CN104362373A - Ion liquid doped solid polymer electrolyte material and preparation method thereof - Google Patents
Ion liquid doped solid polymer electrolyte material and preparation method thereof Download PDFInfo
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- CN104362373A CN104362373A CN201410563412.6A CN201410563412A CN104362373A CN 104362373 A CN104362373 A CN 104362373A CN 201410563412 A CN201410563412 A CN 201410563412A CN 104362373 A CN104362373 A CN 104362373A
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000005518 polymer electrolyte Substances 0.000 title abstract description 8
- 239000007787 solid Substances 0.000 title abstract description 6
- 239000007788 liquid Substances 0.000 title abstract 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 28
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 28
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 16
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 16
- 229920001194 natural rubber Polymers 0.000 claims abstract description 16
- -1 1-carboxymethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ion Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002608 ionic liquid Substances 0.000 claims description 46
- 239000007784 solid electrolyte Substances 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 7
- 238000006735 epoxidation reaction Methods 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000003517 fume Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- WICWEYHSADNZSA-UHFFFAOYSA-N 2-(3-methyl-2h-imidazol-1-yl)acetic acid Chemical compound CN1CN(CC(O)=O)C=C1 WICWEYHSADNZSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 abstract description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 1
- PFMBEKPTRVTVDM-UHFFFAOYSA-O bis(trifluoromethylsulfonyl)azanide 2-(3-methylimidazol-3-ium-1-yl)acetic acid Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C(=O)(O)C[N+]1=CN(C=C1)C PFMBEKPTRVTVDM-UHFFFAOYSA-O 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000010058 rubber compounding Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UCALSOAGXCDLQT-UHFFFAOYSA-N 1-ethyl-3-methylimidazole Chemical compound CCN1[CH]N(C)C=C1 UCALSOAGXCDLQT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to an ion liquid doped solid polymer electrolyte material and a preparation method thereof. Raw materials comprise ENR (epoxidized natural rubber), bistrifluoromethanesulfonimide lithium salt and 1-carboxymethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ion liquid. 1-carboxymethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide is introduced into the solid polymer electrolyte material, carboxyl in the molecular structure of the ion liquid chemically reacts with an epoxy group of the ENR to interlink the ENR, and meanwhile, the ion liquid is taken as a solvent of the lithium salt, so that the solubility of the lithium salt in the material can be improved, a function of plasticizing the material is also realized, and the ionic conductivity of the prepared material is further improved. According to the technical scheme, the introduction of a rubber compounding ingredient such as a plasticizer, an active agent and a vulcanization accelerator is avoided, so that the prepared material is free of other micromolecular product residues, and the electrochemical stability of the solid polymer electrolyte material is favorably improved.
Description
Technical field
The present invention relates to preparation of polymer solid electrolyte, especially relate to a kind of ionic liquid doping type copolymer solid electrolyte material and preparation method thereof.
Background technology
Copolymer solid electrolyte (SPE) is mixed to form primarily of polymer and slaine.Since polyethylene glycol oxide and alkali metal salt complex compound have ionic conductivity from Late Cambrian such as Wright in 1973, the application of the polymer dielectric being matrix with it in chemical power source, sensor causes the great attention of people.Solid electrolyte overcomes liquid electrolyte battery leakage and unstable shortcoming, copolymer solid electrolyte is applied to various electrochemical element simultaneously, while the simplification realizing element manufacture, miniaturization and the lightweight of element self become a reality, not only there is no the danger of leakage, but also the cell device providing reliability high.But the ionic conductivity of SPE is relative to lower liquid and gel electrolyte.
Ionic liquid (IL) i.e. room temperature molten salt, mainly be made up of organic cation and inorganic anion, it has the characteristics such as non-volatile, thermally-stabilised, strong polarity, by the compatibility to the adjustable dissolubility to slaine of the design of cation and anion and it and polymer, so it can be used as the additive of copolymer solid electrolyte material should have certain advantage.The introducing of IL, is conducive to the conductivity and the thermal stability that improve copolymer solid electrolyte material.
