CN100382213C - Organic electrolyte and preparing method thereof - Google Patents
Organic electrolyte and preparing method thereof Download PDFInfo
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- CN100382213C CN100382213C CNB03153693XA CN03153693A CN100382213C CN 100382213 C CN100382213 C CN 100382213C CN B03153693X A CNB03153693X A CN B03153693XA CN 03153693 A CN03153693 A CN 03153693A CN 100382213 C CN100382213 C CN 100382213C
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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
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention discloses organic electrolyte solution for a super capacitor, and a preparation method thereof. The organic electrolyte solution is prepared from inorganic electrolytes, organic electrolytes, organic solvents and polycomponent additives, wherein the positive ions and the negative ions are provided by the dissociation of the organic electrolytes and the inorganic electrolytes in the organic solvents, the organic solvents are nontoxic organic compounds such as dimethylsulphoxide with high decomposition voltage, etc., and simultaneously the polycomponent additives are introduced to reduce the viscosity and the internal resistance of the organic electrolyte solution and improve the electrochemical stability and safety performance of the organic electrolyte solution. The organic electrolyte solution has high decomposition voltage and electrochemical stability, and thus, the organic electrolyte solution is favorable to improving the energy density and the power density of the super capacitor. The present invention has the advantages of low cost, little pollution, high safety, etc., and can be suitable for commercial application.
Description
Technical field
A kind of organic electrolyte that is used for ultracapacitor of the present invention and preparation method thereof belongs to material science, especially technical field of electrochemistry.
Technical background
Ultracapacitor is a kind of novel energy device between rechargeable battery and capacitor, have the dual-use function of electric capacity and battery concurrently, its power density is far above common batteries, energy density is far above conventional physical electric capacity, compare with battery with ordinary capacitor, it is little that ultracapacitor has a volume, capacity is big, charging rate is fast, have extended cycle life, the discharging efficiency height, operating temperature range is wide, advantage such as good reliability and contaminant-free maintenance-free, be a kind of novel, efficiently, practical energy accumulating device, thereby at electric power, railway, traffic, medical treatment, military project, all there is very wide application prospect in fields such as communication, as: the back-up source in (1) data-storage system and the portable electric appts; (2) low-power consumption instrument provides reliable source of power; (3) cooperate battery applications in the electric starting system of various explosive motors; (4) great power pulse power source; (5) electrical source of power of motor vehicle and energy regeneration system; (6) be used for various transformer and distribution power station direct current systems and switch permanent magnet mechanism operating power; (7) uninterruptible power system (UPS); (8) be used for electric power energy-storage systems such as wind power generation, hydroelectric power generation and solar energy power generating.
Ultracapacitor is as a kind of energy storage device of excellent performance, become the U.S., Japan, Russia, Korea S and European developed country at present at one of focus of material, electric power, electronics, physics, chemical multidisciplinary crossing domain research.Main goal in research is the required low-cost electrode material of the fine and close energy of preparation high-energy-density and high power density, with the electrolyte body based material of operating voltage height, stable electrochemical property, conductivity height and long service life, and prepare the ultracapacitor energy storage device of aspects such as the back-up source that can be used for various electronic equipments of high power density, high-energy-density and stable performance and electric automobile hybrid power system on this basis.
In the research of ultracapacitor, the stored energy of ultracapacitor monomer is calculated as follows:
W＝0.5CV
2
W represents energy in the formula, J; C is an electric capacity, F; V is the voltage that puts on the capacitor, V.From following formula as can be seen, the energy that ultracapacitor is stored be proportional to the voltage that applied square, therefore, improve the energy density that the voltage that is applied can increase considerably ultracapacitor.Yet under high voltage condition, electrolyte solution easily decomposes, and causes that internal resistance sharply increases and capacitance reduces rapidly.Therefore electrolytical decomposition voltage is one of key factor that limits its specific power and specific energy always, compares with water base electrolyte, and organic electrolyte has higher decomposition voltage.And because of its no corrosion protection problem is easy to encapsulation, available aluminum has significantly reduced material cost as collector body and encapsulating material.
Because organic electrolyte decomposition voltage height, encapsulation are simply, thereby be subjected to researcher's extensive concern.In order to obtain the high and good organic electrolyte of electrochemical stability of decomposition voltage; usually adopt the strong organic solvent of antioxygenic property; because second cyanogen has very strong electrochemical stability; even under higher voltage, also be difficult for oxidized; so be used in the ultracapacitor of being everlasting; but, be unfavorable for personal safety and environmental protection because it has very strong volatility and toxicity.
