CN103219161B - A kind of electrolyte right based on organic sulfur reduction electricity, preparation method and application - Google Patents

A kind of electrolyte right based on organic sulfur reduction electricity, preparation method and application Download PDF

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CN103219161B
CN103219161B CN201310093613.XA CN201310093613A CN103219161B CN 103219161 B CN103219161 B CN 103219161B CN 201310093613 A CN201310093613 A CN 201310093613A CN 103219161 B CN103219161 B CN 103219161B
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electrolyte
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organic sulfur
sulfosalt
btp
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CN103219161A (en
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韩宏伟
刘林峰
李雄
刘广辉
汪恒
荣耀光
库治良
徐觅
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Huazhong University of Science and Technology
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    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of electrolyte right based on organic sulfur reduction electricity, it is characterized in that, this electrolyte comprises organic sulfur oxidation-reduction pair and crown ether or cave ether, wherein, the right reduction-state component of described organic sulfur reduction electricity is organic sulfosalt, and oxidation state component is the organic disulfide corresponding with this organic sulfur salt.The invention also discloses this electrolyte preparation method and preparing the application in solar cell, fuel cell, lithium ion battery or ultracapacitor.Electrolyte of the present invention adopts the cation of metal cation as electric centering reduction-state component of crown ether or cave ether complexing, redox reaction activity, stability and electrochemical reversibility are good, diffusion velocity is fast, electrolyte intermediate ion is utilized to transmit, method synthesis process for preparation of the present invention is simple, with low cost, has a good application prospect in dye-sensitized nano solar cell.

Description

A kind of electrolyte right based on organic sulfur reduction electricity, preparation method and application
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of solar cell electrolyte, its preparation method and application thereof.
Background technology
The light energy conversion that the sun produces can be become electric energy by dye sensitized nano crystal salar battery, becomes the strong approach that human use's sunlight solves energy problem in recent years.Electrolyte is the key component of dye sensitized nano crystal salar battery, oxidation-reduction pair wherein undertakes following functions: obtain electronics to electrode, diffuse near work electrode, to regenerate the mode of dyestuff by electron injection work electrode, complete the transport of electronics.Electrolytical ability to work depends primarily on the redox active of oxidation-reduction pair, stability, oxidation-reduction potential and electrochemical reversibility.Therefore, the character of oxidation-reduction pair has significant impact to electrolytical performance.
At present in dye sensitized nano crystal salar battery field, based on I -/ I 3 -the electrolyte of redox couple has obtained research extensively and profoundly and has become the mainstay material of Ge great research institute and company's employing, this is because I -/ I 3 -there is the advantage that the other materials such as diffusion coefficient is high, oxidation-reduction potential is suitable are difficult to reach.But, I -/ I 3 -there is again the practical problems such as volatile, the metal material absorbed in sunlight, corrosion device simultaneously, add I -/ I 3 -there is fatal obstruction in the lifting of open-circuit voltage, is badly in need of finding new oxidation-reduction pair, i.e. non-iodine electrolyte and carrys out alternative traditional iodo electrolyte.
Non-iodine electrolyte comparatively ripe is at present mainly right based on metal complex electricity, such electric right redox reaction activity, stability and electrochemical reversibility are good, the more important thing is, can change with the structure of the smaller ligand of metal-complexing, this feature creates the space regulating whole oxidation-reduction pair performance, for exploring I -/ I 3 -substitute provides new method and thinking.The usual molecule of unfortunate this kind of complex compound is huge, causes electrolyte viscosity to rise, and diffusion velocity reduces, and is unfavorable for the ion transfer in electrolyte.
Summary of the invention
An object of the present invention is to provide a kind of electrolyte right based on organic sulfur reduction electricity, its electric right redox reaction activity, stability and electrochemical reversibility are good, diffusion velocity is fast, utilize electrolyte intermediate ion to transmit, it is for having very high conversion efficiency in dye sensitized nano crystal salar battery, fuel cell etc.
The present invention be solve the problems of the technologies described above employing technical scheme be:
A kind of electrolyte right based on organic sulfur reduction electricity, it is characterized in that, this electrolyte comprises organic sulfur oxidation-reduction pair and crown ether or cave ether, wherein, the right reduction-state component of described organic sulfur reduction electricity is organic sulfosalt, and oxidation state component is the organic disulfide corresponding with this organic sulfur salt.