Epoxy natural rubber (ENR) obtains by carrying out epoxidation modification to natural rubber (NR), it not only maintains the premium properties such as high strength and high resiliency of natural rubber, improve its oil resistance, air-tightness and resistance to wet skidding performance simultaneously, and cheap.In addition it provides great convenience for the twice-modified of natural rubber.The elasticity of ENR is higher, good with the adhesiveness of other material, for providing good electrochemical contact between electrode, its with polar group---epoxy radicals is conducive to lithium ion conduction in the electrolyte.
Advanced Materials Research reports the people such as Zainal at the 287th volume 424-427 page in 2011 and to be introduced in ENR-50 and LiTFSI by the IL:1-ethyl-3-methylimidazole two (fluoroform sulphonyl) imines (EMITFSI) based on glyoxaline cation and obtain copolymer solid electrolyte material.At room temperature, when sample is 5.72 × 10 containing high ionic conductivity most during EMITFSI and 50wt%LiTFSI of 20wt%
-4s/cm.Adopt SPE prepared by above method, only just ionic liquid is mixed in electrolyte by physical method.
CN 102368564A discloses a kind of preparation method of gel-type polymer electrolyte, the method is to hold amido acrylonitrile-butadiene rubber (ATBN) as polymeric matrix, epoxidation polyhedral polysilsesquioxane (POSS) is as crosslinking agent, ionic liquid is as organic solvent, lithium perchlorate, as lithium salts, has prepared a kind of polymer dielectric by solution-cast film forming and heat treatment.This electrolytical conductivity can reach 2.00 × 10 at 30 DEG C
-4s/cm.But gel-type polymer electrolyte material is after all containing a large amount of plasticizer, and its thermostability still can not be equal to full solid state polymer electrolyte material.
Summary of the invention
Object of the present invention is exactly the defect existed to overcome prior art, and provides a kind of and have ion doping type copolymer solid electrolyte that conductance is high, Heat stability is good, mechanical performance are high and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions:
A kind of ionic liquid doping type copolymer solid electrolyte material, adopts the raw material of following molar constituent content to prepare and obtains: the epoxy-functional in polymeric matrix: ionic liquid: lithium salts is 0.005-0.007: 0.1-1.5: 0.05 ~ 1.5.
As preferred embodiment, the polymeric matrix of employing to be epoxidation degree be 50% epoxy natural rubber.
As preferred embodiment, ionic liquid is two (fluoroform sulphonyl) inferior amine salt of 1-carboxymethyl-3-methylimidazole of molecular weight 421.29g/mol.
As preferred embodiment, lithium salts is two (fluoroform sulphonyl) imido grpup lithium salts of molecular weight 287.08g/mol.
The preparation method of ionic liquid doping type copolymer solid electrolyte material adopts following steps:
(1) weighing polymer matrix is dissolved in mixed solvent, after swelling, continue to add mixed solvent and magnetic agitation until be dissolved into homogeneous solution;
(2) ionic liquid and lithium salts are joined magnetic agitation 0.5h in tetrahydrofuran solvent by formula, the solution then adding step (1) gained continues to stir 2h;
(3) mixed solution of step (2) gained is cast in Teflon mould, naturally volatilize 12 hours in fume hood, then be transferred in vacuum drying oven and obtain film after drying, be ionic liquid doping type copolymer solid electrolyte material.
As preferred embodiment, mixed solvent is dimethylbenzene and oxolane 4: 6 solvents mixed by volume.
As preferred embodiment, the film prepared is dry 24h at 40 DEG C, or at 80 DEG C, continues dry 10h after dry 24h at 40 DEG C.
The present invention introduces a kind of ionic liquid with carboxyl and a kind of lithium salts in epoxy natural rubber, by the chemical reaction between the carboxyl of IL and the epoxy radicals of ENR, ENR is produced crosslinked, simultaneously, ionic liquid is as the solvent of lithium salts, the solubility of lithium salts in polymeric matrix can be made to improve, again plasticization is served to polymeric matrix, and then improve the ionic conductivity of prepared material.Other the rubber chemicals such as plasticizer, activating agent, vulcanization accelerator are not introduced in technical scheme of the present invention, and reaction condition is gentle, do not have Small molecular product to remain in prepared material, this contributes to improving electrolyte electrochemical stability and ionic conductivity.
