CN101243134A - Electrolyte comprising eutectic mixture and electrochemical device using the same - Google Patents
Electrolyte comprising eutectic mixture and electrochemical device using the same Download PDFInfo
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- CN101243134A CN101243134A CNA2006800302823A CN200680030282A CN101243134A CN 101243134 A CN101243134 A CN 101243134A CN A2006800302823 A CNA2006800302823 A CN A2006800302823A CN 200680030282 A CN200680030282 A CN 200680030282A CN 101243134 A CN101243134 A CN 101243134A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
Disclosed is an electrolyte comprising a eutectic mixture formed of: (a) an amide group-containing compound; and (b) a lithum-free ionizable salt. An electrochemical device comprising the electrolyte is also disclosed. The electrolyte improves the quality of and electrochemical device due to the excellent conductivity of the metal cation contained in the eutectic mixture, a broad electrochemical window and low viscosity. Additionally, since the eutectic mixture has excellent thermal and chemical stability, it is possible to solve the problems of evaporation, exhaustion and ignition of electrolytes, to minimize side reactions between constitutional elements of the device and the electrolyte, and to improve the safety of the electrochemical device.
Description
Technical field
The present invention relates to a kind of ionogen that contains eutectic mixture, it has Gao Re and chemical stability, high conductivity and wide electrochemical window.The invention still further relates to the above-mentioned electrolyte electrochemical device of a kind of use, it has improved security and quality.
Background technology
In recent years, various ionogen have been widely used in the electrochemical appliance, and described electrochemical appliance is for example for lithium secondary battery, electrolytic condenser, two layer capacitances or electrochromic display device and to the following practical dye sensitization solar battery of having done further investigation.Under the situation, this electrolytical importance becomes more and more higher herein.
The most widely used ionogen comprises non-aqueous solution in recent years, it comprises the electrolytic salt that is dissolved in the organic solvent, described organic solvent is ethylene carbonate, Texacar PC, glycol dimethyl ether, gamma-butyrolactone (GBL), N for example, dinethylformamide, tetrahydrofuran (THF) or acetonitrile.This non-aqueous electrolyte carries out the conduction of ion and electronics as medium between two electrodes, keep stable under the drive voltage range of the device that Ying Zaiqi uses, and should demonstrate enough ionic conductivities.Yet be used for this electrolytical organic solvent and have low viscosity, spill easily and have high volatile volatile and cause evaporation.In addition, this organic solvent easily catches fire, thereby is problematic with regard to long-term reliability, weather resistance and stable aspect.Yet conventional ion liquid is very expensive, needs to obtain through complicated preparation and purge process.In addition, the disadvantage of liquid electrolyte is that also it has the possibility that spills, so inapplicable in the device that is designed to large size or little thickness.
Simultaneously, G.Berchiesi and its colleague utilize ethanamide, LiSCN (lithium thiocyanate), CH
3COOLi (lithium acetate), etc. prepared eutectic mixture (Thermochimica Acta, 1983,70, pp317-324).Yet, and the unexposed ionogen that utilizes above-mentioned eutectic mixture as electrochemical appliance.
Summary of the invention
Therefore finished the present invention in view of the above problems.The contriver finds, when use cost effectively has the eutectic mixture of good heat and chemical stability in the ionogen at electrochemical appliance, can solve electrolyte evaporation when using conventional organic solvent, exhaust as ionogen, with flammable problem, thereby improve security.The inventor finds again, because good conductivity of this eutectic mixture and wide electrochemical window, can improve the quality of electrochemical appliance.
The purpose of this invention is to provide a kind of ionogen that comprises eutectic mixture, and provide and have this electrolyte electrochemical device.
According to an aspect of of the present present invention, a kind of ionogen that comprises eutectic mixture is provided, described eutectic mixture is by the compound of (a) amide-containing and (b) the ionizable salt formation of no lithium.Provide in addition to comprise this electrolyte electrochemical device, be preferably electrochromic device.
Hereinafter with more detailed description the present invention.
The invention is characterized in and use eutectic mixture to form the ionogen of electrochemical appliance, wherein this eutectic mixture does not contain lithium.
Generally speaking, eutectic mixture is meant and comprises two or more kinds of material and have the mixture of the fusing point of reduction.Especially, described eutectic mixture comprises the mixing salt that at room temperature exists with liquid phase.Herein, room temperature refers to high to 100 ℃ or the high in some cases temperature to 60 ℃.
According to the present invention, eutectic mixture comprises at least two kinds of materials, and one of them comprises comparing with conventional lithium salts to have more any metal-salt of highly conc.Therefore, because the good conductivity of this metal component, by improving electrolytical ionic conductivity thus, thereby improved the quality of electrochemical appliance.For example when containing sodium salt when the metal-salt, can obtain to compare at least three times of improvement or even ten times or more conductivity with lithium salts.In addition when ionogen comprises this metal-salt, compare with the ionogen that uses lithium salts and can demonstrate significant viscosity and reduce, promoted ion to move and/or transmit thus, thereby caused the improvement of the quality of electrochemical appliance via electrolytical.The reduction of viscosity be commonly considered as since in salt the weakening of bonding force, the bonding force that causes because of this metal weakens greater than the bonding force that causes because of lithium and weakens.In addition, use organic salt to form eutectic mixture according to ionogen of the present invention, conventional electrolysis matter then is to utilize metal-salt to form eutectic mixture.Therefore can overcome the restriction of the composition of eutectic mixture according to the present invention.
In addition, compare with ionic liquid with conventional organic solvent, the ionogen that comprises above-mentioned eutectic mixture shows wideer electrochemical window because of the physical stability of eutectic mixture self, therefore uses above-mentioned electrolyte electrochemical device that the drive voltage range of prolongation can be arranged.In fact, be limited to about 4～4.5V on the conventional electrolysis matter demonstration electrochemical window of use ionic liquid and organic solvent, then show the electrochemical window upper limit of 4.5～5.5V according to eutectic mixture of the present invention, this with compare obvious the prolongation based on ionic liquid with the conventional electrolysis matter of organic solvent.
