CN1880354A - Whole solid state/gelatin polymer solid electrolyte and its dedicated polymer and preparation method - Google Patents
Whole solid state/gelatin polymer solid electrolyte and its dedicated polymer and preparation method Download PDFInfo
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- CN1880354A CN1880354A CNA2005100766577A CN200510076657A CN1880354A CN 1880354 A CN1880354 A CN 1880354A CN A2005100766577 A CNA2005100766577 A CN A2005100766577A CN 200510076657 A CN200510076657 A CN 200510076657A CN 1880354 A CN1880354 A CN 1880354A
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Abstract
This invention discloses a all-solid/gel polymer solid electrolyte and special polymer thereof, and method for making same. The special polymer of this invention is a prepolymer of the three-dimensional network polymer, The structural formula of the polymer is indicated in formula(I), wherein: m+n=100, m=10 or 20 or 30; R1 is the polyethylene oxide/polypropylene oxide chain segment with active double bond at the end, and the said double bond at the end is the double bond with methacrylic acid or acroleic acid structure; R2 is propylmethyl polyethylene oxide or propylmethyl polypropylene oxide; the molar ratio of the said R1 and R2 is 1:1-7; the molecular weight of the said propylmethyl polyethylene oxide is 150-1000. The all-solid/gel polymer solid electrolyte with the prepolymer of the three-dimensional network polymer as active component, comprises the prepolymer of the three-dimensional network polymer, inorganic lithate, and polar small molecular plasticizer at weight ratio of 1:0.05-0.72:0-2.4.
Description
Technical field
The present invention relates to a kind of all solid state/preparation method of gel polymer solid electrolyte and specialty polymer and this polymkeric substance, particularly a kind of all solid state/preparation method of gel polymer solid electrolyte and special-purpose three-dimensional network polymkeric substance and this polymkeric substance.
Background technology
In environmental protection and energy problem increasingly serious today, the research and development of copolymer solid electrolyte has great economic benefit and social benefit.MingKui Wang, Li Qi, Feng Zhao, Shaojun Dong.A novelcomb-like copolymer based polymer electrolyte for Li batteries.J Power Source, 2005,139:223-229 has reported a kind of copolymer solid electrolyte, is to connect poly glycol monomethyl ether behind the methacrylic acid and methyl methacrylate and the copolymerization of vinyl cyanide thermal initiation obtain comb shaped polymer ionogen with the internal plasticization chain.But the electrolytical ionic conductance of this comb shaped polymer shows that with lithium salts and variation of temperature rule the ionic conductance of this system is lower after deliberation, although carried out while and smoke-like SiO
2Blend and the optimization that adds small molecules softening agent propylene carbonate (PC), the highest conductivity at room temperature also only is 10
-4Scm
-1The order of magnitude, and the raw material propylene nitrile is high-risk highly toxic substance is unfavorable for that environmental protection and industry promotes.Z.C.Zhang, J.J.Jin, F.Bautista, L.J.Lyons, N.Shariatzadeh, D.Sherlock.Ion conductive characteristics of cross-linkednetwork polysiloxane-based solid polymer electrolytes.Solid State Ionics, 2004, the another kind of copolymer solid electrolyte of 170:233-238 report, be on full containing hydrogen silicone oil main chain, to connect the PEO segment of methyl blocking earlier as the internal plasticization chain, then with the PEO of the two keys of two ends band as linking agent, the polymer dielectric that utilizes Si-H addition reaction thermofixation to be prepared into, but this system complex synthetic route, and energy expenditure is big in synthetic and curing process, and the highest conductivity at room temperature after the final optimization pass also only is 10
-4Scm
-1The order of magnitude.Copolymer solid electrolyte system in the above-mentioned prior art exists ionic conductance lower, and the solidification process big energy-consuming takes length, and efficient is low, defectives such as electrode and electrolyte interface instability.
Summary of the invention
Purpose of the present invention provides prepolymer of a kind of three-dimensional network polymkeric substance and preparation method thereof, and with all solid state/gel polymer solid electrolyte and the preparation method of the prepolymer of this three-dimensional network polymkeric substance preparation.