Compared with prior art, the present invention take epoxy natural rubber as matrix, add ionic liquid and lithium salts obtains copolymer solid electrolyte material, it is crosslinked that ionic liquid with carboxyl functional group can make epoxy natural rubber matrix produce, simultaneously, due to the adding of ionic liquid of high ionic conductivity, both lithium salts solubility had in the material been added, again plasticization is served to epoxy natural rubber matrix, make that the conductivity of the copolymer solid electrolyte of gained is maximum at normal temperatures reaches 3.0074 × 10
-4s/cm.Feature of the present invention is as follows:
(1) the present invention is by the chemical reaction between the carboxyl in ionic liquid (IL) molecular structure and the epoxy radicals of epoxy natural rubber (ENR), ENR is produced crosslinked;
(2) in technical scheme of the present invention IL both as the solvent of lithium salts, act as again curing agent and the plasticizer of ENR, do not introduce the rubber compositions such as other plasticizer, activator, vulcanization accelerator, in prepared material, there is no the residual of Small molecular product;
(3) reaction condition is gentle, and reaction is carried out all at normal temperatures and pressures;
(4) polymer electrolyte film character is soft, can with electrode good contact, the interface resistance of battery can be reduced;
(5) use of solid polyelectrolyte can avoid the problem of liquid electrolyte leakage, improves fail safe.
Accompanying drawing explanation
Fig. 1 is the AC impedance spectrogram of embodiment 4;
Fig. 2 is the AC impedance spectrogram of embodiment 5;
Fig. 3 is the AC impedance spectrogram of embodiment 8;
Fig. 4 is the AC impedance spectrogram of embodiment 9;
Fig. 5 is the AC impedance spectrogram of embodiment 10
Fig. 6 is the AC impedance spectrogram of embodiment 13;
Fig. 7 is the AC impedance spectrogram of embodiment 14;
Fig. 8 is the AC impedance spectrogram implementing profit 17.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Following examples and comparative example material therefor:
Epoxy natural rubber (ENR50), epoxidation degree is 50%, Chinese Academy of Tropical Agricultural Sciences.
Ionic liquid: two (fluoroform sulphonyl) inferior amine salt ([HOOCMMIm] NTf of 1-carboxymethyl-3-methylimidazole
2), Lanzhou Ao Like Chemical Co., Ltd..
Lithium salts: two (fluoroform sulphonyl) imido grpup lithium salts (LiNTf
2), analyze pure, Lanzhou Ao Like Chemical Co., Ltd..
Embodiment 1 ~ 10
(1) joined in beaker by 1.0g epoxy natural rubber, and add 4ml dimethylbenzene, 6ml oxolane, makes swell rubber.After about 2h, magnetic agitation is carried out to mixture, until rubber dissolves completely.In whipping process, constantly add mixed solvent.
(2) according to table 1 embodiment 1 ~ 10, ionic liquid and lithium salts are dissolved in 20ml tetrahydrofuran solvent, magnetic agitation 0.5h.
(3) solution of (2) gained is joined in rubber solutions and continue to stir 2h.
(4) mixed solution of gained is cast in Teflon mould, is put in fume hood the 12h that naturally volatilizees.Then dry 24h at 40 DEG C is transferred in vacuum drying oven.
(5) cut the thin slice of 5 × 5mm from gained film, test by AC impedence method on Autolab PGSTTA302 electrochemical workstation to it, frequency range is 1e+5 ~ 1Hz, and perturbation is 5mV.
Comparative example
The step adopted is identical with embodiment 1, and concrete raw material composition is in table 1.
Embodiment 11 ~ 17
(1) joined in beaker by 1.0g epoxy natural rubber, and add 4ml dimethylbenzene, 6ml oxolane, makes swell rubber.After about 2h, magnetic agitation is carried out to mixture, until rubber dissolves completely.In whipping process, constantly add mixed solvent.
(2) according to table 2 embodiment 11 ~ 17, ionic liquid and lithium salts are dissolved in 20ml tetrahydrofuran solvent, magnetic agitation 0.5h.