People such as peace Eastcom hero disclose employing ethylene carbonate-dimethyl carbonate in Japanese patent of invention JP28563 be organic solvent, and be that electrolyte is formed organic electrolyte with lithium salts such as lithium hexafluoro phosphates, the electrolyte stable electrochemical property, but have the lower (problem such as 2.0V～3.0V) of the higher and operating voltage of lithium hexafluoro phosphate cost.
People such as palpus township's prestige disclose a kind of electric double-layer capacitors prepared method in Japanese patent of invention JP223680, wherein adopting tetrafluoro boric acid amine amine salt and lithium salts in the organic electrolyte is electrolyte, do not use additive to improve the performance of organic electrolyte, therefore have the big and shortcomings such as electrochemical stability difference and electrode swelling ratio height of internal resistance.
People such as Wu Huanxi propose a kind of organic electrolyte in Korea S patent of invention KR56438, this electrolyte is by lithium salts, nonaqueous solvents, alkylene unsaturated compound or fluorobenzene are formed, electrolyte is mainly inorganic lithium salt, do not adopt amine salt, nonaqueous solvents is an ethylene carbonate, propene carbonate etc., wherein the alkylene unsaturated compound is in containing the electrolyte of lithium salts, when being higher than 1.0V, voltage is reduced the coating-alkylene unsaturated compound layer that is formed on the anode surface, the electrode swelling that prevention causes in the anode surface reaction because of nonaqueous solvents, the formation of this layer has simultaneously overcome because of internal resistance increase and discharge capacity reduce the other problems that is produced, but exists the low and cost of organic electrolyte operating voltage than problems such as height.
People such as Fujimoto have proposed a kind of organic solvent that contains the inferior ethene fat of 20%～80% carbonic acid in U.S. Pat 5352548, in order to improve the low temperature performance of lithium secondary battery, but owing to the inferior ethene fat of carbonic acid costs an arm and a leg, so this organic solvent is unfavorable for commercial applications.
From above analysis as can be known, though some organic electrolytes have more stable operating voltage and chemical stability, but still have that ionic conductivity is low, internal resistance is big, operating voltage low (＜3.0V), cost is higher and problem such as strong toxicity, therefore development voltage height (＞3.0V), the little low-cost low toxicity of ionic conductivity height and internal resistance or the non-toxic organic electrolyte energy density and the power density that become present raising ultracapacitor, and the effective way that is implemented in the widespread commercial application of energy field and power system of electric automobile.
Summary of the invention
Subject matter solved by the invention is: a kind of organic electrolyte that is used for ultracapacitor and preparation method thereof is provided, and it has advantages such as low viscosity, conductivity height, decomposition voltage height and toxicity are little, and the commerce that is easy to low cost is used.
Technical solution of the present invention is: a kind of organic electrolyte that is used for ultracapacitor, it is characterized in that: each constituent content is organic solvent, additive 0.01%～5% (based on containing electrolytical organic solvent quality), and contains the inorganic electrolyte of 0.01mol/L～2.5mol/L and the organic bath of 0.01mol/L～2.5mol/L.
Above-mentioned preferred content is: organic solvent, additive 0.5%～3.5% (based on containing electrolytical organic solvent quality), and contain the inorganic electrolyte of 0.1mol/L～1.5mol/L and the organic bath of 0.1mol/L～1.5mol/L.
Above-mentioned inorganic electrolyte is one or more in the lithium salts such as lithium iodide, lithium perchlorate, lithium hexafluoro phosphate, LiBF4.
Above-mentioned organic bath is tetrafluoro boric acid tetraethyl amine, tetramethyl ammonium tetrafluoroborate, tetrapropyl ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, trimethyl ethyl ammonium tetrafluoroborate, diethyl-dimethyl ammonium tetrafluoroborate, N-ethyl-N-crassitude tetrafluoro boric acid amine, N-N-tetramethylene pyrrolidines tetrafluoro boric acid amine, 1-ethyl-3-methylimidazole tetrafluoro boric acid amine etc.; Ammonium perchlorate class such as tetraethyl ammonium perchlorate, tetramethyl ammonium perchlorate, tetrapropyl ammonium perchlorate, tetrabutylammonium perchlorate, trimethyl ethyl ammonium perchlorate, N-ethyl-N-crassitude perchlorate, N-N-tetramethylene pyrrolidines perchlorate, 1-ethyl-3-methylimidazole perchlorate etc.; In ammonium hexafluorophosphate class such as tetraethyl ammonium hexafluorophosphate, tetramethyl ammonium hexafluorophosphate, tetrapropyl ammonium hexafluorophosphate, tetrabutyl ammonium hexafluorophosphate, trimethyl ethyl ammonium hexafluorophosphate, triethyl group methyl ammonium hexafluorophosphate, the diethyl-dimethyl ammonium hexafluorophosphate etc. one or more.