The prepolymer of a kind of three-dimensional network polymkeric substance provided by the present invention, the molecular structure of its structural unit is suc as formula shown in the I:
Wherein, m+n=100, m=10 or 20 or 30; R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, the activated double bonds that described end has is two keys of methacrylic acid or acrylic acid structure; R
2Be trimethylene methyl polyoxyethylene (APEOM) or trimethylene methyl polyoxytrimethylene (APPOM); Described R
1With R
2Mol ratio be 1: 1-7; The molecular weight of described trimethylene methyl polyoxyethylene (APEOM) is 150-1000,390-790 preferably wherein, most preferably 590.
The prepolymer of described three-dimensional network polymkeric substance is to prepare with following method:
1) containing hydrogen silicone oil (PMHS), the poly-ethylene-propylene ether alcohol (PEO-PPOH) of trimethylene, trimethylene methyl polyoxyethylene (APEOM) are dissolved in the toluene, reacting by heating obtains the presoma of the prepolymer of three-dimensional network polymkeric substance, and wherein the molfraction ratio of Si-H, the poly-ethylene-propylene ether alcohol of trimethylene, trimethylene methyl polyoxyethylene is 1: 0.125-0.875: 0.875-0.125;
2) presoma that step 1) is generated is dissolved in benzene, and adds behind the acid absorber triethylamine and the methacrylic chloride reaction, obtains the prepolymer (PMS-APEOM) of three-dimensional network polymkeric substance.
Provided by the present invention all solid state/gel polymer solid electrolyte, comprise that ratio of weight and number is 1: the prepolymer of the three-dimensional network polymkeric substance of 0.01-0.05: 0.05-0.72: 0-2.4, initiator, inorganic lithium salt, small molecules softening agent.
Described initiator is light trigger or thermal initiator; Described light trigger is benzoin dimethylether (DMPA) or benzophenone (DPK); Described thermal initiator is azo isobutyronitrile (AIBN), benzoyl peroxide (BPO) or peroxy dicarbonate di-t-butyl cyclohexyl (DBHPC); Described inorganic lithium salt comprises LiClO
4, LiPF
6, LiCF
3SO
3Or LiN (CF
3SO
2)
2Described small molecules softening agent is an annular lactone, and annular lactone is vinyl carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC) or butyrolactone (γ-BL) preferably.
The preparation method of all solid state/gel polymer solid electrolyte may further comprise the steps:
1) prepolymer, initiator, dry inorganic lithium salt and the polarity small molecules softening agent with exsiccant three-dimensional network polymkeric substance is 1 by ratio of weight and the number of copies: 0.01-0.05: 0.05-0.72: 0-2.4 mixes;
2) mixture that step 1) is formed carries out induction stirring, obtains tool flowing property viscous liquid;
3) with step 2) liquid that obtains directly exposes to the open air under UV-light or at high temperature is cured, and generates conductive film;
4) conductive film is carried out vacuum-drying after, obtain gel polymer solid electrolyte.
Wherein, when preparation full solid state polymer solid electrolyte, in the mixture that step 1) forms, also need to add solvents tetrahydrofurane (THF), and then carry out induction stirring.In preparation process, the described induction stirring time is 15-30 minute; When adopting light trigger, ultraviolet wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2, be 5～15 minutes set time; When adopting thermal initiator, N
2Gas shiled, solidification value are 75～95 ℃, and be 12 hours set time; Described vacuum-drying temperature is 80 ℃, and be 24 hours time of drying.
The present invention has the three-dimensional network polymkeric substance of internal plasticization chain, its internal plasticization chain is trimethylene methyl polyoxyethylene (APEOM) or trimethylene methyl polyoxytrimethylene (APPOM), is by prepolymer (PMS-APEOM) network polymer that crosslinking reaction generates to take place under the initiator effect.The three-dimensional network polymkeric substance that has the internal plasticization chain with the present invention is a kind of specialty polymer, adopt UV-light room temperature solidified one one-step film forming method, all solid state/gel polymer solid electrolyte the film of preparation, it is simple and easy to do to have working method, energy consumption is few, solidifies rapid efficient height, and the small molecules losses of plasticizer is few in the solidification process, help improving the room-temperature ion conductivity of ionogen conductive film, advantages such as good stability.The three-dimensional network polymkeric substance can play the effect of serving as support frame, guarantee that electrolyte has good three-dimensional dimension stability and processing characteristics, simple plasticizer in the network has reduced the second-order transition temperature of whole electrolyte system, simultaneously except and three-dimensional network between exist interact, softening agent also and exist intensive to interact between the internal plasticization chain that hangs on the network, therefore alleviate escaping of simple plasticizer, improved the stability of gelling system greatly.The three-dimensional network polymkeric substance that has the internal plasticization chain with the present invention is a kind of specialty polymer, adopts an one-step film forming method of thermofixation, the gel polymer solid electrolyte film of preparation, and its room-temperature ion conductivity is up to 10
-3Scm
-1The order of magnitude.The cross-linked network of the band internal plasticization chain of the present invention preparation is all solid state/the gel polymer solid electrolyte film, can be applied to especially be applied to field of lithium ion secondary in the electronic devices and components.
