CN1680482A - Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof - Google Patents
Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof Download PDFInfo
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- CN1680482A CN1680482A CNA2005100182509A CN200510018250A CN1680482A CN 1680482 A CN1680482 A CN 1680482A CN A2005100182509 A CNA2005100182509 A CN A2005100182509A CN 200510018250 A CN200510018250 A CN 200510018250A CN 1680482 A CN1680482 A CN 1680482A
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Abstract
The invention is about a gel electrolyte of nonaqueous/aqueous biphase and the battery. The principle is: the electrolyte is made up of hydrophobic gel electrolyte film which includes hydrophobic ionic liquid and hydrophobic polymer and hydrophilic gel electrolyte film which include water and hydrophilic polymer. So the product has the both merits of the nonaqueous electrolyte and the aqueous electrolyte; it can provide the base condition to the biphase electrode reaction.
Description
Technical field
The present invention is a kind of preparation method and application of non-water/aqueous/aqueous two-phase gel electrolyte, belongs to technical field of chemical power.
Background technology
Along with a large amount of of the develop rapidly of electronic technology, various portable type electronic products popularize, people constantly increase, its performance requriements are also improved constantly the demand of chemical power source.Under this background, develop chemical power source system novel, high-energy-density and become the important requirement of social development.
The related data of several possible metal negative poles of table 1
Metal | Negative reaction | Negative pole electromotive force V vs.NHE | Theoretical specific capacity mAh/g | Applicable system |
????Zn | ????Zn+2OH. -=Zn(OH) 2+2e | ????-1.24 | ????824 | The aqueous solution |
????Fe ????Al ????Li ????Mg ????Ca | ????Fe+2OH. -=Fe(OH) 2+2e ????Al+3OH. -=Al(OH) 3+3e ????Li=Li -+e ????Mg=Mg 2++2e ????Ca=Ca 2++2e | ????-0.85 ????-1.706 ????-3.05 ????-2.69 ????-3.01 | ????957 ????2978 ????3829 ????2233 ????1340 | The aqueous solution aqueous solution, organic |
The related data of several possible positive electrode materials of table 2
Anodal | Electrode reaction | Electrode potential V vs.NHE | Theoretical specific capacity mAh/g | Applicable system |
??Ni(OH) 2??MnO 2??O 2??LiCoO 2??LiMn 2O 4 | ?Ni(OH) 2+OH. -=NiOOH+H 2O+e ?MnO 2+H 2O+e=MnOOH+OH -?O 2+H 2O+4e=4OH -?LiCoO 2=xLi ++Li 1-xCoO 2+xe ?LiMn 2O 4=Li ++Mn 2O 4+e | ????0.4 ????0.65 ????0.401 ????0.6 ????0.7 | 286 300 unlimited 145 (x=0.5) 148 | The aqueous solution aqueous solution aqueous solution is organic |
Table 1 has been listed the electrochemical data of several metal negative materials.As can be seen from the table, the current potential of metallic lithium is the most negative, and theoretical capacity is the highest negative material of energy density up to 3828mAh/g.Yet, with the same active metal of lithium (as magnesium, calcium, aluminium etc.) since with water generation vigorous reaction, can only be applied to organic system.Table 2 has been listed the electrochemical data of several positive electrode materials.Know the positive electrode material (LiCoO in the organic system by table
2) capacity generally has only about 150mAh/g, and in the aqueous solution positive electrode material (Ni (OH)
2, MnO
2) capacity is all near 300mAh/g, as positive pole employing air electrode, theoretical capacity is then infinitely great.Thus,, then can form more high-octane chemical power source system, but wherein most critical is to have simultaneously hydrophobic, the hydrophilic two-phase electrolysis matter of one side if high-energy negative material in the organic system and the positive electrode material in the aqueous solution are combined.
Summary of the invention:
The objective of the invention is to develop a kind of novel non-water/aqueous/aqueous two-phase gel electrolyte, wherein the nonaqueous phase ionogen has strong-hydrophobicity matter, and the most negative metallic lithium of current potential is stable existence therein; And water ionogen possess hydrophilic property matter can be applicable to the water solution system positive electrode material; Nonaqueous phase and water are by ion migration, and the realization ionic conduction.