Above-mentioned organic solvent is two or more in sulfolane, methyl-sulfoxide, ethylene carbonate, propene carbonate, butylene carbonate fat, dimethyl carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat, dimethylacetylamide, nitroethylene etc. and the derivative thereof, dielectric constant is in 28～100 scope, and decomposition voltage is between 3.2V～6.2V.
Above-mentioned additive is one or more during aluminium oxide, magnesium oxide, calcium oxide calcium carbonate and lithium carbonate weigh; Or in acetyl ammonia and the derivative thereof one or more; Or in the alkylene unsaturated compounds such as inferior ethene fat of carbonic acid and vinyl sulfone(Remzaol one or more; Or in the fluoric cyclic carbonic ether compounds such as a fluoro methyl carbonic acid ethene fat, two fluoro methyl carbonic acid ethene fat and three fluoro methyl carbonic acid ethene fat one or more; Also above-mentioned various additives can be combined, form two or more additive, but total amount ranges was 0.01%～5% (based on containing electrolytical organic solvent quality), and preferred amount ranges was 0.5%～3.5% (based on containing electrolytical organic solvent quality).
The present invention includes inorganic electrolyte, organic bath, organic solvent and additive, adopt inorganic electrolyte and organic amine salt or lithium salts electrolyte such as lithium salts simultaneously, improve electrolyte in organic solvent dissolution and the ability of dissociating, improve the ionic conducting property of electrolyte, to reduce the internal resistance of organic electrolyte.
The present invention adopts high-k, low viscosity, high de-agglomeration voltage, low toxicity or nontoxic binary or ternary organic solvent system, wherein the organic solvent of high-k and high de-agglomeration voltage provides required organic electrolyte high de-agglomeration voltage, low viscous organic solvent can be used to reduce the viscosity of high-k organic solvent and improves ionic conductivity, low toxicity or nonpoisonous organic solvent mainly are to reduce its harm and environmental pollution to human body, improve its safe application performance.
The present invention adopts the multicomponent additive, can prevent the electrode swelling, reduces internal resistance, improves the conductivity and the electrochemistry cyclical stability of electrolyte, and safety in utilization.Wherein carbonate is joined in the electrolyte as additive, can with the hydrofluoric acid reaction of trace in the electrolyte, stop hydrofluoric acid to the destruction of electrode with to the catalytic action of inorganic lithium salt decomposition reaction, improve the stability of electrolyte; Acetamide and derivative etc. thereof have larger molecular weight can strong coordination take place with the lithium ion in the electrolyte, reduces its solvation radius, thereby improves the conductance of electrolyte significantly, can significantly improve the electrochemistry cyclical stability of electrolyte; Alkylene unsaturated compounds such as the inferior ethene fat of carbonic acid are in containing the electrolyte of lithium salts, when voltage is higher, be reduced the face coat that forms the alkylene unsaturated compound at anode surface, stop nonaqueous solvents at the anode surface generated reactive gas, prevent the electrode swelling, the formation of this alkylene unsaturated compound stable coatings simultaneously, can be lowered into the consumption of electrolyte in the membrane process, thereby play ionic conductivity that improves electrolyte and the effect that reduces the electrolyte internal resistance, the cyclical stability and the useful life of improving electrolyte; The introducing of fluoric cyclic carbonic ether compounds such as one fluoro methyl carbonic acid ethene fat, two fluoro methyl carbonic acid ethene fat and three fluoro methyl carbonic acid ethene fat, owing to have better chemical stability, higher lightning and higher dielectric constant, can dissolve electrolyte lithium salt, and dissolve each other with other organic solvents, therefore can improve the charge-discharge performance and the security performance of organic solvent.
Prepare the above-mentioned organic electrolyte that is used for ultracapacitor, it is characterized in that: comprise following process steps: organic solvent, inorganic electrolyte liquid, organic electrolyte and the additive of described concentration and ratio are placed the sealing mixer respectively, on planetary ball mill, mix then, rotating speed 150rpm～300rpm, ball milling time 10min～60min, form uniform mixture, promptly obtain uniform organic electrolyte.