Embodiment
Embodiment 1: with trimethylene methyl polyoxyethylene (APEO
550M) be the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of internal plasticization chain
550M) preparation
At first handle as follows in earlier stage to the raw material chemical substance:
Containing hydrogen silicone oil (PMHS), trimethylene methyl polyoxyethylene (APEO
550M), the poly-ethylene-propylene ether alcohol (PEO-PPOH) of trimethylene is with 1 week of 4 molecular sieve dryings; Before using, triethylamine purifies through distilling again; Methacrylic chloride underpressure distillation purifying; Solvent benzol, toluene reflux with sodium Metal 99.5 and are blue until the indication of benzophenone indicator; The catalyzer Platinic chloride directly uses.
With 50g containing hydrogen silicone oil (PMHS), the poly-ethylene-propylene ether alcohol (PEO-PPOH) of 173g trimethylene, 15g trimethylene methyl polyoxyethylene (APEO
550M), 238g toluene, join in the reactor, feed N
2Protection; heat to 60 ℃; add the 30ppm chloroplatinic acid catalyst; continue to be warmed up to 80-90 ℃; keep this temperature to continue reaction 12-24h; the decompression rotary evaporation is removed solvent toluene, changes product over to another reactor, with an amount of benzene dissolving; and adding 12g triethylamine; in ice-water bath, under the vigorous stirring, slowly drip the methacrylic chloride of 12.5g, after being added dropwise to complete; the 24-48h of induction stirring reaction at room temperature; remove by filter triethylamine hydrochloride, the decompression rotary evaporation is removed solvent benzol, obtains the prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of internal plasticization chain
550M), with PMS-APEO
550M is above standby with 1 week of 4 molecular sieve dryings.
After testing, product (PMS-APEO
550M) infrared spectrum absorpting peak data are as follows: 2968-2869cm
-1(CH
3), 1727cm
-1(-COO), 1455cm
-1(C-H), 1373cm
-1(CH
3), 1250
-1260cm
-1(Si-C), 1106-1112cm
-1(H
2C-O-CH
2), 804cm
-1(C=C), in the product spectrogram: Si-H (2160cm
-1) ,-OH (3482cm
-1) the absorption peak completely dissolve, illustrate that reaction carries out fully, obtain product and be really the prepolymer (PMS-APEO of required three-dimensional network polymkeric substance
550M).
Embodiment 2: a kind of preparation of full solid state polymer solid electrolyte film
It is as follows at first the raw material chemical substance not to be had water treatment:
Get solvent THF, it is refluxed through sodium Metal 99.5 is blue until the indication of benzophenone indicator;
Get inorganic lithium salt LiN (CF
3SO
2)
2, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of full solid state polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.01g light trigger benzoin dimethylether (DMPA), 1.0g solvent THF and 0.05g (5%) or 0.10g (10%) or 0.15g (15%) or 0.20g (20%) exsiccant LiN (CF
3SO
2)
2Under dry atmosphere, join in the 25ml single port flask, fast sealing carries out violent induction stirring 15-30min then, mixture is mixed and dissolves, with the lysate rotary evaporation that reduces pressure, THF eliminates until the system constant weight, obtains tool flowing property viscous liquid, it is cast in the tetrafluoroethylene mould then, directly exposing to the open air at wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2UV-light under solidified 10 minutes, obtain having internal plasticization chain (APEO
550M) full solid state polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, carry out performance test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiN (CF
3SO
2)
2The full solid state polymer solid electrolyte film.As LiN (CF
3SO
2)
2Content is 20% o'clock, and the room-temperature ion conductivity of this thin film system reaches 1.01 * 10
-4Scm
-1, because this thin film system is all solid state, dielectric film has good thermostability and electrochemical stability, and has the favorable mechanical mechanical property.