Technical scheme of the present invention is: non-water/aqueous/aqueous two-phase gel electrolyte is characterized in that it is formed by organophilic gel electrolyte body and the applying of hydrophilic gel electrolyte body surface;
Described organophilic gel electrolyte body is made up of hydrophobic ionic liquid and hydrophobic polymer;
Hydrophobic ionic liquid is the hydrophobicity quaternary ammonium salt: comprise quaternary ammonium salt and negatively charged ion, or add electrolytic salt therein; Wherein quaternary ammonium salt is one of imidazoles, piperidines, pyrrolidines, piperazines, and negatively charged ion is hexafluoro-phosphate radical (PF
6 -), two (three fluorosulfonyls) acyl imonium root ((CF
3SO
2)
2N
-, one of TFSI), add lithium, sodium, the sylvite that electrolytic salt is generally phosphofluoric acid, two (three fluorosulfonyls) acyl imonium, the concentration that adds salt is 0.2~5mol/; The overall mass fraction of the shared organophilic gel electrolyte body of hydrophobic ionic liquid is 20~95wt%;
Hydrophobic polymer is one of vinylidene (PVDF), copolymer from vinylidene fluoride and hexafluoropropylene (P (VDF-HFP)), polyacrylic ester, and the overall mass fraction of shared organophilic gel electrolyte body is 5~80wt%;
Described hydrophilic gel electrolyte body is made up of the aqueous solution and hydrophilic polymer, or directly uses proton exchange membrane such as perfluoro sulfonic acid membrane (Nafion);
The aqueous solution comprises basic solution, acidic solution and neutral solution, and wherein basic solution is KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution is HCl, HNO
3, H
2SO
4One of; Neutral solution is one of NaCl, KCl, MgCl, and the overall mass fraction of shared hydrophilic gel electrolyte body is 20~95wt%;
Hydrophilic polymer is one of polyacrylate, polyoxyethylene, polyvinyl alcohol, and the overall mass fraction of shared hydrophilic gel electrolyte body is 5~80wt%.
Aforesaid non-water/aqueous/aqueous two-phase gel electrolyte is characterized in that organophilic gel electrolyte body and hydrophilic gel electrolyte body are membranaceous.
Principle of the present invention is: non-water/aqueous/aqueous two-phase gel electrolyte, it is made up of organophilic gel electrolyte body and hydrophilic gel electrolyte body two portions, the organophilic gel electrolyte body not only has stable chemical property (but active metal stable existence) therein, and have than strong-hydrophobicity, air and moisture are isolated in outside the dielectric film, thereby make therein active metal not be subjected to the influence of external environment, can be used for electrode air, water sensitive; And the hydrophilic gel electrolyte body has high conductivity, better physical strength, can be used for hydrophilic electrode, gives full play to aqueous solution positive electrode material chemical property.Pass through special ion migration at organophilic gel and hydrophilic gel interface, to reach the effect of conducting ion.
A kind of preparation method of non-water/aqueous/aqueous two-phase gel electrolyte is characterized in that organophilic gel electrolyte body and hydrophilic gel electrolyte body surface are fit together to the surface.
The preparation method of aforesaid non-water/aqueous/aqueous two-phase gel electrolyte, the preparation method who it is characterized in that described organophilic gel electrolyte body is dissolved in hydrophobic polymer in the organic solvent, as acetone, N, one of dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), tetrahydrofuran (THF) or both mixtures, add hydrophobic ionic liquid then by a certain percentage, after stirring, be placed on 120 ℃ of following vacuum 12 hours, promptly obtain the hydrophobic electrolyte body of gel state.
The preparation method of aforesaid organophilic gel electrolyte body, it is characterized in that described hydrophobic polymer is one of vinylidene (PVDF), copolymer from vinylidene fluoride and hexafluoropropylene (P (VDF-HFP)), polyacrylic ester, wherein the overall mass fraction of the shared organophilic gel electrolyte body of hydrophobic polymer is 5~80wt%.
The preparation method of aforesaid organophilic gel electrolyte body, it is characterized in that described hydrophobic ionic liquid is the hydrophobicity quaternary ammonium salt: comprise quaternary ammonium salt and macroanion, or add electrolytic salt therein, wherein quaternary ammonium salt is for being one of imidazoles, piperidines, pyrrolidines, piperazines; Macroanion is hexafluoro-phosphate radical (PF
6 -), two (three fluorosulfonyls) acyl imonium root ((CF
3SO
2)
2N
-, TFSI); Add lithium, sodium, the sylvite that electrolytic salt is generally phosphofluoric acid, two (three fluorosulfonyls) acyl imonium, the concentration that adds salt is 0.2~5mol/; And the overall mass fraction of the shared organophilic gel electrolyte body of hydrophobic ionic liquid is 20~95wt%;
The preparation method of aforesaid non-water/aqueous/aqueous two-phase gel electrolyte, the preparation method who it is characterized in that described hydrophilic gel electrolyte body is dissolved in aqueous electrolyte in the solution that contains hydrophilic polymer, make gelation by thermal treatment, perhaps adopt the polymer monomer direct polymerization to form the gel electrolyte body.