Principle of the present invention is: adopt high-k, low viscosity, high de-agglomeration voltage, low toxicity or nontoxic binary or ternary organic solvent system, wherein the organic solvent of high-k and high de-agglomeration voltage provides required organic electrolyte high de-agglomeration voltage, low viscous organic solvent can be used to reduce the viscosity of high-k organic solvent and improves ionic conductivity, low toxicity or nonpoisonous organic solvent mainly are to reduce its harm and environmental pollution to human body, improve its safe application performance.
Adopt the multicomponent additive simultaneously, can prevent the electrode swelling, reduce internal resistance, improve the conductivity and the electrochemistry cyclical stability of electrolyte, and safety in utilization.Wherein carbonate is joined in the electrolyte as additive, can with the hydrofluoric acid reaction of trace in the electrolyte, stop hydrofluoric acid to the destruction of electrode with to the catalytic action of inorganic lithium salt decomposition reaction, improve the stability of electrolyte; Acetamide and derivative etc. thereof have larger molecular weight can strong coordination take place with the lithium ion in the electrolyte, reduces its solvation radius, thereby improves the conductance of electrolyte significantly, can significantly improve the electrochemistry cyclical stability of electrolyte; Alkylene unsaturated compounds such as the inferior ethene fat of carbonic acid are in containing the electrolyte of lithium salts, when voltage is higher, be reduced the face coat that forms the alkylene unsaturated compound at anode surface, stop nonaqueous solvents at the anode surface generated reactive gas, prevent the electrode swelling, the formation of this alkylene unsaturated compound stable coatings simultaneously, can be lowered into the consumption of electrolyte in the membrane process, thereby play ionic conductivity that improves electrolyte and the effect that reduces the electrolyte internal resistance, the cyclical stability and the useful life of improving electrolyte; The introducing of fluoric cyclic carbonic ether compounds such as one fluoro methyl carbonic acid ethene fat, two fluoro methyl carbonic acid ethene fat and three fluoro methyl carbonic acid ethene fat, owing to have better chemical stability, higher lightning and higher dielectric constant, can dissolve electrolyte lithium salt, and dissolve each other with other organic solvents, therefore can improve the charge-discharge performance and the security performance of organic solvent.
The advantage that the present invention compared with prior art has is: prior art mostly is to be utilized lithium salts separately or adopts amine salt dissociating in organic solvent separately, form ion, and normal employing of organic solvent has high-volatile toxic solvent, mainly utilize the lower organic solvent systems of decomposition voltage such as ethylene carbonate, mostly be and contain high-k and low viscous binary organic solvent system, though electrochemical stability is preferably arranged, but exist the organic electrolyte decomposition voltage low, internal resistance is big, critical defects such as strong toxicity and cost height, finally cause the energy density and the power density of ultracapacitor to be limited in very limited level, and have serious potential safety hazard.The present invention utilizes inorganic and organic lithium salt and amine salt electrolyte, and the ability that has kept lithium salts and amine salt highly to dissociate in different organic solvents has simultaneously improved the ionic conductivity of organic electrolyte, has reduced internal resistance; Adopt low-cost nontoxic polynary organic solvent system, employing has on the basis of nontoxic methyl-sulfoxide human subject organic solvent of higher decomposition voltage, low viscosity organic solvent of Cai Yonging and multicomponent additive simultaneously, improve the ionic conductance characteristic of organic solvent, reduce the internal resistance of organic electrolyte, improve the fail safe of organic electrolyte, obtain high de-agglomeration voltage, internal resistance is little, avirulence or hypotoxicity, the organic electrolyte of stable electrochemical property safe in utilization, increase substantially the energy density and the power density of ultracapacitor, and the gained organic electrolyte is with low cost, is easy to commercial applications.
Embodiment
Further specify the present invention with specific embodiment below.But the present invention is not limited to embodiment.Agents useful for same purity is chemical pure, analyzes more than the pure and mild spectroscopic pure in following examples.