Embodiment 3: a kind of preparation of gel polymer solid electrolyte film
It is as follows at first the raw material chemical substance not to be had water treatment:
Get inorganic lithium salt LiClO
4, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get polarity small molecules softening agent propylene carbonate (PC), it is purified through underpressure distillation in advance, use 1 week of 4 molecular sieve dryings then;
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of gel polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.03g light trigger benzoin dimethylether (DMPA), 0.3g LiClO
4And the propylene carbonate (PC) of 0.5g (50%) or 1.0g (100%) or 1.5g (150%) or 2.0g (200%), under dry atmosphere, join in the 25ml single port flask, fast sealing, carry out violent induction stirring 15-30min then, mixture is mixed, obtain the viscous liquid of tool flowability, it is cast in the tetrafluoroethylene mould then, directly exposing to the open air at wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2UV-light under solidified 7 minutes, obtain having internal plasticization chain (APEO
550M) gel polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiClO
4/ PC gel polymer solid electrolyte film, its room-temperature ion conductivity detected result sees Table 1.
Embodiment 4: a kind of preparation of gel polymer solid electrolyte film
It is as follows at first the raw material chemical substance not to be had water treatment;
Get inorganic lithium salt LiN (CF
3SO
2)
2, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get polarity small molecules softening agent propylene carbonate (PC), it is purified through underpressure distillation in advance, use 1 week of 4 molecular sieve dryings then;
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of gel polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.03g light trigger benzoin dimethylether (DMPA), 0.50g LiN (CF
3SO
2)
2And the propylene carbonate (PC) of 0.5g (50%) or 1.0g (100%) or 1.5g (150%) or 2.0g (200%), under dry atmosphere, join in the 25ml single port flask, fast sealing, carry out violent induction stirring 15-30min then, mixture is mixed, obtain the viscous liquid of tool flowability, it is cast in the tetrafluoroethylene mould then, directly exposing to the open air at wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2UV-light under solidified 7 minutes, obtain having internal plasticization chain (APEO
550M) gel polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiN (CF
3SO
2)
2/ PC gel polymer solid electrolyte film.The maximum room-temperature ion conductivity of this thin film system is 2.23 * 10
-3Scm
-1,, mainly be because the anion N (CF in the lithium salts than embodiment 2 height
3SO
2)
2 -Have due to the plasticization effect.
Embodiment 5: a kind of preparation of gel polymer solid electrolyte film
It is as follows at first the raw material chemical substance not to be had water treatment:
Get inorganic lithium salt LiClO
4, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get polarity small molecules softening agent vinyl carbonate (EC), it is purified through underpressure distillation in advance, use 1 week of 4 molecular sieve dryings then;
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of gel polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.03g light trigger benzoin dimethylether (DMPA), 0.3g LiClO
4And the vinyl carbonate (EC) of 0.5g (50%) or 1.0g (100%) or 1.5g (150%) or 2.0g (200%), under dry atmosphere, join in the 25ml single port flask, fast sealing, carry out violent induction stirring 15-30min then, mixture is mixed, obtain the viscous liquid of tool flowability, it is cast in the tetrafluoroethylene mould then, directly exposing to the open air at wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2UV-light under solidified 7 minutes, obtain having internal plasticization chain (APEO
550M) gel polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiClO
4/ EC gel polymer solid electrolyte film, its room-temperature ion conductivity detected result sees Table 1.