In addition, opposite with conventional solvent, do not have vapour pressure according to contained eutectic mixture in the ionogen of the present invention, so ionogen does not have evaporation and the problem that exhausts.And eutectic mixture tool flame resistivity, thereby improved the security of electrochemical appliance.In addition, eutectic mixture self is highly stable, therefore can suppress side reaction and take place in electrochemical appliance.In fact, eutectic mixture has the wide temperature range that exists with liquid form, has the high solvent ability, has non-coordinate feature, or the like.Therefore well-known, eutectic mixture has as the physical and chemical performance that can replace the environmentally friendly solvent of conventional harmful organic solvent.In addition, with conventional ion liquid phase ratio, eutectic mixture is via simple relatively method preparation, and has high ion concentration.Therefore expect that this eutectic mixture has wide range of application.
According to preferred implementation of the present invention, a kind of integrant that forms eutectic mixture is the compound of amide-containing, and it has two dissimilar polarity functional groups, i.e. carbonyl and amido in molecule.Yet any compound that has at least two polar functional groups (for example acidic-group and basic group) in molecule all can use, and is without particular limitation to it.
The effect of complexing agent is played by described mutual dissimilar polarity functional group, and combining between this positively charged ion that has reduced ionizable salt and negatively charged ion forms eutectic mixture thus, and cause the reduction of temperature of fusion.Except that above-mentioned functional group, thereby comprise the compound that bonded polar functional group between the positively charged ion that can weaken ionizable salt and negatively charged ion can form eutectic mixture, be also contained in the scope of the present invention.
The compound of amide-containing can be have linear structure, the amide-containing compound of ring texture or its combination.Nonrestrictive amino-contained examples of compounds comprises C1～C10 alkylamide, alkenyl amide, arylamide or alkaryl amide compound.Also can use primary amide, secondary amide or teritary amide compound.The preferred cyclic amide compound that shows wideer electrochemical window that uses because this cyclic amide compound has number of hydrogen atoms still less, can prevent its decomposition thereby under high pressure stablize.The example that can be used for non-limiting amide compound of the present invention comprises ethanamide, urea, methyl urea, hexanolactam, Valerolactim, carbamate, methane amide and above-mentioned mixture.
Another integrant that forms eutectic mixture according to the present invention comprises the ionizable salt of any no lithium.The non-limitative example of this salt comprises metal-salt, organic salt or its mixing salt, and this salt comprises at least a metal of the basic metal that is selected from except that lithium, alkaline-earth metal, transition metal, metalloid, lanthanon, actinide elements.
Can be by as shown in the formula 1 expression according to eutectic mixture of the present invention, but unrestricted in this:
[formula 1]
R wherein
1Be hydrogen atom, C1～C20 alkyl, C1～C20 alkylamino radical, thiazolinyl, aryl or alkylaryl;
R
2Be hydrogen atom, halogen atom, C1～C20 alkyl, thiazolinyl, aryl or alkylaryl;
A is selected from carbon, oxygen, hydrogen, nitrogen, sulphur, and condition is R when A is hydrogen
2Be empty;
The X representative is selected from least a metallic cation or the organic cation of basic metal, alkaline-earth metal, transition metal, metalloid, lanthanon and actinide elements except that lithium;
Y representative can with the salifiable negatively charged ion of X-shaped; And
N represents integer 0～10, and when n be 1 or when bigger, A is selected from carbon, oxygen, nitrogen and sulphur, and hydrogen is left out.
Preferably, in compound with above-mentioned formula 1 expression, positively charged ion X represents the second month in a season, uncle and quaternary ammonium, phosphorus , magnesium, potassium, or calcium, and negatively charged ion Y is thiocyanate ion, formate, acetate moiety, nitrate radical, perchlorate, sulfate radical, oxyhydroxide root, alkoxide root, halogenide root, carbonate root, oxalate or tetrafluoroborate.
As mentioned above, the integrant of eutectic mixture, i.e. the ionizable salt (XY) of the compound of amide-containing and no lithium causes metal or organic cation (X at the ionizable salt of the carbonyl of the compound of amide-containing and no lithium
+) between form coordinate bond, and at the negatively charged ion (Y of described salt
-) and the amido that in the compound of amide-containing, exists between form hydrogen bond, shown in the reaction formula 1 described as follows.The chemical bond of every kind of compound is all weakened.The result causes the compound of amide-containing and the ionizable salt of no lithium (it was solid-state originally) to demonstrate the fusing point (mp) of reduction, thereby at room temperature promptly forms liquid eutectic mixture when it.
[reaction formula 1]
Though according to the present invention the fusing point of eutectic mixture is not had special restriction, its preferably when temperature height to 100 ℃ eutectic mixture be liquid, be more preferably at room temperature for liquid.Though according to the present invention the viscosity of eutectic mixture is not had special restriction yet, the preferred viscosity of eutectic mixture is 100cp or littler.
Described eutectic mixture can be by the ordinary method preparation that those skilled in the art knew.For example, the compound that will have amide group at room temperature mixes with the ionizable salt of no lithium, and this mixture reacts subsequent purificn being heated under 70 ℃ or the lower suitable temp then.Herein, the compound with acidic functionality and basic functionality is 1: 1 to 8: 1 than the OK range of the mol ratio (%) of lithium salts, more preferably by 2: 1 to 6: 1.