Embodiment 1
At first ethylene carbonate is placed glass container, under the nitrogen protection condition, slowly be heated to 50 ℃, up to fusing fully.Methyl-sulfoxide, propene carbonate and ethylene carbonate are become organic solvent with 80: 10: 10 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with lithium hexafluoro phosphate, according to the concentration (based on the organic solvent that is disposed) of 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with the tetrapropyl ammonium tetrafluoroborate, concentration (based on the organic solvent that is disposed) according to 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the aluminium oxide of difference weighing 0.5%, 0.5% acetyl ammonia, the content of the inferior ethene fat of 0.5% carbonic acid, 0.5% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 150rpm, ball milling time 10min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 2
At first ethylene carbonate is placed glass container, under the nitrogen protection condition, slowly be heated to 90 ℃, up to fusing fully.With sulfolane, dimethyl carbonate, methyl ethyl carbonate fat and ethylene carbonate with 40: 30: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium hexafluoro phosphate and lithium iodide, respectively according to the concentration (based on the organic solvent that is disposed) of 0.01mol/L and 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetrafluoro boric acid tetraethyl amine, concentration (based on the organic solvent that is disposed) according to 1.0mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 60min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the magnesium oxide of difference weighing 0.4%, 1.5% acetyl ammonia, the content of the inferior ethene fat of 1.0% carbonic acid and the inferior ethene fat of 1.0% carbonic acid; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 300rpm, ball milling time 60min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 3
At first ethylene carbonate is placed glass container, under the nitrogen protection condition, slowly be heated to 70 ℃, up to fusing fully.With methyl-sulfoxide, dimethyl carbonate, carbonic acid 2 first and second fat and ethylene carbonate with 60: 20: 10: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate and lithium hexafluoro phosphate, all according to the concentration (based on the organic solvent that is disposed) of 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with N-N-tetramethylene pyrrolidines tetrafluoro boric acid amine, concentration (based on the organic solvent that is disposed) according to 1.0mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 120min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the calcium oxide of difference weighing 1.0%, 0.5% acetyl second ammonia, the content of 1.0% vinyl sulfone(Remzaol, 0.1% three fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 30min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 4
At first methyl-sulfoxide, propene carbonate, dimethyl carbonate are become organic solvent with 40: 30: 30 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with LiBF4, all according to the concentration (based on the organic solvent that is disposed) of 1.5mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with the tetraethyl ammonium hexafluorophosphate, concentration (based on the organic solvent that is disposed) according to 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 40min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the calcium carbonate of difference weighing 4.7%, 0.1% acetyl ammonia, 0.1% vinyl sulfone(Remzaol, 0.1% three fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 260rpm, ball milling time 20min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 5
At first sulfolane, propene carbonate, dimethyl carbonate are become organic solvent with 50: 30: 20 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with LiBF4, all according to the concentration (based on the organic solvent that is disposed) of 2.4mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with the tetraethyl ammonium hexafluorophosphate, concentration (based on the organic solvent that is disposed) according to 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 40min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, weighing respectively, 4.5% acetyl ammonia, the inferior ethene fat of 0.4% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 260rpm, ball milling time 20min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 6
At first methyl-sulfoxide, propene carbonate, dimethyl carbonate are become organic solvent with 30: 60: 10 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with lithium hexafluoro phosphate and LiBF4, respectively according to 0.2mol/L and 0.3mol/L concentration (based on the organic solvent that is disposed), add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetramethyl ammonium tetrafluoroborate and tetraethyl ammonium hexafluorophosphate, respectively according to the concentration (based on the organic solvent that is disposed) of 0.4mol/L and 0.6mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 40min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the calcium carbonate of difference weighing 0.1%, 0.1% acetyl ammonia, the inferior ethene fat of 4.7% carbonic acid, 0.1% two fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 30min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 7
At first methyl-sulfoxide and propene carbonate are become organic solvent according to 50: 50 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force blender; Then with lithium hexafluoro phosphate and LiBF4, respectively according to 0.1mol/L and 0.1mol/L concentration (based on the organic solvent that is disposed), add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with the tetramethyl ammonium tetrafluoroborate, concentration (based on the organic solvent that is disposed) according to 2.3mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the calcium carbonate of difference weighing 0.1%, 4.9% two fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer on planetary ball mill, to mix rotating speed 200rpm, ball milling time 30min, form uniform mixing material, promptly obtain the target organic electrolyte.