Embodiment 6: a kind of preparation of gel polymer solid electrolyte film
It is as follows at first the raw material chemical substance not to be had water treatment:
Get inorganic lithium salt LiClO
4, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get polarity small molecules softening agent vinyl carbonate and propylene carbonate, it is purified through underpressure distillation respectively, use 1 week of 4 molecular sieve dryings then;
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of gel polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.05g light trigger benzoin dimethylether (DMPA), 0.3g LiClO
4And vinyl carbonate/propylene carbonate (EC/PC=3: 1w/w) of 0.5g (50%) or 1.0g (100%) or 1.5g (150%) or 2.0g (200%), under dry atmosphere, join in the 25ml single port flask, fast sealing, carry out violent induction stirring 15-30min then, mixture is mixed, obtain the viscous liquid of tool flowability, it is cast in the tetrafluoroethylene mould then, directly exposing to the open air at wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2UV-light under solidified 5 minutes, obtain having internal plasticization chain (APEO
550M) gel polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiClO
4/ EC/PC (3: 1w/w) gel polymer solid electrolyte film.The room-temperature ion conductivity of this thin film system reaches 2.83 * 10
-3Scm
-1, all higher than embodiment 2 and embodiment 4, illustrate that composite elasticizer has synergistic effect.
Embodiment 7: a kind of preparation of gel polymer solid electrolyte film
It is as follows at first the raw material chemical substance not to be had water treatment:
Get inorganic lithium salt LiPF
6, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get polarity small molecules softening agent vinyl carbonate and diethyl carbonate, it is purified through underpressure distillation respectively, use 1 week of 4 molecular sieve dryings then;
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of gel polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.05g thermal initiator benzoyl peroxide (BPO), 0.64g LiPF
6And vinyl carbonate/diethyl carbonate (EC/DEC=1: 1w/w) of 0.5g (50%) or 0.65g (65%) or 0.85g (85%) or 1.0g (100%); under dry atmosphere, join in the 25ml single port flask; fast sealing; carry out violent induction stirring 15-30min then; mixture is mixed; obtain the viscous liquid of tool flowability; then it is cast in the mould of inflated with nitrogen protection; the fastening mould makes it to seal fully; place 85 ℃ of baking ovens to solidify 12 hours, obtain having internal plasticization chain (APEO
550M) gel polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiPF
6(1: 1w/w) gel polymer solid electrolyte film, its room-temperature ion conductivity detected result sees Table 1 to/EC/DEC.
Embodiment 8: a kind of preparation of gel polymer solid electrolyte
It is as follows at first the raw material chemical substance not to be had water treatment:
Get inorganic lithium salt LiPF
6, with its vacuum (＜carried out 140 ℃ of pyroprocessing 12 hours under 1mmHg);
Get polarity small molecules softening agent vinyl carbonate and diethyl carbonate, it is purified through underpressure distillation respectively, use 1 week of 4 molecular sieve dryings then;
Get the prepolymer (PMS-APEO of the three-dimensional network polymkeric substance of embodiment 1 preparation
550M), wherein: R
1Be the polyethylene oxide/polypropylene oxide segment (PEO-PPOMA) of end band activated double bonds, R
2Be with trimethylene methyl polyoxyethylene (APEO
550) be the internal plasticization chain (APEO of composition
550M); R
1And R
2Mol ratio be 1: 5, with it with 1 week of 4 molecular sieve dryings.
The preparation process of gel polymer solid electrolyte film is as follows:
Prepolymer (PMS-APEO with the three-dimensional network polymkeric substance of 1.0g embodiment 1 preparation
550M), 0.05g light trigger benzoin dimethylether (DMPA), 0.72g LiPF
6And vinyl carbonate/diethyl carbonate (EC/DEC=1: 1w/w) of 0.5g (50%) or 1.0g (100%) or 1.5g (150%) or 2.0g (200%), under dry atmosphere, join in the 25ml single port flask, fast sealing, carry out violent induction stirring 15-30min then, mixture is mixed, obtain the viscous liquid of tool flowability, it is cast in the tetrafluoroethylene mould then, directly exposing to the open air at wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2UV-light under solidified 5 minutes, obtain having internal plasticization chain (APEO
550M) gel polymer solid electrolyte film sample, then with sample 80 ℃ of vacuum (＜1mmHg) in the baking oven dry 24 hours, in the glove box of applying argon gas, be cooled to room temperature, test then.
After testing, that the present embodiment preparation is PMS-APEO
550M/LiPF
6/ EC/DEC (1: 1 w/w) gel polymer solid electrolyte film, what its room-temperature ion conductivity detected the results are shown in Table 1.
All solid state/gel polymer solid electrolyte film that embodiment 2～8 is prepared, the test result of its room-temperature ion conductivity is as shown in table 1.