＜comprise the ionogen of eutectic mixture 〉
Can be applicable to any ionogen according to eutectic mixture of the present invention, no matter which kind of form described ionogen is.Preferably, this eutectic mixture can be applicable to the ionogen of two kinds of forms, i.e. liquid electrolyte and gel polymer electrolyte.
Herein, ionogen can further comprise at least a salt, is preferably ionizable lithium salts.The anionic unrestricted example that can be used for the lithium salts among the present invention comprises F
-, Cl
-, Br
-, I
-, NO
3 -, BF
4 -, PF
6 -, N (CN)
2 -, SCN, ClO
4 -, (CF
3)
3PF
3 -, (CF
3)
4PF
2 -, (CF
3)
5PF
-, (CF
3)
6P
-, (CF
3CF
2SO
2 -)
2N, (CF
3SO
2)
2N
-, CF
3SO
3 -, CF
3CF
2(CF
3)
2CO
-, (CF
3SO
2)
2CH
-, (CF
3SO
2)
3C
-, CF
3(CF
2)
7SO
3 -, CF
3CO
2 -, CH
3CO
2 -, or resemblance.If possible, described negatively charged ion is preferably identical with the negatively charged ion that forms eutectic mixture.This is that lithium salts can reduce the electrolytical solubleness that comprises eutectic mixture because when the negatively charged ion in lithium salts is different from the negatively charged ion of eutectic mixture.The preferred working concentration of lithium salts is 0～1 mole/L, but is not to be limited to this.
(1) according to embodiments of the present invention, ionogen is the liquid-type ionogen that comprises eutectic mixture, and it obtains by the combination of independent use by the eutectic mixture of the compound of above-mentioned amide-containing and the ionizable salt formation of no lithium or itself and at least a salt.
(2) according to another embodiment of the present invention, described ionogen is the gelatin polymer type ionogen that comprises eutectic mixture.Gelatin polymer plays the effect of carrying eutectic mixture.Therefore in the case, it can solve the problem that ionogen leaks outside, and forms the electrochemical appliance of film or other form membrane.
The method that gel polymer electrolyte can utilize those skilled in the art to know is prepared.Described method can be carried out according to following three types embodiment.Certainly, described eutectic mixture can further comprise at least a above-mentioned salt.
1. according to the preferred implementation of this method, in the presence of eutectic mixture, carry out monomeric polymerization, to form gel polymer electrolyte.The described method that forms gel polymer electrolyte via monomer polymerization can be undertaken by in-situ polymerization in electrochemical appliance inside.Or opposite, can after forming gel polymer electrolyte, described gel polymer electrolyte be introduced in the electrochemical appliance.
Described gel polymer electrolyte can be formed by the polymerization of ionogen pre-gelled solution (electrolyte precursors solution), this ionogen pre-gelled solution comprises (i) eutectic mixture, it comprises the compound of amide-containing and the ionizable salt that does not have lithium, and the monomer that (ii) can form gelatin polymer through polymerization.
To monomeric kind and unrestricted, as long as it can form gelatin polymer through polymerization, this monomeric special example comprises vinyl monomer etc.The advantage that vinyl monomer has is for providing the transparent polymeric product when mixing with eutectic mixture, and easy polymerizing condition can be realized polymerization.
According to the non-limitative example of the spendable vinyl monomer of the present invention comprise vinyl cyanide, methyl methacrylate, methyl acrylate, methacrylonitrile, vinyl toluene, vinyl ester, vinylchlorid, vinylidene chloride, acrylamide, tetrafluoroethylene, vinyl-acetic ester, methyl vinyl ketone, ethene, vinylbenzene, to methoxy styrene, to cyano-styrene etc.
Preferably, the monomer that can form gelatin polymer by polymerization provides low volumetric shrinkage when polymerization, and allows to carry out polymerization in the inner original position of electrochemical appliance.
Monomeric polymerization is generally carried out under heat or UV irradiation, so ionogen pre-gelled solution can further comprise polymerization starter or light trigger.
Initiator is decomposed to form free radical because of heat or UV ray, forms gel polymer electrolyte by radical polymerization with monomer reaction subsequently.Monomeric polymerization also can be carried out under the situation without any initiator.Generally speaking, radical polymerization comprises the initiation step, forms transient state molecule or the active site with strong reactivity in causing step; Growth steps, monomer adds to the living chain end to form another active site of chain end in growth steps; The chain transfer step, active site is transferred to other molecules in the chain transfer step; And the termination step, in stopping step, the center burst of living chain.
Can be used for the polymeric thermal initiator and comprise organo-peroxide or hydroperoxide for example benzoyl peroxide, acetyl peroxide, dilauryl superoxide, ditertiary butyl peroxide, cumene hydroperoxide, hydrogen peroxide etc., and azo-compound for example 2,2-azo two (2-cyano group butane), 2,2-azo two (methylbutyronitrile), AIBN (azobis isobutyronitrile), AMVN (the two methyl pentane nitriles of azo), organometallic compound be alkylating silver compound etc. for example.In addition, allow by light for example the UV ray non-limitative example that forms the light trigger of free radical comprise chloracetophenone, diethoxy acetophenone (DEAP), 1-phenyl-2-hydroxy-2-methyl acetone (HMPP), 1-hydroxycyclohexylphenylketone, alpha-aminoacetophenone, benzoin ether, benzyl dimethyl ketone acetal, benzophenone, thioxanthone, 2-ethyl-anthraquinone (2-ETAQ) etc.
In addition, according to the present invention's ratio of mixture based on weight in electrolyte precursors solution, i.e. (eutectic mixture) x: (can form the monomer of gelatin polymer) y: the weight ratio of (polymerization starter) z by polymerization, be 0.5～0.95: 0.05～0.5: 0.00～0.05, condition is x+y+z=1.Preferably, x is 0.7～0.95, y is 0.05～0.3 and z is 0.00～0.01.