Embodiment 8
At first sulfolane, propene carbonate and dimethylacetylamide are become organic solvent according to 60: 40: 10 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with lithium perchlorate, according to 0.5mol/L concentration (based on the organic solvent that is disposed), add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with the diethyl-dimethyl ammonium hexafluorophosphate, concentration (based on the organic solvent that is disposed) according to 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 50min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the calcium carbonate of difference weighing 1.0%, 0.5% acetyl ammonia, the inferior ethene fat of 3.0% carbonic acid, 1.5% two fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 60min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 9
At first with sulfolane, propene carbonate, dimethylacetylamide and nitroethylene according to 35: 25: 15: 25 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium hexafluoro phosphate, according to 1.0mol/L concentration (based on the organic solvent that is disposed), add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with two 1-ethyl-3-methylimidazole perchlorate, concentration (based on the organic solvent that is disposed) according to 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 60min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the calcium carbonate of difference weighing 2.0%, 0.5% acetyl ammonia, 2.5% two fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 10
At first methyl-sulfoxide, propene carbonate and butylene carbonate fat are become organic solvent with 75: 15: 10 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with lithium hexafluoro phosphate, according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; With tetrafluoro boric acid amine, according to the concentration (based on the organic solvent that is disposed) of 1.4mol/L, adding holds in the glass container of the organic solvent of preparing after the weighing again, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of weighing 1.5% respectively, 0.5% vinyl sulfone(Remzaol, the inferior ethene fat of 2.0% carbonic acid, 0.3% fluoro methyl carbonic acid ethene fat and 0.7% two fluoro methyl carbonic acid ethene fat and; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 60min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 11
At first methyl-sulfoxide, dimethyl carbonate and ethylene carbonate are become organic solvent with 60: 20: 20 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with lithium iodide, according to the concentration (based on the organic solvent that is disposed) of 1.5mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetrabutyl ammonium tetrafluoroborate and trimethyl ethyl ammonium tetrafluoroborate respectively after concentration (based on the organic solvent that the is disposed) weighing according to 1.4mol/L and 0.1mol%, add and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of weighing 1.5% respectively, 0.5% vinyl sulfone(Remzaol, the inferior ethene fat of 2.0% carbonic acid, 0.3% fluoro methyl carbonic acid ethene fat and 0.7% two fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 60min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 12
At first methyl-sulfoxide, propene carbonate and carbonic acid diethyl ester are become organic solvent with 25: 30: 45 proportional arrangement, place glass container, stir, obtain uniform organic solvent with the bidirectional magnetic force heating stirrer; Then with lithium iodide, according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetramethyl ammonium tetrafluoroborate and tetrapropyl ammonium tetrafluoroborate respectively according to the concentration (based on the organic solvent that is disposed) of 1.4mol/L and 1.0mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of weighing 1.5% respectively, 0.5% vinyl sulfone(Remzaol, the inferior ethene fat of 2.0% carbonic acid, 0.3% fluoro methyl carbonic acid ethene fat and 0.7% two fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 60min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 13
At first with methyl-sulfoxide, propene carbonate, dimethylacetylamide, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate, according to the concentration (based on the organic solvent that is disposed) of 2.49mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with the concentration (based on the organic solvent that disposed) of tetramethyl ammonium tetrafluoroborate according to 0.01mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 4.7%, 0.1% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 14
At first with sulfolane, propene carbonate, dimethylacetylamide, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate, according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with diethyl-dimethyl ammonium tetrafluoroborate, N-ethyl-N-crassitude tetrafluoro boric acid amine, respectively according to the concentration (based on the organic solvent that is disposed) of 1.4mol/L and 1.0mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 15
At first with sulfolane, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate, according to the concentration (based on the organic solvent that is disposed) of 0.01mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with N-N-tetramethylene pyrrolidines tetrafluoro boric acid amine and 1-ethyl-3-methylimidazole tetrafluoro boric acid amine respectively according to the concentration (based on the organic solvent that is disposed) of 2.48mol/L and 0.01mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 15
At first with sulfolane, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate, according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetraethyl ammonium perchlorate and tetrapropyl ammonium perchlorate respectively according to the concentration (based on the organic solvent that is disposed) of 1.4mol/L and 1.0mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 16
At first with sulfolane, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate, according to the concentration (based on the organic solvent that is disposed) of 0.01mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again will, tetrabutylammonium perchlorate and trimethyl ethyl ammonium perchlorate be respectively according to the concentration (based on the organic solvent that is disposed) of 2.48mol/L and 0.01mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 17