In electrolyte of the present invention, organic sulfosalt can be oxidized to corresponding organic disulfide, and organic sulfur compound also can be reduced into corresponding organic sulfosalt, and this to reactivity and invertibity good.
As present invention further optimization, described crown ether or cave ether corresponding with the cation in organic sulfosalt, namely the intracavity diameter size of crown ether or cave ether and cation diameter match.Crown ether or cave ether can form complex compound with cation, wrap the cation with positive charge.
As present invention further optimization, the organic sulfur cation in described organic sulfosalt is metal cation, is preferably Li+, Na+ or K+.
As present invention further optimization, described crown ether is 12-crown-4,15-crown-5 or 18-crown-6, and described cave ether is (2.1.1cryptand), (2.2.1cryptand) or (2.2.2cryptand).
As present invention further optimization, described organic sulfur cation is Na +, corresponding crown ether is 15-crown-4 or 18-crown-5, and corresponding cave ether is (2.2.1cryptand) or (2.2.2cryptand).
As present invention further optimization, described organic sulfur cation is K +, corresponding crown ether is 18-crown-5, and corresponding cave ether is (2.2.2cryptand).
As present invention further optimization, the anion in described organic sulfosalt is Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -, Tp nO2 -one of them.
As present invention further optimization, the organic disulfide of described correspondence is BTe, BTp, BTp cl, BTp me, BTp meO, BTp cF3or BTp nO2.
As present invention further optimization, wherein, described Te -for 2-ehtylmercapto tetrazolium anion, Tp -for 2-phenylmercapto tetrazolium anion, Tp cl -for 2-rubigan mercapto-tetrazole anion, Tp me -for 2-p-methylphenyl mercapto-tetrazole anion, Tp meO -for 2-p-methoxyphenyl mercapto-tetrazole anion, Tp cF3 -for 2-p-trifluoromethyl phenyl mercapto-tetrazole anion, Tp nO2 -for 2-p-nitrophenyl mercapto-tetrazole anion.
As present invention further optimization, wherein, described BTe is two (1-ethyl tetrazolium-5-) disulphide, and BTp is two (1-phenyltetrazole-5-) disulphide, BTp clfor two (1-rubigan tetrazolium-5-) disulphide, BTp mefor two (1-p-methylphenyl tetrazolium-5-) disulphide, BTp meOfor two (1-p-methoxyphenyl tetrazolium-5-) disulphide, BTp cF3for two (1-p-trifluoromethyl phenyl tetrazolium-5-) disulphide, BTp nO2for two (1-nitrobenzophenone tetrazolium-5-) disulphide.
As present invention further optimization, in described electrolyte, organic sulfur reduction electricity is 1:(0.1-1 to the mol ratio with crown ether or cave ether).
As present invention further optimization, in described electrolyte, also comprise lithium perchlorate, 4-tert .-butylpyridine, acetonitrile and/or ethylene carbonate.
Two of object of the present invention is to provide a kind of electrolyte preparation method right based on organic sulfur reduction electricity, comprising:
The back flow reaction a few hours in ethanol by organic mercaptan and metal carbonate, be spin-dried for solvent, vacuumize obtains organic sulfosalt;
Organic mercaptan and hydrogen peroxide are heated in ethanol and is spin-dried for solvent, the disulphide that vacuumize must be corresponding with described organic sulfur salt after stoichiometric number hour;
In the mixture of organic sulfosalt and described disulphide, add corresponding crown ether or cave ether, can electrolyte be obtained.
As present invention further optimization, at least one in lithium perchlorate, 4-tert .-butylpyridine, acetonitrile and ethylene carbonate can also be added.
Preparation method's technique of the present invention is simple, with low cost, efficiency is higher, and redox electricity electrolyte prepared by the method, for dye sensitized nano crystal salar battery, has higher conversion efficiency.
Three of object of the present invention is to provide above-mentioned electrolyte to apply in dye sensitized nano crystal salar battery as redox mediator.
Four of object of the present invention is to provide a kind of dye sensitized nano crystal salar battery, comprising the above-mentioned electrolyte right based on organic sulfur reduction electricity.
