrylic acid fluoro heptyl ester.
Second step: the preparation of gel-form solid polymer electrolyte
Preparation iodide/I 2Electrolyte solution: take by weighing NaI 7.5 g, I 21.27 g, solvent gamma-butyrolacton 112.5 g join in the flask, stir preparation electrolyte solution 121.2 g; Iodide NaI, I 2With the mass ratio of solvent gamma-butyrolacton be 1:0.169:15.
Above-mentioned NaI can replace with KI or LiI, and the solvent gamma-butyrolacton can replace to N, dinethylformamide.
PA/PEG polymer 5 g that the first step of learning from else's experience is handled join in the above-mentioned electrolyte solution of 20 g, are sealed in the flask, and at the viscous solution of 80 ℃ of following heated and stirred formation homogeneous phases, cool to room temperature promptly gets gel-form solid polymer electrolyte 25 g then.
Wherein, PA/PEG polymer: the electrolyte solution weight ratio is 1:4.
After first step reaction finishes, can also increase purification step, process is seen embodiment 1, gets PA/PEG polymer white solid powder 26.7 g, yield 93.5%.
The conductivity of gel-form solid polymer electrolyte is 2.1 mS.cm when recording 30 ℃ -1

Claims (9)

1. a hybridized polymer gel electrolyte is characterized in that, the structure of said hybridized polymer gel electrolyte is represented by following chemical formula (I):
Figure 84713DEST_PATH_IMAGE001
Wherein, M +Represent Na +, K +Or Li +R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15R 4Represent CH 3Perhaps H.
2. the preparation method of hybridized polymer gel electrolyte according to claim 1 is characterized in that, said preparation method is through polyacrylate/polyethylene glycol polymer and redox couple iodide/I 2Mix, reaction obtains said hybridized polymer gel electrolyte.
3. like the preparation method of the said hybridized polymer gel electrolyte of claim 2, it is characterized in that, may further comprise the steps successively: (1) is dissolved in acrylic ester monomer in the solvent, and initator is dissolved in the solvent; Mixture to polyethylene glycol and solvent feeds nitrogen and intensification, adds said acrylic ester monomer and initator again, and the PA structure is shown in chemical formula (II) in hydridization polyacrylate/polyethylene glycol polymer that reaction obtains;
Figure 1854DEST_PATH_IMAGE002
Wherein, the number of x:y:z is than being (128 ~ 572): 10: (53 ~ 307); R 1Represent CH 3Perhaps H; R 2Represent H or CH 3R 3Represent C 4H 9, CH 2CH 2OH or CH 2CH 2CH 2OH or C 7F 15R 4Represent CH 3Perhaps H;
(2) will pass through hydridization polyacrylate/polyethylene glycol polymer that step (1) handles and join iodide/I 2In the electrolyte solution, add additive agent electrolyte again, in sealed environment,, be cooled to room temperature again and obtain hybridized polymer gel electrolyte as claimed in claim 1 in 60-90 ℃ of heating, stirring; Wherein, said iodide/I 2Electrolyte solution is with iodide, I 2Obtain with solvent, after stirring.
4. like the preparation method of the said hybridized polymer gel electrolyte of claim 3, it is characterized in that polyacrylate/polyethylene glycol polymer: iodide/I in the said step (2) 2Electrolyte solution: the weight ratio of additive agent electrolyte is 1: (2.34 ~ 9): (0 ~ 0.25).
5. like the preparation method of the said hybridized polymer gel electrolyte of claim 3; It is characterized in that acrylic ester monomer described in the said step (1) is methyl methacrylate MMA, methyl acrylate, butyl acrylate BA, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid fluoro heptyl ester, methacrylic acid fluoro heptyl ester, methacrylic acid MAA, acrylic acid; Said solvent is tetrahydrofuran THF, toluene, ethyl acetate; Said initator is azodiisobutyronitrile, dibenzoyl peroxide.
6. like the preparation method of the said hybridized polymer gel electrolyte of claim 5; It is characterized in that said methyl methacrylate MMA or methyl acrylate: butyl acrylate BA or hydroxyethyl methacrylate or hydroxypropyl acrylate or acrylic acid fluoro heptyl ester or methacrylic acid fluoro heptyl ester: methacrylic acid MAA or acrylic acid: initator: polyethylene glycol: the mass ratio of solvent is 1: (0.062 ~ 0.1): (0.18 ~ 0.9): (0.012 ~ 0.031): (0.54 ~ 0.86): (1.53 ~ 6.2).
7. like the preparation method of the said hybridized polymer gel electrolyte of claim 3, it is characterized in that iodide/I in the said step (2) 2Iodide in the electrolyte solution: I 2: the mass ratio of solvent is 1:0.169: (10.7 ~ 25); Said iodide are NaI, KI or LiI, and said solvent is gamma-butyrolacton, N, dinethylformamide, N-methyl pyrrolidone.
8. like the preparation method of the said hybridized polymer gel electrolyte of claim 3, it is characterized in that additive agent electrolyte is pyridine PY, tert .-butylpyridine TBP, guanidinium isothiocyanate GuSCN in the said step (2).
9. like the preparation method of the said hybridized polymer gel electrolyte of claim 2, it is characterized in that said step (1) is carried out purification step after accomplishing, and said polyacrylate/polyethylene glycol polymer is dried to constant weight through revolving dried solvent final vacuum.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1529385A (en) * 2003-10-10 2004-09-15 复旦大学 Chargeable lithium ion cell polymer electrolyte and preparing method thereof
CN101939869A (en) * 2008-01-16 2011-01-05 西奥公司 Gel polymer electrolytes for batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1529385A (en) * 2003-10-10 2004-09-15 复旦大学 Chargeable lithium ion cell polymer electrolyte and preparing method thereof
CN101939869A (en) * 2008-01-16 2011-01-05 西奥公司 Gel polymer electrolytes for batteries

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