Except above-mentioned materials, randomly further comprise other additive well known to those skilled in the art according to the precursor solution of gel polymer electrolyte of the present invention.
As mentioned above, in-situ polymerization forms gel polymer electrolyte thus by irradiation heat or UV ray and cause.Herein, the polymerization degree of gelatin polymer depends on reaction conditions, promptly at the polymerization time under the thermopolymerization situation and temperature or the photoirradiation dosage under UV polymerization situation.Therefore, can comprise polymerization time, polymerization temperature or photoirradiation dosage by control reaction shape condition, thereby control the polymerization degree of gelatin polymer according to expectation like that.In addition, polymerization time depends on and is used for polymeric initiator type and polymerization temperature.Preferably, in the time period that described polymerization is carried out spilling of gel polymer electrolyte can not be taken place, and the excessively polymerization and cause the degree of volumetric shrinkage of described ionogen.For example polymerization is general implemented about 40～80 ℃ of temperature about 20～60 minutes.
2. according to another preferred implementation of the present invention, eutectic mixture is injected in preformed polymkeric substance or the gelatin polymer, make in this polymkeric substance or the gelatin polymer and be impregnated with eutectic mixture.
The non-limitative example that can be used for the polymkeric substance among the present invention comprises polymethylmethacrylate, poly(vinylidene fluoride), polyvinyl chloride, polyoxyethylene, poly hydroxy ethyl acrylate etc.Also can use the gel quav polymkeric substance known to those skilled in the art.In this case, compare, can simplify treatment step with above-mentioned in-situ polymerization.
3. according to another preferred implementation of the present invention, polymkeric substance and eutectic mixture are dissolved in the solvent, solvent removal is to form gel polymer electrolyte subsequently.Herein, eutectic mixture is included in this polymeric matrix.
Though do not have special restriction for choice of Solvent, the non-limitative example of solvent comprises toluene, acetone, acetonitrile, THF etc.In addition, the method that removes solvent has no particular limits, and any conventional heating means all can be used.Yet the third method has its shortcoming need to be post-processing step to form gel polymer electrolyte to remove solvent.
＜use comprises the electrolyte electrochemical device of eutectic mixture 〉
The ionogen that comprises eutectic mixture according to the present invention can be applicable on the common electrical chemical devices known to those skilled in the art, and this electrochemical appliance is according to practical use and the various chemical properties of needs.The ionogen that comprises eutectic mixture is also applicable as antistatic coating agent, the solvent that is used for various chemical reaction types, extraction solvent, electroplating solution, additive or the like.
Herein, electrochemical appliance comprises the various types of devices that wherein carry out electrochemical reaction.The specific examples of electrochemical appliance comprises any galvanic cell and secondary cell, fuel cell, solar cell, electrochromic device or electrical condenser.More particularly, described electrochemical appliance comprises lithium secondary battery, for example the solar cell of lithium metal secondary batteries, lithium-ion secondary cell, lighium polymer secondary battery or lithium ion polymer battery, double layer capacitor, dye sensitization, electrochromic device or the like.
Method manufacturing known to electrochemical appliance is can be by those skilled in the art general.According to an embodiment of this method, two electrodes (negative electrode and anode) are piled up to form electrode assemblie, ionogen injects wherein subsequently.Electrochemical appliance such as needs can further comprise for example dividing plate of other composed components.
The present invention also provides and uses the described electrolytical described electrochemical appliance that comprises described eutectic mixture, is preferably electrochromic device.
Electrochromic device comprises first electrode, second electrode and ionogen as herein described, and it is arranged on the transparent or semitransparent base material, and wherein first electrode, second electrode, ionogen or its combination can comprise electrochromic material.
The non-limitative example of the electrochromic material that can use in the present invention comprises for example WO of inorganic, metal oxide
3, Ir (OH)
x, MoO
3, V
2O
5, TiO
2, NiO
x, LiNiO
x, Li
2NiO
xDeng; Conductive polymers is polypyrrole, polyaniline, poly-azulene cyclopentacycloheptene, polypyridine, poly-indoles, polycarbazole, polyazine, Polythiophene for example; The organic electrochromic material is purpurine (viologen), anthraquinone, phenocyazine etc. for example; And above-mentioned mixture.
More particularly, one of first electrode and second electrode or both can be formed by nesa coating.The non-limitative example of nesa coating comprises thin metal film for example metal oxide for example ITO (tin indium oxide), FTO (the adulterated stannic oxide of fluorine) or the IZO (indium zinc oxide) or the above mixture of silver or chromium, stannic oxide, zinc oxide, doping trace elements.Though the method that forms ELD is had no particular limits, can use the ordinary method known to those skilled in the art, comprise vacuum vapor deposition method, ion plating method, electron beam vacuum deposition method and sputtering method.
Electrochromic device can be according to the ordinary method manufacturing known to those skilled in the art.In one embodiment, this method comprises the steps: first electrode and second electrode are carried out lamination by tackiness agent, injects above-mentioned ionogen by inlet to first electrode and second gaps between electrodes, and seals described inlet.
The electrolytical form that is injected into electrochromic device be there is no particular restriction, can use ionogen according to above-mentioned two embodiments.Especially, preferably between two electrodes of electrochromic device, form the gel polymer electrolyte that contains eutectic mixture by in-situ polymerization.This is because inject the ionogen that comprises eutectic mixture between two electrodes, it is more easy to compare injection or pile up the gel polymer electrolyte that is impregnated with eutectic mixture, and can obtain good wetting and contact performance between gel polymer electrolyte that contains eutectic mixture and electrode.In addition, under enough temperature, form, thereby make the process of making electrochromic device become simple via the in-situ polymerization that contains eutectic mixture and monomeric mixture with predetermined proportion because gel polymer electrolyte forms.