Electrolyte of the present invention, it has the substituted radical of different push-and-pull electronic capability by introducing, affect the cloud density on tetrazolium conjugate ring, and then can regulate electrolytical oxidation-reduction potential, be conducive to obtaining higher open circuit voltage.Adopt the metal cation of crown ether or cave ether complexing as electrolyte cation, metal cation absorption on the titanium dioxide can be weakened thus raise work electrode conduction band positions to obtain higher open circuit voltage, simultaneously by forming passivation layer at titanium dioxide surface, dye sensitized nano crystal salar battery interface charge compound can be reduced on the impact of device performance.
Electrolyte of the present invention is reactivity and electron recombination and I not only -/ I 3 -outside electrolyte quite all satisfies condition, the absorption in visible region is far below I -/ I 3 -electrolyte, as the redox mediator of dye sensitized nano crystal salar battery, be conducive to the abundant sorption enhanced of dyestuff to sunlight, dye sensitized nano crystal salar battery conversion efficiency can be improved, and effectively prevent the drawback of elemental iodine volatilization, metal complex diffusion hindered, also therefore have more potential quality in transparent battery applications.In addition, this compounds is organic molecule, its skeleton and substituting group all can change, larger than the improvement space of metal complex, that is, its physicochemical properties and electrochemical properties can be improved by Molecular Design and adjustment, thus improve the performance of DSSC.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic sulfur alkoxide and disulphide.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The electrolyte right based on organic sulfur reduction electricity of the present embodiment, comprises organic sulfur oxidation-reduction pair RS -m +/ RS-SR, also comprises crown ether or cave ether.Wherein organic sulfur reduction electricity is to RS -m +/ RS-SR is by the organic sulfosalt RS of reduction-state component -m +form with the oxidation state component disulphide RS-SR of correspondence, R is any substituted radical.
Organic sulfosalt RS in electrolyte -m +can be oxidized to corresponding organic disulfide RS-SR, organic sulfur compound RS-SR also can be reduced into corresponding organic sulfosalt RS -m +, and this to reactivity and invertibity good.
In the present embodiment, can preferred reduction-state component RS -m +concentration be 0.1-1mol/L, but being not limited to above-mentioned concentration, also can be other values.
Also comprise lithium perchlorate, 4-tert .-butylpyridine and the auxiliary agent such as acetonitrile and ethylene carbonate mixed solvent in electrolyte, the mol ratio of each solute can be preferably RS -m +: RS-SR: crown ether or cave ether: lithium perchlorate: 4-tert .-butylpyridine=1:(0.1-1): (0-1): (0.05-1): (0.05-1), but be only a kind of preferred embodiment of the present invention, in ratio the present invention of each solute, be not limited to above-mentioned ratio range.
Crown ether or cave ether corresponding with the cation in organic sulfosalt, namely the size of crown ether or cave ether and cation diameter match.Crown ether or cave ether can form complex compound with cation, wrap the cation with positive charge.
Adopt the metal cation of crown ether or cave ether complexing as electrolyte cation, metal cation absorption on the titanium dioxide can be weakened thus raise work electrode conduction band positions to obtain higher open circuit voltage, simultaneously by forming passivation layer at titanium dioxide surface, dye sensitized nano crystal salar battery interface charge compound can be reduced on the impact of device performance.
RS -m +cation M +be selected from Li +, Na +, K +one of them.
Crown ether can be selected from any one in 12-crown-4,15-crown-5,18-crown-6, and cave ether can be any one in (2.1.1cryptand), (2.2.1cryptand) and (2.2.2cryptand).Such as, if organic sulfosalt RS -m +in cation be Li +, crown ether can be 12-crown-4 or 15-crown-5, and cave ether can be (2.1.1cryptand) or (2.2.1cryptand), if organic sulfosalt RS -m +in cation be Na +, corresponding crown ether can be 15-crown-5 or 18-crown-6, and cave ether can be (2.2.1cryptand) or (2.2.2cryptand).If organic sulfosalt RS -m +in cation be K+, corresponding crown ether can be 18-crown-6, and cave ether can be (2.2.2cryptand).
Organic sulfosalt RS -m +in anion RS -can be Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF 3 -, Tp nO2 -one of them.Wherein, Te -for 2-ehtylmercapto tetrazolium anion, Tp -for 2-phenylmercapto tetrazolium anion, Tp cl -for 2-rubigan mercapto-tetrazole anion, Tp me -for 2-p-methylphenyl mercapto-tetrazole anion, Tp meO -for 2-p-methoxyphenyl mercapto-tetrazole anion, Tp cF3 -for 2-p-trifluoromethyl phenyl mercapto-tetrazole anion, Tp nO2 -for 2-p-nitrophenyl mercapto-tetrazole anion.