Aforesaid hydrophilic gel electrolyte body preparation method is characterized in that described aqueous electrolyte is basic solution or acidic solution or neutral solution, and wherein basic solution is KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution is HCl, HNO
3, H
2SO
4One of; Neutral solution is one of NaCl, KCl, MgCl, and strength of solution is 0.5~10mol/L; Wherein the overall mass fraction of the shared hydrophilic gel electrolyte body of aqueous electrolyte is 20~95wt%.Or directly use proton exchange membrane such as perfluoro sulfonic acid membrane (Nafion).
Aforesaid hydrophilic gel electrolyte body preparation method is characterized in that described hydrophilic polymer is one of polyacrylate, polyoxyethylene, polyvinyl alcohol, and the overall mass fraction of shared hydrophilic gel electrolyte body is 5~80wt%.
A kind of battery is characterized in that used ionogen is above-mentioned non-water/aqueous/aqueous two-phase gel electrolyte film.
The invention has the advantages that and adopt non-water and hydrogel ionogen to form the two-phase gel electrolyte body.Compare with the conventional gel ionogen, prepared two-phase gel electrolyte body combines the advantage of nonaqueous electrolyte and aqueous electrolyte, the negative pole of chemical power source even can use metallic lithium like this, and the anodal electrode materials that can adopt heavy body, even can use the air electrode of no capacity limit, thereby make up the chemical power source system of novel high-energy-density; This in addition colloidal electrolyte is easy to realize the conception of all-solid-state battery and realize particular design such as chemical power source microminiaturization, slimming, can extensively make up multiple novel battery systems such as the empty battery of lithium, the empty battery of magnesium, lithium nickel-based battery.
Description of drawings
Fig. 1 is that the embodiment of the invention 3 adopts non-water/aqueous/aqueous two-phase gel electrolyte film as electrolytical lithium-air battery discharge curve.Wherein discharge current density is 0.1mA/cm
2
Concrete embodiment
Embodiment 1 non-water/aqueous/aqueous two-phase gel electrolyte membrane prepare 1
At first polyvinylidene difluoride (PVDF) (PVDF) is dissolved in N, in the dinethylformamide (DMF), forms 10% PVDF solution, take by weighing 1.6g methyl-butyl imidazole hexafluorophosphate (BMIPF then
6), and join in the above-mentioned PVDF solution of 4g, after mixing, be placed on dry 12h in 120 ℃ the vacuum drying oven, promptly obtain the organophilic gel dielectric film.
The hydrophilic gel dielectric film is that the potassium hydroxide aqueous solution that adopts 8g 6mol/L mixes with the 2g polyvinyl alcohol, after the gelation.
Non-water/aqueous/aqueous two-phase gel electrolyte film is that above-mentioned organophilic gel dielectric film and hydrophilic gel dielectric film directly forced together.
Embodiment 2 non-water/aqueous/aqueous two-phase gel electrolyte membrane prepares 2
At first copolymer from vinylidene fluoride and hexafluoropropylene (P (VDF-HFP)) is dissolved in the N-Methyl pyrrolidone (NMP); form 10% P (VDF-HFP) solution; weigh two (three fluorosulfonyls) the acyl imonium salt (PP18TFSI) of 0.8g methyl-octyl group piperidines then; and join in above-mentioned P (VDF-HFP) solution of 2g; after mixing; be placed on dry 12h in 120 ℃ the vacuum drying oven, promptly obtain the organophilic gel ionogen.
The hydrophilic gel dielectric film is to adopt following method preparation:
In following ratio preparation mixed solution, after stirring, as the polymer dielectric precursor solution.
Vinylformic acid: 12.5%
Linking agent (N, N '-methylene-bis (acrylamide)): 0.06%
KOH solution (10mol/L): 87.44%
Under agitation, in the polymer dielectric precursor solution, add 50mg 4% initiator (Na
2SO
3+ K
2S
2O
81: 1wt) solution, treat promptly to form the hydrophilic gel dielectric film after the solution polymerization.
Non-water/aqueous/aqueous two-phase gel electrolyte film is that above-mentioned organophilic gel dielectric film and hydrophilic gel dielectric film are superimposed together, push a little.
Embodiment 3 non-water/aqueous/aqueous two-phase gel electrolyte films are used for lithium-air battery
It is the double-deck air electrode of catalyzer that the positive pole of the air electrode of lithium described in this example adopts with Manganse Dioxide, and negative pole is a metal lithium sheet, and ionogen is embodiment 2 described non-water/aqueous/aqueous two-phase gel electrolyte films.The assembling of battery is the hydrophilic gel film outside of the Catalytic Layer of air electrode being close to non-water/aqueous/aqueous two-phase gel electrolyte film, and metal lithium sheet is contained in the organophilic gel film of non-water/aqueous/aqueous two-phase gel electrolyte film.The lead-in wire of drawing from positive and negative electrode is connected cell tester and carries out discharge test.