Table 1. is all solid state/the room-temperature ion conductivity (Scm of gel polymer solid electrolyte film
-1)
| Real | LiN(CF 3SO 2) 2Content (wt%) | 5％ | 10％ | 15％ | 20％ |
| Execute example 2 | Room temperature conductivity (Scm -1) | 5.12×10 -6 | 2.73×10 -5 | 6.58×10 -5 | 1.01×10 -4 |
| Embodiment 3 | Softening agent and content (wt%) | PC％＝50 | PC％＝100 | PC％＝150 | PC％＝200 |
| Room temperature conductivity (Scm -1) | 3.79×10 -5 | 2.73×10 -4 | 7.9×10 -4 | 1.13×10 -3 | |
| Embodiment 4 | Softening agent and content (wt%) | PC％＝50 | PC％＝100 | PC％＝150 | PC％＝200 |
| Room temperature conductivity (Scm -1) | 8.39×10 -5 | 7.47×10 -4 | 1.10×10 -3 | 2.23×10 -3 | |
| Embodiment 5 | Softening agent and content (wt%) | EC％＝50 | EC％＝100 | EC％＝150 | EC％＝200 |
| Room temperature conductivity (Scm -1) | 5.85×10 -5 | 4.77×10 -4 | 9.96×10 -4 | 2.45×10 -3 | |
| Embodiment 6 | Softening agent and content (wt%) | EC/PC％＝50 | EC/PC％＝100 | EC/PC％＝150 | EC/PC％＝200 |
| Room temperature conductivity (Scm -1) | 9.56×10 -5 | 8.63×10 -4 | 1.71×10 -3 | 3.23×10 -3 | |
| Embodiment 7 | Softening agent and content (wt%) | EC/DEC％＝ 50 | EC/DEC％＝65 | EC/DEC％＝85 | EC/DEC％＝ 100 |
| Room temperature conductivity (Scm -1) | 1.05×10 -4 | 5.25×10 -4 | 1.07×10 -3 | 1.30×10 -3 | |
| Embodiment 8 | Softening agent and content (wt%) | EC/DEC％＝ 50 | EC/DEC％＝100 | EC/DEC％＝150 | EC/DEC％＝ 200 |
| Room temperature conductivity (Scm -1) | 1.10×10 -5 | 1.5×10 -3 | 2.71×10 -3 | 3.34×10 -3 |
In embodiment 2～8, when polarity small molecules plasticizer loading was increased to 150% by 50%, the room-temperature ion conductivity increased obviously, and when being increased to 200% by 150%, the room-temperature ion conductivity increases slack-off.Experimental study shows that composite elasticizer has higher room-temperature ion conductivity than single softening agent, and process for photocuring is better than thermal curing methods.Composite elasticizer content is 200% o'clock, compound plastifying embodiment 6 and embodiment 8, and the room-temperature ion conductivity reaches 3.23 * 10 respectively
-3Scm
-1With 3.34 * 10
-3Scm
-1, reach actual application level fully, and the electrolytic thin-membrane mechanical mechanics property, thermostability and the electrochemical stability that obtain are good, be a kind of polymer electrolyte film with actual application value.
Claims (10)
1, a kind of prepolymer of three-dimensional network polymkeric substance, the molecular structure of its structural unit is suc as formula shown in the I:
(formula 1)
Wherein, m+n=100, m=10 or 20 or 30; R
1Be the polyethylene oxide/polypropylene oxide segment of end band activated double bonds, the activated double bonds that described end has is two keys of methacrylic acid or acrylic acid structure; R
2Be trimethylene methyl polyoxyethylene or trimethylene methyl polyoxytrimethylene; Described R
1With R
2Mol ratio be 1: 1-7; The molecular weight of described trimethylene methyl polyoxyethylene is 150-1000.
2, the prepolymer of three-dimensional network polymkeric substance as claimed in claim 1 is characterized in that: the molecular weight of described trimethylene methyl polyoxyethylene is 390-790.
3, the prepolymer of three-dimensional network polymkeric substance as claimed in claim 2 is characterized in that: the molecular weight of described trimethylene methyl polyoxyethylene is 590.