(3) solution of (2) gained is joined in rubber solutions and continue to stir 2h.
(4) mixed solution of gained is cast in Teflon mould, is put in fume hood the 12h that naturally volatilizees.Then transfer in vacuum drying oven and at 80 DEG C, continue dry 10h after dry 24h at 40 DEG C.
(5) cut the thin slice of 5 × 5mm from gained film, test by AC impedence method on Autolab PGSTTA302 electrochemical workstation to it, frequency range is le+5 ~ 1Hz, and perturbation is 5mV.
Table 1 prepares formula and the performance test results (dried strip of ionic liquid doping type copolymer solid electrolyte
Part: 40 DEG C of 24h)
| Embodiment | ENR(mol) | 1L(mol) | Li Salt(mol) | σ(S/cm) |
| 1 | 6.58×10 -3 | 0.25 | 0.0625 | 5.1094×10 -7 |
| 2 | 6.58×10 -3 | 0.25 | 0.125 | 1.8708×10 -6 |
| 3 | 6.58×10 -3 | 0.25 | 0.25 | 3.4993×10 -6 |
| 4 | 6.58×10 -3 | 0.25 | 0.5 | 9.9687×10 -5 |
| 5 | 6.58×10 -3 | 0.5 | 0.125 | 3.6117×10 -6 |
| 6 | 6.58×10 -3 | 0.5 | 0.25 | 3.9462×10 -6 |
| 7 | 6.58×10 -3 | 0.5 | 0.5 | 1.0926×10 -6 |
| 8 | 6.58×10 -3 | 1 | 0.25 | 1.2305×10 -5 |
| 9 | 6.58×10 -3 | 1 | 0.5 | 1.3055×10 -5 |
| 10 | 6.58×10 -3 | 1 | 1 | 3.0074×10 -4 |
| Comparative example | 6.58×10 -3 | 0 | 0.25 | 7.5997×10 -8 |
Table 2 prepares formula and the performance test results (drying condition: 40 DEG C of 24h+80 DEG C of 10h) of ionic liquid doping type copolymer solid electrolyte
| Embodiment | ENR(mol) | 1L(mol) | LiSalt(mol) | σ(S/cm) |
| 11 | 6.58×10 -3 | 0.25 | 0.5 | 3.1611×10 -6 |
| 12 | 6.58×10 -3 | 0.5 | 0.125 | 1.8924×10 -6 |
| 13 | 6.58×10 -3 | 0.5 | 0.25 | 2.3965×10 -6 |
| 14 | 6.58×10 -3 | 0.5 | 0.5 | 1.2022×10 -5 |
| 15 | 6.58×10 -3 | 1 | 0.25 | 1.3690×10 -5 |
| 16 | 6.58×10 -3 | 1 | 0.5 | 8.0398×10 -6 |
| 17 | 6.58×10 -3 | 1 | 1 | 7.8509×10 -5 |
As seen from Table 1, adopt the preparation method of a kind of ionic liquid doping type copolymer solid electrolyte material of the present invention, do not add ionic liquid, when the addition of lithium salts is 20mol%, the conductivity of copolymer solid electrolyte film is 7.5997 × 10
-8s/cm.
When the mol ratio of epoxy radicals and IL is 1: 0.25, along with the increase of lithium salt content, the ionic conductivity of material also constantly increases.As seen from Figure 1, now ionic conductivity can reach 9.9687 × 10
-5s/cm.
When the mol ratio of epoxy radicals and IL is 1: 0.5, the increase of lithium salt content can't cause the significantly change of material ions conductivity; Ionic conductivity can reach 10
-6s/cm.
From Fig. 2 and Fig. 4, when the mol ratio of ionic liquid and lithium salts is 2: 1, along with the increase of both content in system, ionic conductivity also can raise.
As seen from Figure 5, when epoxy radicals: ionic liquid: lithium salts=1: when 1: 1, the ionic conductivity of material is 3.0074 × 10
-4s/cm.
As seen from Figure 6, when the mol ratio of epoxy radicals and lithium salts is 1: 0.25, ionic conductivity and film substantially close not in the drying of 80 DEG C of 10h of the dried film of 80 DEG C of 10h.