Claims (9)
1, non-water/aqueous/aqueous two-phase gel electrolyte is characterized in that it is formed by organophilic gel electrolyte body and the applying of hydrophilic gel electrolyte body surface;
Described organophilic gel electrolyte body is made up of hydrophobic ionic liquid and hydrophobic polymer;
Hydrophobic ionic liquid is the hydrophobicity quaternary ammonium salt: comprise quaternary ammonium salt and negatively charged ion, or add electrolytic salt therein; Wherein quaternary ammonium salt is one of imidazoles, piperidines, pyrrolidines, piperazines, negatively charged ion is one of hexafluoro-phosphate radical, two acyl imonium roots, add electrolytic salt and be generally phosphofluoric acid, the lithium of two acyl imonium, sodium, sylvite, the concentration that adds salt is 0.2~5mol/; The overall mass fraction of the shared organophilic gel electrolyte body of hydrophobic ionic liquid is 20~95wt%;
Hydrophobic polymer is one of vinylidene, copolymer from vinylidene fluoride and hexafluoropropylene, polyacrylic ester, and the overall mass fraction of shared organophilic gel electrolyte body is 5~80wt%;
Described hydrophilic gel electrolyte body is made up of the aqueous solution and hydrophilic polymer, or directly uses proton exchange membrane;
The aqueous solution comprises basic solution, acidic solution and neutral solution, and wherein basic solution is KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution is HCl, HNO
3, H
2SO
4One of; Neutral solution is one of NaCl, KCl, MgCl, and the overall mass fraction of shared hydrophilic gel electrolyte body is 20~95wt%;
Hydrophilic polymer is one of polyacrylate, polyoxyethylene, polyvinyl alcohol, and the overall mass fraction of shared hydrophilic gel electrolyte body is 5~80wt%.
2, aforesaid non-water/aqueous/aqueous two-phase gel electrolyte is characterized in that organophilic gel electrolyte body and hydrophilic gel electrolyte body are membranaceous.
3, a kind of preparation method of non-water/aqueous/aqueous two-phase gel electrolyte is characterized in that organophilic gel electrolyte body and hydrophilic gel electrolyte body surface are fit together to the surface.
4, the preparation method of non-water/aqueous/aqueous two-phase gel electrolyte as claimed in claim 3, the preparation method who it is characterized in that described organophilic gel electrolyte body is dissolved in hydrophobic polymer in the organic solvent, add hydrophobic ionic liquid then by a certain percentage, after stirring, be placed on 120 ℃ of following vacuum 12 hours, promptly obtain the hydrophobic electrolyte body of gel state.
5, the preparation method of organophilic gel electrolyte body as claimed in claim 4, it is characterized in that described hydrophobic polymer is one of vinylidene, copolymer from vinylidene fluoride and hexafluoropropylene, polyacrylic ester, wherein the overall mass fraction of the shared organophilic gel electrolyte body of hydrophobic polymer is 5~80wt%;
Described hydrophobic ionic liquid is the hydrophobicity quaternary ammonium salt: comprise quaternary ammonium salt and macroanion, or add electrolytic salt therein that wherein quaternary ammonium salt is for being one of imidazoles, piperidines, pyrrolidines, piperazines; Macroanion is hexafluoro-phosphate radical, two acyl imonium root; Add electrolytic salt and be generally phosphofluoric acid, the lithium of two acyl imonium, sodium, sylvite, the concentration that adds salt is 0.2~5mol/; And the overall mass fraction of the shared organophilic gel electrolyte body of hydrophobic ionic liquid is 20~95wt%;
6, as the preparation method of claim 3 or 4 described non-water/aqueous/aqueous two-phase gel electrolytes, the preparation method who it is characterized in that described hydrophilic gel electrolyte body is dissolved in aqueous electrolyte in the solution that contains hydrophilic polymer, make gelation by thermal treatment, perhaps adopt the polymer monomer direct polymerization to form the gel electrolyte body.
7, hydrophilic gel electrolyte body preparation method as claimed in claim 6 is characterized in that described aqueous electrolyte is basic solution or acidic solution or neutral solution, and wherein basic solution is KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution is HCl, HNO
3, H
2SO
4One of; Neutral solution is one of NaCl, KCl, MgCl, and strength of solution is 0.5~10mol/L; Wherein the overall mass fraction of the shared hydrophilic gel electrolyte body of aqueous electrolyte is 20~95wt%.
8, hydrophilic gel electrolyte body preparation method as claimed in claim 6 is characterized in that described hydrophilic polymer is one of polyacrylate, polyoxyethylene, polyvinyl alcohol, and the overall mass fraction of shared hydrophilic gel electrolyte body is 5~80wt%.
9, a kind of battery is characterized in that used ionogen is above-mentioned non-water/aqueous/aqueous two-phase gel electrolyte film.
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