Electrochromic device can be applied in the various application that need various chemical properties.This application comprises but is non-limiting in motor vehicle mirror, smart windows, vehicle dormer window, display unit etc.
Description of drawings
From following detailed description and in conjunction with the accompanying drawings, will make of the present inventionly above-mentionedly to become more obvious with other purpose, feature and advantage, wherein:
Figure 1 shows that the synoptic diagram of conventional electrochromic device;
Fig. 2 is transparency change and the time relation figure that uses the electrolytical electrochromic device that comprises ethanamide-NaSCN (Sodium Thiocyanate 99) eutectic mixture (mol ratio 3: 1) according to embodiment 1; And
Fig. 3 is transparency change and the time relation figure that uses the electrolytical electrochromic device that comprises hexanolactam-LiTFSI (trifluoromethane sulfimide lithium) eutectic mixture (mol ratio 3: 1) according to comparative example 2.
[embodiment]
Hereinafter will be detailed with reference to preferred implementation of the present invention, only be the illustration purpose but should understand following examples, the invention is not restricted to this.
Preparation embodiment 1: under the situation that no ionogen exists, utilize based on the electrochromic material of inorganic, metal oxide and make electrochromic device
Go up the film WO that forms thick 150nm by sputter procedure at ITO (tin indium oxide) glass (SamsungCorning Co.) as transparency electrode
3(electrochromic material) produces working electrode.In the same manner as described above, also made the counter electrode of the film NiO that is provided with thickness 150nm.Utilization comprises the sealing agent of glass sphere pad, and working electrode and the counter electrode angle along them is sealed (except that a part), as shown in Figure 1, thereby provides no electrolytical electrochromic device.
Preparation embodiment 2: under the situation that no ionogen exists, utilize based on the electrochromic material of conductive polymers and make electrochromic device
By the electroinitiated polymerisation process, the PEDOT of the about 150nm of coating thickness on as the ito glass of transparency electrode (poly--3,4-ethylene two oxy thiophene) electrode materials, thus make working electrode.Make counter electrode in the same manner as described above, described counter electrode is provided with PAN (polyaniline) coating of the about 150nm of thickness as electrode materials.The processing of working electrode and counter electrode is identical with the mode of above-mentioned preparation embodiment 1, thereby no electrolytical electrochromic device is provided.
Preparation embodiment 3: under the situation that no ionogen exists, utilize based on the electrochromic material of inorganic, metal oxide and make electrochromic device
By vapor deposition processes, go up the film WO that forms thickness 200nm at FTO (the adulterated stannic oxide of fluorine) glass (Libby-Owens-Ford Glass Co.) as transparency electrode
3Thereby, make working electrode.Make counter electrode in the same manner as described above, described counter electrode is provided with the film LiNiO of thickness 230nm
xThe processing of working electrode and counter electrode is identical with the mode of above-mentioned preparation embodiment 1, thereby no electrolytical electrochromic device is provided.
[embodiment 1-9]
Embodiment 1
1-1. preparation ethanamide-NaSCN eutectic mixture
4.4 the NaSCN (thiocyanic acid is received) of the purifying ethanamide of gram and 2 grams adds in the round-bottomed flask, and at room temperature stirs 12 hours gradually so that the 11 gram eutectic mixtures of ethanamide and NaSCN to be provided in nitrogen containing atmosphere.
1-2. comprise the electrochromic device (1) of ethanamide-NaSCN eutectic mixture as liquid electrolyte
At first, with 0.1M LiBF
4Be dissolved in the ethanamide-NaSCN eutectic mixture that obtains by embodiment 1-1.Subsequently gained solution is injected by what preparation embodiment 1 was obtained and have an inorganic, metal oxide WO
3/ NiO
xIn the electrochromic device of electrode.Electrochromic device develops for light transmission blue and demonstration 35% when developing, shows 72% light transmission during cancellation.
1-3. comprise the electrochromic device (2) of ethanamide-NaSCN eutectic mixture as liquid electrolyte
To inject the electrochromic device that is obtained by preparation embodiment 3 by ethanamide-NaSCN eutectic mixture that embodiment 1-1 obtains.Electrochromic device develops and is the light transmission of black and demonstration 34% when developing, and shows 74% light transmission during cancellation.
1-4. comprise the electrochromic device (1) of ethanamide-NaSCN eutectic mixture as gel electrolyte
At first, ethanamide-NaSCN eutectic mixture, the 0.1M LiBF that will be obtained by embodiment 1-1
4, HEMA (methacrylic acid 2-hydroxyl ethyl ester) monomer, mix at 8: 2: 0.01 with weight ratio as the AMVN (azo methyl pentane nitrile) of thermal polymerization.According to, the gained mixture is injected the electrochromic device that is obtained by preparation embodiment 1.Subsequently the ionogen inlet is sealed with the UV sealing agent, the polymerization of carrying out 1 hour 55 ℃ of temperature is to form gel polymer electrolyte.Electrochromic device develops and is the light transmission of mazarine and demonstration 32% when developing, and shows 71% light transmission during cancellation.
1-5. comprise the electrochromic device (2) of ethanamide-NaSCN eutectic mixture as gel electrolyte
Form gel polymer electrolyte in the mode identical with embodiment 1-4, difference is, will be injected into by ethanamide-NaSCN eutectic mixture that embodiment 1-1 is obtained in the electrochromic device according to preparation embodiment 3.Electrochromic device develops and is the light transmission of black and demonstration 32% when developing, and shows 74% light transmission during cancellation.
1-6. comprise the electrochromic device (3) of ethanamide-NaSCN eutectic mixture as gel electrolyte
In the mode same with the foregoing description 1-3, provide to use and comprise the gelatin polymer of eutectic mixture as electrolytical electrochromic device, difference is, uses the electrochromic device that replaces foundation preparation embodiment 1 according to the electrochromic device of preparation embodiment 2.Electrochromic device develops and is the light transmission of mazarine and demonstration 33% when developing, and shows 73% light transmission during cancellation.