From Fig. 7 and Fig. 8, when ionic liquid and lithium salts etc. mole add fashionable, increase on the contrary in the ionic conductivity of the dry post-consumer polymer solid electrolyte of 80 DEG C of 10h.
Claims (7)
1. an ionic liquid doping type copolymer solid electrolyte material, it is characterized in that, this electrolyte adopts the raw material of following molar constituent content to prepare and obtains: the epoxy-functional in polymeric matrix: ionic liquid: lithium salts is 0.005-0.007: 0.1-1.5: 0.05 ~ 1.5.
2. a kind of ionic liquid doping type copolymer solid electrolyte material according to claim 1, is characterized in that, polymeric matrix to be epoxidation degree be 50% epoxy natural rubber.
3. a kind of ionic liquid doping type copolymer solid electrolyte material according to claim 1, is characterized in that, described ionic liquid is two (fluoroform sulphonyl) inferior amine salt of 1-carboxymethyl-3-methylimidazole of molecular weight 421.29g/mol.
4. a kind of ionic liquid doping type copolymer solid electrolyte material according to claim 1, is characterized in that, described lithium salts is two (fluoroform sulphonyl) imido grpup lithium salts of molecular weight 287.08g/mol.
5. the preparation method of the ionic liquid doping type copolymer solid electrolyte material according to any one of claim 1-4, is characterized in that, the method adopts following steps:
(1) weighing polymer matrix is dissolved in mixed solvent, after swelling, continue to add mixed solvent and magnetic agitation until be dissolved into homogeneous solution;
(2) ionic liquid and lithium salts are joined magnetic agitation 0.5h in tetrahydrofuran solvent by formula, the solution then adding step (1) gained continues to stir 2h;
(3) mixed solution of step (2) gained is cast in Teflon mould, naturally volatilize 12 hours in fume hood, then be transferred in vacuum drying oven and obtain film after drying, be ionic liquid doping type copolymer solid electrolyte material.
6. the preparation method of a kind of ionic liquid doping type copolymer solid electrolyte material according to claim 5, is characterized in that, described mixed solvent is dimethylbenzene and oxolane 4: 6 solvents mixed by volume.
7. the preparation method of a kind of ionic liquid doping type copolymer solid electrolyte material according to claim 5, it is characterized in that, the film prepared is dry 24h at 40 DEG C, or at 80 DEG C, continues dry 10h after dry 24h at 40 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206872A (en) * | 2015-09-23 | 2015-12-30 | 上海交通大学 | Grafting type comb polymer solid electrolyte material and preparation method thereof |
| CN112851871A (en) * | 2021-02-05 | 2021-05-28 | 北京航空航天大学 | Elastic solid electrolyte material and preparation method thereof |
| CN113437359A (en) * | 2021-05-18 | 2021-09-24 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440177A (en) * | 2008-12-11 | 2009-05-27 | 上海交通大学 | Preparation of polymer solid electrolyte |
| CN101908632A (en) * | 2010-07-15 | 2010-12-08 | 上海大学 | Ternary doping modified SPEEK proton exchange membrane and preparation method |
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| CN101440177A (en) * | 2008-12-11 | 2009-05-27 | 上海交通大学 | Preparation of polymer solid electrolyte |
| CN101908632A (en) * | 2010-07-15 | 2010-12-08 | 上海大学 | Ternary doping modified SPEEK proton exchange membrane and preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206872A (en) * | 2015-09-23 | 2015-12-30 | 上海交通大学 | Grafting type comb polymer solid electrolyte material and preparation method thereof |
| CN112851871A (en) * | 2021-02-05 | 2021-05-28 | 北京航空航天大学 | Elastic solid electrolyte material and preparation method thereof |
| CN112851871B (en) * | 2021-02-05 | 2021-10-26 | 北京航空航天大学 | Elastic solid electrolyte material and preparation method thereof |
| CN113437359A (en) * | 2021-05-18 | 2021-09-24 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
| CN113437359B (en) * | 2021-05-18 | 2023-04-07 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
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| CN104362373B (en) | 2017-01-11 |
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