At first with methyl-sulfoxide, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium perchlorate, according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with N-ethyl-N-crassitude amine perchlorate, N-N-tetramethylene pyrrole slightly alkane amine perchlorate and 1-ethyl-3-methylimidazole amine perchlorate respectively according to the concentration (based on the organic solvent that is disposed) of 0.5mol/L, 0.1mol% and 0.5mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 18
At first with methyl-sulfoxide, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium hexafluoro phosphate, according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetraethyl ammonium hexafluorophosphate, tetramethyl ammonium hexafluorophosphate and tetrapropyl ammonium hexafluorophosphate respectively according to the concentration (based on the organic solvent that is disposed) of 0.1mol/L, 2.2mol% and 0.1mol/L, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 19
At first with methyl-sulfoxide, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium hexafluoro phosphate, according to the concentration (based on the organic solvent that is disposed) of 2.48mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with tetrabutyl ammonium hexafluorophosphate and trimethyl ethyl ammonium hexafluorophosphate respectively according to the concentration (based on the organic solvent that is disposed) of 0.01mol/L and 0.01mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 0.1%, 4.7% vinyl sulfone(Remzaol, the inferior ethene fat of 0.1% carbonic acid, 0.1% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 200rpm, ball milling time 40min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
Embodiment 20
At first with methyl-sulfoxide, propene carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat were with 50: 20: 20: 10 proportional arrangement becomes organic solvent, places glass container, stirs with the bidirectional magnetic force heating stirrer, obtains uniform organic solvent; Then with lithium hexafluoro phosphate, according to the concentration (based on the organic solvent that is disposed) of 0.01mol/L, add after the weighing and hold in the glass container of the organic solvent of prepare, the continuation stirring makes electrolyte dissolution; Again with triethyl group methyl ammonium hexafluorophosphate and diethyl-dimethyl ammonium hexafluorophosphate respectively according to the concentration (based on the organic solvent that is disposed) of 2.48mol/L and 0.01mol%, add after the weighing and hold in the glass container of the organic solvent of preparing, stir 30min, make the electrolyte uniform dissolution in organic solvent, formation contains electrolytical organic solvent uniformly, seals stand-by.At last, based on the quality that contains electrolytical organic solvent, the lithium carbonate of difference weighing 1.5%, 0.7% vinyl sulfone(Remzaol, the inferior ethene fat of 1.0% carbonic acid, 0.3% a fluoro methyl carbonic acid ethene fat; Each compound with institute's weighing adds prepared containing in the electrolytical organic solvent then, again this mixture is placed the sealing mixer, on planetary ball mill, mix, rotating speed 150rpm, ball milling time 60min, form uniform mixing material, thereby obtain can be used for the target organic electrolyte of ultracapacitor.
In a word, the resulting organic electrolyte of the present invention has stable electrochemical property, operating voltage height, viscosity is low, internal resistance is little, cost is low, low toxicity or avirulence, characteristics such as safe in utilization, can be used as the electrolyte of low-cost and high-performance ultracapacitor.
Claims (6)
1. the organic electrolyte that is used for ultracapacitor, it is characterized in that: each component and content are that organic solvent, content are the additive that contains electrolytical organic solvent quality 0.01%～5%, and content is that inorganic electrolyte and the content of 0.01mol/L～2.5mol/L is the organic bath of 0.01mol/L～2.5mol/L; Described additive is two or more in the inferior ethene fat of aluminium oxide, magnesium oxide, calcium oxide, calcium carbonate, lithium carbonate, acetyl ammonia and derivative thereof, carbonic acid, vinyl sulfone(Remzaol unsaturated compound, a fluoro methyl carbonic acid ethene fat, two fluoro methyl carbonic acid ethene fat and the three fluoro methyl carbonic acid ethene fat.
2. organic electrolyte according to claim 1, it is characterized in that: wherein: additive level is to contain 0.5%～3.5% of electrolytical organic solvent quality, inorganic electrolyte content is: 0.1mol/L～1.5mol/L, organic bath content are 0.1mol/L～1.5mol/L.
3. organic electrolyte according to claim 1 and 2 is characterized in that: described inorganic electrolyte is one or more in lithium iodide, lithium perchlorate, lithium hexafluoro phosphate, the LiBF4.
4. organic electrolyte according to claim 1 and 2 is characterized in that: described organic bath is tetrafluoro boric acid tetraethyl amine, tetramethyl ammonium tetrafluoroborate, tetrapropyl ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, trimethyl ethyl ammonium tetrafluoroborate, diethyl-dimethyl ammonium tetrafluoroborate, N-ethyl-N-crassitude tetrafluoro boric acid amine, N-N-tetramethylene pyrrolidines tetrafluoro boric acid amine, 1-ethyl-3-methylimidazole tetrafluoro boric acid amine etc.; Ammonium perchlorate class such as tetraethyl ammonium perchlorate, tetramethyl ammonium perchlorate, tetrapropyl ammonium perchlorate, tetrabutylammonium perchlorate, trimethyl ethyl ammonium perchlorate, N-ethyl-N-crassitude perchlorate, N-N-tetramethylene pyrrolidines perchlorate, 1-ethyl-3-methylimidazole perchlorate etc.; In ammonium hexafluorophosphate class such as tetraethyl ammonium hexafluorophosphate, tetramethyl ammonium hexafluorophosphate, tetrapropyl ammonium hexafluorophosphate, tetrabutyl ammonium hexafluorophosphate, trimethyl ethyl ammonium hexafluorophosphate, triethyl group methyl ammonium hexafluorophosphate, the diethyl-dimethyl ammonium hexafluorophosphate one or more.