Correspondingly, with organic sulfosalt RS -m +corresponding organic disulfide RS-SR can be BTe, BTp, BTp cl, BTp me, BTp meO, BTp cF3, BTp nO2one of them.It corresponds respectively to organic sulfosalt RS -m +in anion RS -(Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -, Tp nO2 -).Particularly, Te -corresponding BTe, Tp -corresponding BTp, Tp cl -corresponding BTp cl, Tp me -corresponding BTp me, Tp meO -corresponding BTp me o, Tp cF3 -corresponding BTp cF3, Tp nO2 -corresponding BTp nO2.
Wherein, BTe is two (1-ethyl tetrazolium-5-) disulphide, and BTp is two (1-phenyltetrazole-5-) disulphide, BTp clfor two (1-rubigan tetrazolium-5-) disulphide, BTp mefor two (1-p-methylphenyl tetrazolium-5-) disulphide, BTp meOfor two (1-p-methoxyphenyl tetrazolium-5-) disulphide, BTp cF3for two (1-p-trifluoromethyl phenyl tetrazolium-5-) disulphide, BTp nO2for two (1-nitrobenzophenone tetrazolium-5-) disulphide.
Electrolyte has the substituted radical of different push-and-pull electronic capability by introducing, affect the cloud density on tetrazolium conjugate ring, and then can regulate electrolytical oxidation-reduction potential, be conducive to obtaining higher open circuit voltage.
Embodiment 1
The electrolyte of the present embodiment is prepared by the following method: by organic sulfosalt (such as 2-ehtylmercapto tetrazolium lithium salts, consumption can be 6.8mg, concentration can for 0.05mmol) and disulphide pair (1-ethyl tetrazolium-5-) disulphide of its correspondence (such as consumption can be 6.5mg, concentration is 0.00625mmol) mixing, add crown ether (such as 12-crown-4) and acetonitrile (being preferably 0.25mL) and ethylene carbonate (preferably 0.25mL) again, ultrasonicly to dissolve completely, obtain liquid electrolyte.
In the present embodiment, organic sulfosalt is not limited to this, such as, can also be 2-ehtylmercapto tetrazolium sodium salt or sylvite.
This electrolyte is assembled into liquid dye sensitized nanocrystalline solar cell.Be 100mWcm in intensity -2analog solar photoelectric properties test show, this solar cell obtain closed-circuit photoelectric current density J sc=8.80mA/cm 2, open circuit voltage V oc=607mV, fill factor, curve factor FF=0.61, photoelectric conversion efficiency η=3.28%.
Embodiment 2
The electrolyte of the present embodiment is prepared by the following method: by organic sulfosalt (such as 2-phenylmercapto tetrazolium sodium salt, consumption can be 14.9mg, concentration can be 0.075mmol), (such as consumption can be 22mg for crown ether (such as the 15-crown-5 of 8.1 μ L0.05mmol) and two (1-phenyltetrazole-5-) disulphide of corresponding disulphide, concentration is 0.00625mmol) mixing, add a certain amount of acetonitrile (such as 0.5mL), ultrasonicly to dissolve completely, obtain liquid electrolyte.
This electrolyte is assembled into liquid dye sensitized nanocrystalline solar cell.Be 100mWcm in intensity -2analog solar photoelectric properties test show, this solar cell obtain closed-circuit photoelectric current density J sc=9.26mA/cm 2, open circuit voltage V oc=632mV, fill factor, curve factor FF=0.71, photoelectric conversion efficiency η=4.16%.
In the present embodiment, crown ether also can be 18-crown-6 or other, or crown ether can be replaced cave ether, such as (2.2.1cryptand) or (2.2.2cryptand) etc.
Embodiment 3
The electrolyte of the present embodiment is prepared by the following method: by organic sulfosalt (such as 2-p-methoxyphenyl mercapto-tetrazole sylvite, consumption can be 49.2mg, concentration can for 0.2mmol), crown ether (such as the 18-crown-6 of 32.4 μ L0.2mmol) and two (the 1-p-methoxyphenyl tetrazolium-5-) disulphide (such as consumption can be 0.1mmol for 42mg concentration) of corresponding disulphide mixes, add a certain amount of ethylene carbonate (such as 0.5mL), ultrasonicly to dissolve completely, obtain liquid electrolyte.