1-7. the electrochromic device (4) that uses ethanamide-NaSCN eutectic mixture to obtain by the UV polymerization
At first, will be by ethanamide-NaSCN eutectic mixture, the 0.1MLiBF of embodiment 1-1 acquisition
4, as the TAEI (three [2-(acryloxy) ethyl] isocyanuric acid ester) of linking agent, as monomeric MPEGM (methoxyl group gathers (ethylene glycol) methacrylic ester) and as the Irgacure-184 (Ciba) of UV polymerization starter with weight ratio 50: 0.5: 50: 10 mix so that electrolyte precursors to be provided.Then the gained precursor is injected and have an inorganic, metal oxide WO according to preparation embodiment 1
3/ NiO
xIn the electrochromic device of electrode.The ionogen inlet is sealed by the UV sealing agent subsequently, and the polymerization of implementing 30 minutes under irradiation UV ray is to form gel polymer electrolyte.The electrochromic device development that utilizes the clear gel polymer dielectric is mazarine and shows 32% light transmission when developing, shows 75% light transmission during cancellation.
1-8. comprise the electrochromic device (5) of ethanamide-NaSCN eutectic mixture as gel electrolyte
In the mode identical with the foregoing description 1-7, provide to use and comprise the gelatin polymer of eutectic mixture as electrolytical electrochromic device, difference is, uses the electrochromic device that replaces foundation preparation embodiment 1 according to the electrochromic device of preparation embodiment 3.Electrochromic device develops and is the light transmission of black and demonstration 29% when developing, and shows 75% light transmission during cancellation.
Embodiment 2: preparation methyl urea-NaSCN eutectic mixture
In round-bottomed flask, add 4.5g purifying methyl urea and 2g NaSCN (Sodium Thiocyanate 99).Under nitrogen atmosphere, in the time of 70 ℃, mixture is stirred 10 hours gradually to obtain 6.5g methyl urea-NaSCN eutectic mixture.
Embodiment 3: preparation ethanamide-urea-NaSCN eutectic mixture
In round-bottomed flask, add 3.3g purifying ethanamide, 3.3g purifying urea and 2g NaSCN.Under nitrogen atmosphere, in the time of 30 ℃, mixture is stirred 5 hours gradually to obtain 8.6g ethanamide-urea-NaSCN eutectic mixture.
Embodiment 4
4-1. preparation Urethylane-NaSCN eutectic mixture
In round-bottomed flask, add the purifying Urethylane of 13.7 grams and the NaSCN (Sodium Thiocyanate 99) of 5 grams, and under the nitrogen atmosphere, stir the mixture 50 minutes gradually so that the Urethylane-NaSCN eutectic mixture of 18.7 grams to be provided at 50 ℃.
4-2. comprise the electrochromic device of Urethylane-NaSCN eutectic mixture as liquid electrolyte
Make electrochromic device in the mode identical with embodiment 1-2, difference is, uses Urethylane-NaSCN eutectic mixture to replace ethanamide-NaSCN eutectic mixture.Electrochromic device develops for light transmission blue and demonstration 30% when developing, shows 72% light transmission during cancellation.
4-3. comprise the electrochromic device of Urethylane-NaSCN eutectic mixture as gel electrolyte
Make electrochromic device in the mode identical with embodiment 1-4, difference is, uses Urethylane-NaSCN eutectic mixture to replace ethanamide-NaSCN eutectic mixture.Electrochromic device develops for light transmission blue and demonstration 34% when developing, shows 75% light transmission during cancellation.
Embodiment 5: preparation N-phenmethyl methane amide-NaSCN eutectic mixture
In round-bottomed flask, add the purifying N-phenmethyl methane amide of 9.9 grams and the NaSCN (Sodium Thiocyanate 99) of 4 grams, and mixture was stirred 40 minutes gradually under the nitrogen atmosphere at 30 ℃, at room temperature leave standstill 5 hours subsequently so that the N-phenmethyl methane amide-NaSCN eutectic mixtures of 10.7 grams to be provided.
Embodiment 6: preparation ethanamide-NH
4The SCN eutectic mixture
In round-bottomed flask, add the purifying ethanamide (trifluoroacetamide) of 6.9 grams and the NH of 3 grams
4SCN (ammonium thiocyanate).Under the nitrogen atmosphere, mixture is stirred 50 minutes gradually so that the ethanamide-NH of 9.9 grams to be provided at 40 ℃
4The SCN eutectic mixture.
Embodiment 7: preparation hexanolactam-NH
4The SCN eutectic mixture
In round-bottomed flask, add the purifying hexanolactam of 8.92 grams and the NH of 2 grams
4SCN (ammonium thiocyanate).Under the nitrogen atmosphere, mixture was stirred 4 hours and was cooled to room temperature gradually so that the hexanolactam-NH of 10.9 grams to be provided at 50 ℃
4The SCN eutectic mixture.
Embodiment 8: preparation ethanamide-urea-NH
4The SCN eutectic mixture
In round-bottomed flask, add the purifying ethanamide of 3.6 grams, the urea of 3.6 grams and the NH of 3 grams
4SCN (ammonium thiocyanate).Under the nitrogen atmosphere, mixture is stirred 10 hours gradually so that the ethanamide-urea-NH of 10 grams to be provided at 30 ℃
4The SCN eutectic mixture.
Embodiment 9: preparation ethanamide-urea-NH
4NO
3Eutectic mixture
In round-bottomed flask, add the purifying ethanamide of 3 grams, the urea of 3 grams and the NH of 1.6 grams
4NO
3Under the nitrogen atmosphere, mixture was stirred 4 hours and was cooled to room temperature gradually so that the ethanamide-urea-NH of 7.6 grams to be provided at 50 ℃
4NO
3Eutectic mixture.