4,, be to prepare with following method as the prepolymer of claim 1 or 2 or 3 described three-dimensional network polymkeric substance:
1) containing hydrogen silicone oil, the poly-pure and mild trimethylene methyl of the ethylene-propylene ether polyoxyethylene of trimethylene are dissolved in the toluene, reacting by heating obtains the presoma of the prepolymer of three-dimensional network polymkeric substance, and wherein the molfraction ratio of Si-H, the poly-ethylene-propylene ether alcohol of trimethylene, trimethylene methyl polyoxyethylene is 1: 0.125-0.875: 0.875-0.125;
2) presoma that step 1) is generated is dissolved in benzene, and adds behind the acid absorber triethylamine and the methacrylic chloride reaction, obtains the prepolymer of three-dimensional network polymkeric substance.
5, a kind of all solid state/gel polymer solid electrolyte, comprise that ratio of weight and number is 1: the prepolymer of the three-dimensional network polymkeric substance of 0.01-0.05: 0.05-0.72: 0-2.4, initiator, inorganic lithium salt, small molecules softening agent.
6, ionogen as claimed in claim 5 is characterized in that: described initiator is light trigger or thermal initiator; Described light trigger is benzoin dimethylether or benzophenone; Described thermal initiator is azo isobutyronitrile, benzoyl peroxide or peroxy dicarbonate di-t-butyl cyclohexyl; Described inorganic lithium salt comprises LiClO
4, LiPF
6, LiCF
3SO
3Or LiN (CF
3SO
2)
2Described small molecules softening agent is an annular lactone.
7, ionogen as claimed in claim 6 is characterized in that: described annular lactone is vinyl carbonate, diethyl carbonate, propylene carbonate or butyrolactone.
8, a kind of all solid state/preparation method of gel polymer solid electrolyte, may further comprise the steps:
1) prepolymer, initiator, dry inorganic lithium salt and the polarity small molecules softening agent with exsiccant three-dimensional network polymkeric substance is 1 by ratio of weight and the number of copies: 0.01-0.05: 0.05-0.72: 0-2.4 mixes;
2) mixture that step 1) is formed carries out induction stirring, obtains tool flowing property viscous liquid;
3) with step 2) liquid that obtains directly exposes to the open air under UV-light or at high temperature is cured, and generates conductive film;
4) conductive film is carried out vacuum-drying after, obtain gel polymer solid electrolyte.
9, method as claimed in claim 8 is characterized in that: when preparation full solid state polymer solid electrolyte, also need to add solvents tetrahydrofurane in the mixture that step 1) forms, and then carry out induction stirring.
10, method as claimed in claim 8 or 9, it is characterized in that: described initiator is light trigger or thermal initiator; Described light trigger is benzoin dimethylether or benzophenone; Described thermal initiator is azo isobutyronitrile, benzoyl peroxide or peroxy dicarbonate di-t-butyl cyclohexyl; Described inorganic lithium salt is LiClO
4, LiPF
6, LiCF
3SO
3Or LiN (CF
3SO
2)
2Described polarity small molecules softening agent is an annular lactone, and annular lactone is vinyl carbonate, diethyl carbonate, propylene carbonate or butyrolactone preferably; In preparation process, the described induction stirring time is 15-30 minute; When adopting light trigger, ultraviolet wavelength is 365 nanometers, power be 10 milliwatts/centimetre
2, be 5～15 minutes set time; When adopting thermal initiator, N
2Gas shiled, solidification value are 75～95 ℃, and be 12 hours set time; Described vacuum-drying temperature is 80 ℃, and be 24 hours time of drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106165179A (en) * | 2014-03-21 | 2016-11-23 | 巴斯夫欧洲公司 | Solid electrolyte |
| CN106549187A (en) * | 2016-10-27 | 2017-03-29 | 浙江大学 | A kind of dielectric film containing amphion full solid state polymer and its production and use |
-
2005
- 2005-06-13 CN CNA2005100766577A patent/CN1880354A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106165179A (en) * | 2014-03-21 | 2016-11-23 | 巴斯夫欧洲公司 | Solid electrolyte |
| CN106549187A (en) * | 2016-10-27 | 2017-03-29 | 浙江大学 | A kind of dielectric film containing amphion full solid state polymer and its production and use |
| CN106549187B (en) * | 2016-10-27 | 2018-11-02 | 浙江大学 | A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer |
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