This electrolyte being assembled into liquid dye sensitized nanocrystalline solar cell, is 100mWcm in intensity -2analog solar photoelectric properties test show, this solar cell obtain closed-circuit photoelectric current density J sc=12.2mA/cm 2, open circuit voltage V oc=629mV, fill factor, curve factor FF=0.70, photoelectric conversion efficiency η=5.40%.
In the present embodiment, organic sulfosalt is not limited to this, and such as p-methoxyphenyl can be ethyl, phenyl, rubigan, p-methylphenyl, p-nitrophenyl or p-trifluoromethyl phenyl etc.
Embodiment 4
The electrolyte of the present embodiment is prepared by the following method: by organic sulfosalt (such as 2-ehtylmercapto tetrazolium lithium salts, consumption can be 27.2mg, concentration can be 0.2mmol), crown ether (such as the 12-crown-4 of 32.4 μ L0.4mmol), (such as consumption can be 13mg to two (the 1-ethyl tetrazolium-5-) disulphide of corresponding disulphide, concentration is 0.0125mmol) and lithium perchlorate (such as 2.66mg) mixing, add acetonitrile (such as 0.2mL) and ethylene carbonate (such as 0.3mL), ultrasonicly to dissolve completely, 4-tert .-butylpyridine (such as 37 μ L) is added with liquid-transfering gun, obtain liquid electrolyte.
This electrolyte being assembled into liquid dye sensitized nanocrystalline solar cell, is 100mWcm in intensity -2analog solar photoelectric properties test show, this solar cell obtain closed-circuit photoelectric current density J sc=14.3mA/cm 2, open circuit voltage V oc=670mV, fill factor, curve factor FF=0.69, photoelectric conversion efficiency η=6.61%.
In the various embodiments described above, organic sulfosalt is not limited to above-mentioned several, and other organic sulfosalts are also applicable, and disulphide is corresponding disulphide.
In the various embodiments described above, crown ether can be selected from any one in 12-crown-4,15-crown-5,18-crown-6, and cave ether can be any one in (2.1.1cryptand), (2.2.1cryptand) and (2.2.2cryptand).Such as, if organic sulfosalt RS -m +in cation be Li +, crown ether can be 12-crown-4 or 15-crown-5, and cave ether can be (2.1.1cryptand) or (2.2.1cryptand), if organic sulfosalt RS -m +in cation be Na +, corresponding crown ether can be 15-crown-5 or 18-crown-6, and cave ether can be (2.2.1cryptand) or (2.2.2cryptand).If organic sulfosalt RS -m +in cation be K +, corresponding crown ether can be 18-crown-6, and cave ether can be (2.2.2cryptand).
In the various embodiments described above, organic sulfosalt RS -m +in anion RS -can be Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -, Tp nO2 -one of them.Wherein, Te -for 2-ehtylmercapto tetrazolium anion, Tp -for 2-phenylmercapto tetrazolium anion, Tp cl -for 2-rubigan mercapto-tetrazole anion, Tp me -for 2-p-methylphenyl mercapto-tetrazole anion, Tp meO -for 2-p-methoxyphenyl mercapto-tetrazole anion, Tp cF3 -for 2-p-trifluoromethyl phenyl mercapto-tetrazole anion, Tp nO2 -for 2-p-nitrophenyl mercapto-tetrazole anion.
Correspondingly, with organic sulfosalt RS -m +corresponding organic disulfide RS-SR can be BTe, BTp, BTp cl, BTp me, BTp meO, BTp cF3, BTp nO2one of them.It corresponds respectively to organic sulfosalt RS -m +in anion RS -(Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -, Tp nO2 -).Particularly, Te -corresponding BTe, Tp -corresponding BTp, Tp cl -corresponding BTp cl, Tp me -corresponding BTp me, Tp meO -corresponding BTp me o, Tp cF3 -corresponding BTp cF3, Tp nO2 -corresponding BTp nO2.
Wherein, BTe is two (1-ethyl tetrazolium-5-) disulphide, and BTp is two (1-phenyltetrazole-5-) disulphide, BTp clfor two (1-rubigan tetrazolium-5-) disulphide, BTp mefor two (1-p-methylphenyl tetrazolium-5-) disulphide, BTp meOfor two (1-p-methoxyphenyl tetrazolium-5-) disulphide, BTp cF3for two (1-p-trifluoromethyl phenyl tetrazolium-5-) disulphide, BTp nO2for two (1-nitrobenzophenone tetrazolium-5-) disulphide.