[comparative example 1 and 2]
Comparative example 1: the electrochromic device that comprises liquid electrolyte
Make electrochromic device in the mode identical with the foregoing description 1-2, difference is, uses to comprise 1M LiClO
4Gamma-butyrolactone as liquid electrolyte.The electrochromic device of finishing develops and is the light transmission of mazarine and demonstration 34% when developing, and shows 76% light transmission during cancellation.Yet, because the use of organic solvent causes ionogen volatilization and dry easily.After repeating development-cancellation circulation, also can include the side reaction that organic compounds decomposes.
Comparative example 2: preparation hexanolactam-LiTFSI eutectic mixture
In round-bottomed flask, add the purifying hexanolactam of 9.6 grams and the LiTFSI of 8.16 grams.Under the nitrogen atmosphere, mixture was stirred 4 hours and was cooled to room temperature gradually so that the hexanolactam-LiTFSI eutectic mixture of 17 grams to be provided at 50 ℃.
Experimental example 1: the physicals that thinks poorly of eutectic mixture
Carry out following test, to estimate physicals according to eutectic mixture of the present invention.Will be according to the eutectic mixture of embodiment 1～9 as sample and will be in contrast according to the eutectic mixture of comparative example 2.In every kind of eutectic mixture, the usage ratio of amide compound and salt is 3: 1.The fusing point of every kind of eutectic mixture is measured by DSC (differential scanning calorimeter), and the decomposition temperature of every kind of eutectic mixture is measured by TGA (thermogravimetric analysis).In addition, 25 ℃ of measurements, the result is as shown in table 1 below by the RS150 viscometer for the viscosity of every kind of eutectic mixture.
[table 1]
| Compound with acidic-group and basic group | Salt | Fusing point (℃) | Decomposition temperature (℃) | Viscosity (cP) | Electric conductivity (mS/cm) | |
| Embodiment 1 | Ethanamide | NaSCN | 10 | 100 | 152 | 2.45 |
| Embodiment 2 | The methyl urea | NaSCN | 10 | 140 | 265 | 0.85 |
| Embodiment 3 | Ethanamide+urea | NaSCN | 10 | 100 | 132 | 2.90 |
| Embodiment 4 | Urethylane | NaSCN | 5 | 60 | 48 | 1.4 |
| Embodiment 5 | N-phenmethyl methane amide | NaSCN | -46.56 | 145 | 155 | 0.34 |
| Embodiment 6 | Ethanamide | NH 4SCN | 5 | 100 | 16 | 17.2 |
| Embodiment 7 | Hexanolactam | NH 4SCN | 0 | 130 | 620 | 0.26 |
| Embodiment 8 | Ethanamide+urea | NH 4SCN | 10 | 100 | 22 | 15.1 |
| Embodiment 9 | Ethanamide+urea | NH 4NO 3 | 20 | 110 | 50 | 0.02 |
| Comparative example 2 | Hexanolactam | LiTFSI | -38 | 120 | 3100 | 0.03 |
Experimental example 2: the quality of estimating electrochromic device
To using according to no lithium eutectic mixture of the present invention and using that to contain the lithium eutectic mixture as follows as the quality evaluation of electrolytical every kind of electrochromic device.
Use is according to the electrolytical electrochromic device that contains ethanamide-NaSCN eutectic mixture of embodiment 1.Use according to the electrolytical electrochromic device that contains hexanolactam-LiTFSI eutectic mixture of comparative example 2 in contrast.
After the painted/scope of discoloring of measuring color development/cancellation rate and each electrochromic device, use the electrolytical electrochromic device of eutectic mixture that comprises lithium according to comparative example 2, when this electrochromic device is developed/during cancellation, it demonstrates narrow transparence (color change interval: 42～65) (please refer to Fig. 3).On the contrary, the no lithium eutectic mixture that use is obtained by embodiment 1 is as electrolytical electrochromic device, contain the lithium eutectic mixture as electrolytical electrochromic device compared to using according to comparative example 2, demonstrate the significantly wideer painted/scope of discoloring, and demonstrate good color development/extinctivity (please refer to Fig. 2).
Industrial application
Found out by above-mentioned, comprise eutectic mixture according to the ionogen of electrochemical appliance of the present invention, its cost is low and have good heat and a chemical stability.So the problem that can solve electrolyte evaporation, exhaust and catch fire, thereby the side reaction between device composed component and the ionogen is minimized, and improved the security of electrochemical appliance.In addition, owing to contained metallic cation in the eutectic mixture has good conductivity, wide electrochemical window, therefore need can be applicable to the electrochemical appliance of the special energy of various electrochemistry according to ionogen of the present invention.
Although the invention has been described in conjunction with thinking the most practical and most preferred way of example at present, but should be appreciated that the present invention is confined to embodiment disclosed herein and accompanying drawing, on the contrary, the present invention expection is encompassed in various modifications and the variation of being done under the spirit of claims and the scope.
Claims (21)
1. ionogen that contains eutectic mixture, this eutectic mixture is formed by following:
(a) compound of amide-containing; And
(b) ionizable salt of no lithium.
2. ionogen as claimed in claim 1, wherein the ionizable salt of this no lithium is a metal-salt, comprises at least a element of the basic metal, alkaline-earth metal, transition metal, metalloid, lanthanon and the actinide elements that are selected from except that lithium; Or be organic salt.