5. organic electrolyte according to claim 1 and 2, it is characterized in that: described organic solvent is two or more in sulfolane, methyl-sulfoxide, ethylene carbonate, propene carbonate, butylene carbonate fat, dimethyl carbonate, carbonic acid diethyl ester, carbonic acid 2 first and second fat, dimethylacetylamide, nitroethylene and the derivative thereof, the dielectric constant of organic solvent is in 28～100 scope, and decomposition voltage is between 3.2V～6.2V.
6. prepare the described organic electrolyte of claim 1, it is characterized in that comprising following process steps:
(1) described organic solvent is placed glass container, as when being solid-state organic compound, then under inert atmosphere or vacuum condition, and slowly be heated to 50 ℃～90 ℃, up to melting fully; As then placing glass container, stand-by for liquid state;
(2) with described inorganic electrolyte, press the concentration of 0.01mol/L～2.5mol/L, add after the weighing in the glass container;
(3) with described organic bath, press the concentration of 0.01mol/L～2.5mol/L, add after the weighing in the glass container;
(4) with the content of gained organic solvent in the above-mentioned steps (1) according to electrolytical concentration requirement in step (2) or (3), join in the glass container, stir on the bidirectional magnetic force heating stirrer, mixing time is 30min-120min, the thing that is uniformly mixed, stand-by;
(5) with described additive according to the content that contains electrolytical organic solvent 0.1%～5.0%, join in the resulting mixture of step (4), place the sealing mixer, on planetary ball mill, mix, rotating speed 150rpm～300rpm, ball milling time 10min～60min forms uniform mixture, promptly obtains uniform organic electrolyte.Organic solvent, inorganic electrolyte liquid, organic electrolyte and the additive of described concentration and ratio are placed the sealing mixer respectively, on planetary ball mill, mix then, rotating speed 150rpm～300rpm, ball milling time 10min～60min, form uniform mixture, promptly obtain uniform organic electrolyte.
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| EP2037468B1 (en) * | 2006-06-30 | 2012-10-24 | Otsuka Chemical Co., Ltd. | Additive for electrolyte solution and electrolyte solution |
| CN102760574B (en) * | 2011-04-27 | 2015-08-26 | 海洋王照明科技股份有限公司 | A kind of double electric layer capacitor electrolytic solution and use the double electric layer capacitor of this electrolyte |
| CN102543446B (en) * | 2012-01-16 | 2013-07-24 | 武汉大学 | Electrolyte for dye sensitized solar cells |
| CN103021671A (en) * | 2012-11-28 | 2013-04-03 | 惠州亿纬锂能股份有限公司 | Capacitor of lithium ion battery |
| CN103730263A (en) * | 2013-12-27 | 2014-04-16 | 深圳新宙邦科技股份有限公司 | Organic electrolytic solution for super capacitor and super capacitor |
| CN103943882A (en) * | 2014-03-27 | 2014-07-23 | 北京化学试剂研究所 | Preparation method of lithium battery electrolyte |
| CN105161795A (en) * | 2015-06-19 | 2015-12-16 | 深圳大学 | Electrolyte for lithium air battery and preparation method for electrolyte, and lithium air battery |
| CN106449162B (en) * | 2016-11-14 | 2018-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of ultracapacitor of high voltage |
| CN109003834A (en) * | 2018-07-20 | 2018-12-14 | 安徽旭峰电容器有限公司 | A kind of supercapacitor high-voltage electrolyte |
| CN109004263B (en) * | 2018-07-25 | 2022-08-26 | 湖南立方新能源科技有限责任公司 | Electrolyte and high-safety lithium ion battery containing same |
| CN113972395B (en) * | 2020-07-23 | 2023-08-08 | 比亚迪股份有限公司 | Lithium battery electrolyte and lithium battery |
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| EP1329974A1 (en) * | 2000-09-07 | 2003-07-23 | Bridgestone Corporation | Additive for non-aqueous liquid electrolyte, non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor |
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