In the various embodiments described above, organic sulfosalt is by the back flow reaction a few hours in ethanol by organic mercaptan and metal carbonate, and be spin-dried for solvent, vacuumize obtains.
In the various embodiments described above, corresponding disulphide can by heating (being such as heated to 40 degree) and being spin-dried for solvent, the disulphide that vacuumize must be corresponding with organic sulfur salt after stoichiometric number hour in ethanol by organic mercaptan and hydrogen peroxide.
At least one in lithium perchlorate, 4-tert .-butylpyridine, acetonitrile and ethylene carbonate can also be added in electrolyte.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (14)

1. one kind based on the right electrolyte of organic sulfur reduction electricity, it is characterized in that, this electrolyte comprises organic sulfur oxidation-reduction pair and crown ether or cave ether, wherein, the right reduction-state component of described organic sulfur reduction electricity is organic sulfosalt, and oxidation state component is the organic disulfide corresponding with this organic sulfur salt.
2. according to claim 1ly a kind ofly to it is characterized in that based on the right electrolyte of organic sulfur reduction electricity, described crown ether or cave ether corresponding with the cation in organic sulfosalt.
3. a kind of electrolyte right based on organic sulfur reduction electricity according to claim 1, it is characterized in that, the organic sulfur cation in described organic sulfosalt is metal cation.
4. a kind of electrolyte right based on organic sulfur reduction electricity according to claim 1, it is characterized in that, the organic sulfur cation in described organic sulfosalt is Li+, Na+ or K+.
5. a kind of electrolyte right based on organic sulfur reduction electricity according to any one of claim 1-4, it is characterized in that, described crown ether is 12-crown-4,15-crown-5 or 18-crown-6.
6. a kind of electrolyte right based on organic sulfur reduction electricity according to any one of claim 1-4, it is characterized in that, described cave ether is (2.1.1cryptand), (2.2.1cryptand) or (2.2.2cryptand).
7. a kind of electrolyte right based on organic sulfur reduction electricity according to claim 5, it is characterized in that, described cave ether is (2.1.1cryptand), (2.2.1cryptand) or (2.2.2cryptand).
8. a kind of electrolyte right based on organic sulfur reduction electricity according to any one of claim 1-4 and 7, it is characterized in that, the anion in described organic sulfosalt is Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -and Tp nO2 -one of them.
9. a kind of electrolyte right based on organic sulfur reduction electricity according to claim 5, it is characterized in that, the anion in described organic sulfosalt is Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -and Tp nO2 -one of them.
10. a kind of electrolyte right based on organic sulfur reduction electricity according to claim 6, it is characterized in that, the anion in described organic sulfosalt is Te -, Tp -, Tp cl -, Tp me -, Tp meO -, Tp cF3 -and Tp n o2 -one of them.
11. according to claim 1-4,7 and 9-10 according to any one of a kind of based on the right electrolyte of organic sulfur reduction electricity, it is characterized in that, the organic disulfide of described correspondence is BTe, BTp, BTp cl, BTp me, BTp meO, BTp cF3or BTp nO2.
12. according to claim 1-4,7 and 9-10 according to any one of a kind of based on the right electrolyte of organic sulfur reduction electricity, it is characterized in that, in described electrolyte, also comprise lithium perchlorate, 4-tert .-butylpyridine, acetonitrile and/or ethylene carbonate.
13. 1 kinds, based on the right electrolyte preparation method of organic sulfur reduction electricity, comprising:
The back flow reaction a few hours in ethanol by organic mercaptan and metal carbonate, be spin-dried for solvent, vacuumize obtains organic sulfosalt;
Organic mercaptan and hydrogen peroxide are heated in ethanol and is spin-dried for solvent, the disulphide that vacuumize must be corresponding with described organic sulfur salt after stoichiometric number hour;
In the mixture of described organic sulfosalt and corresponding disulphide, add corresponding crown ether or cave ether, described electrolyte can be formed.
Described a kind of of one of 14. claim 1-12 is preparing the application in solar cell, fuel cell, lithium ion battery or ultracapacitor based on the right electrolyte of organic sulfur reduction electricity.
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