3. ionogen as claimed in claim 1, wherein this eutectic mixture is by representing as shown in the formula 1:
[formula 1]
R wherein
1Be hydrogen atom, C1～C20 alkyl, C1～C20 alkylamine, thiazolinyl, aryl or alkaryl;
R
2Be hydrogen atom, halogen atom, C1～C20 alkyl, thiazolinyl, aryl or alkaryl;
A is selected from carbon, oxygen, hydrogen, nitrogen and sulphur, and condition is when A is hydrogen, R
2Be empty;
The X representative is selected from least a metallic cation or the organic cation of basic metal, alkaline-earth metal, transition metal, metalloid, lanthanon and actinide elements except that lithium;
Y representative can with the salifiable negatively charged ion of X-shaped; And
N represents integer 0～10, and when n be 1 or when bigger, A is selected from carbon, oxygen, nitrogen and sulphur, and hydrogen is left out.
4. ionogen as claimed in claim 3, wherein X represents secondary ammonium, tertiary amine, quaternary ammonium, phosphorus , magnesium, potassium or calcium, and Y represents thiocyanate ion, formate, acetate moiety, nitrate radical, perchlorate, sulfate radical, oxyhydroxide root, alkoxide root, halogenide root, carbonate, oxalate or tetrafluoroborate.
5. ionogen as claimed in claim 1, it further comprises lithium salts.
6. ionogen as claimed in claim 5, wherein this lithium salts has and is selected from following at least a negatively charged ion: F
-, Cl
-, Br
-, I
-, NO
3 -, BF
4 -, PF
6 -, N (CN)
2 -, SCN, ClO
4 -, (CF
3)
3PF
3 -, (CF
3)
4PF
2 -, (CF
3)
5PF
-, (CF
3)
6P
-, (CF
3CF
2SO
2 -)
2N, (CF
3SO
2)
2N
-, CF
3SO
3 -, CF
3CF
2(CF
3)
2CO
-, (CF
3SO
2)
2CH
-, (CF
3SO
2)
3C
-, CF
3(CF
2)
7SO
3 -, CF
3CO
2 -With CH
3CO
2 -
7. ionogen as claimed in claim 1, this ionogen are the liquid-type ionogen, the combination that it only comprises this eutectic mixture or comprises this eutectic mixture and lithium salts.
8. ionogen as claimed in claim 1, this ionogen are served as reasons and are selected from the gel polymer electrolyte that any one following ionogen pre-gelled solution forms by polymerization:
(i) ionogen pre-gelled solution comprises this eutectic mixture and the monomer that can form gelatin polymer via polymerization; And
(ii) ionogen pre-gelled solution comprises this eutectic mixture, can form the monomer and the lithium salts of gelatin polymer via polymerization.
9. ionogen as claimed in claim 1, wherein this monomer is a vinyl monomer.
10. ionogen as claimed in claim 9, wherein this vinyl monomer is to be selected from following at least a monomer: vinyl cyanide, methyl methacrylate, methyl acrylate, methacrylonitrile, vinyl toluene, vinyl ester, vinylchlorid, vinylidene chloride, acrylamide, tetrafluoroethylene, vinyl-acetic ester, methyl vinyl ketone, ethene, vinylbenzene, to methoxy styrene with to cyano-styrene.
11. ionogen as claimed in claim 8, wherein this ionogen pre-gelled solution further comprises polymerization starter or light trigger.
12. ionogen as claimed in claim 8, wherein this ionogen pre-gelled solution comprises that weight ratio is the eutectic mixture (x) of x: y: z, can forms the monomer (y) and the polymerization starter (z) of gelatin polymer by polymerization, wherein x is 0.5～0.95, y is 0.05～0.5, z is 0.00～0.05, and condition is x+y+z=1.
13. ionogen as claimed in claim 8, it is by obtaining at the inner in-situ polymerization of electrochemical appliance.
14. ionogen as claimed in claim 1, it comprises polymkeric substance or the gelatin polymer that is impregnated with this eutectic mixture.
15. ionogen as claimed in claim 14, wherein this polymkeric substance is selected from polymethylmethacrylate, poly(vinylidene fluoride), polyvinyl chloride, polyoxyethylene and poly hydroxy ethyl acrylate.
16. an electrochemical appliance, it comprises by each defined ionogen in the claim 1 to 15.
17. an electrochromic device, it comprises:
(a) first electrode;
(b) second electrode;
(c) electrochromic material; And
(d) by each defined ionogen in the claim 1 to 15.
18. electrochromic device as claimed in claim 17, wherein this electrochromic material be included in this first electrode, this second electrode and this electrolytical one of at least in.
19. electrochromic device as claimed in claim 17, wherein this electrochromic material comprises: (a) inorganic, metal oxide, it is selected from WO
3, Ir (OH)
x, MoO
3, V
2O
5, TiO
2, NiO
x, LiNiO
xWith Li
2NiO
x(b) conductive polymers, it is selected from polypyrrole, polyaniline, poly-azulene cyclopentacycloheptene, polypyridine, poly-indoles, polycarbazole, polyazine and Polythiophene; Or (c) organic electrochromic material, it is selected from purpurine, anthraquinone and phenocyazine.
20. electrochromic device as claimed in claim 17, wherein one of this first electrode and this second electrode or both comprise nesa coating.
21. electrochromic device as claimed in claim 20, wherein this nesa coating comprises and is selected from following at least a material: Ag, Cr, stannic oxide, zinc oxide, ITO (tin indium oxide), FTO (the adulterated stannic oxide of fluorine) and IZO (indium zinc oxide).
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|---|---|---|---|
| CN201210226695.6A CN102780033B (en) | 2005-08-19 | 2006-08-18 | Electrolyte, electrochemical appliance containing eutectic mixture and electrochromic device |
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|---|---|---|---|
| KR1020050076149 | 2005-08-19 | ||
| KR20050076149 | 2005-08-19 | ||
| KR1020050123942 | 2005-12-15 |
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|---|---|---|---|
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|---|---|
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Application publication date: 20080813 |