CN101587777A - Difunctional electrolyte and preparation method thereof - Google Patents
Difunctional electrolyte and preparation method thereof Download PDFInfo
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- CN101587777A CN101587777A CNA2009100437258A CN200910043725A CN101587777A CN 101587777 A CN101587777 A CN 101587777A CN A2009100437258 A CNA2009100437258 A CN A2009100437258A CN 200910043725 A CN200910043725 A CN 200910043725A CN 101587777 A CN101587777 A CN 101587777A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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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
- 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 relates to a difunctional electrolyte and preparation method thereof. The electrolyte is prepared by dissolving LiODFB, TEAODFB and additives to PC radical nonaqueous organic solvent. The PC radical nonaqueous organic solvent is one or multiple-solvent system at least containing propene carbonate, and ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl methyl carbonate, ethyl, methyl acetate, ethyl acetate, ethylene sulfite, propylene sulfite, acetonitrile, gamma-D lactone. The electrolyte of the invention has difunctional characteristic, which not only satisfies the request for the lithium ion battery by Li[+] chemical energy saving, but also satisfies the request for a super capacitor double electrode layer energy saving, at the same time being the difunctional electrolyte suitable for the super capacitor battery. The electrolyte is beneficial to promote the contribution for the energy and environment problem solution and provides a developing way for the electrolyte development.
Description
Technical field
The present invention relates to the electrolyte that multiple electrochemical energy storage device is used, especially relate to electrolyte and preparation thereof that a kind of super capacitance cell is used.
Background technology
Being on the rise of global environmental pollution and energy crisis forces various countries to strive to find the novel energy of sustainable development, is that the environmental protection energy storage device of representative has become current focus and research focus with lithium ion battery and ultracapacitor.But, the energy storage device of performances such as high-energy-density, high power density and long-life is badly in need of having concurrently in fields such as Aero-Space, defence and military, motor vehicle, electronic information and instrument and meter, and independent use of lithium ion battery or ultracapacitor all is difficult to satisfy simultaneously these requirements.
Ultracapacitor carries out the physics energy storage by the interfacial electric double layer electric capacity of electrode and electrolyte, the advantage that have the power density height, has extended cycle life, but energy density is relatively low; And lithium ion battery is by Li
+Embedding off line system carry out chemical energy storage, have energy density height, the little characteristics of self discharge, but high rate performance is undesirable, power density is lower.In order to satisfy the demand, people are used in combination this two classes device of battery and capacitor outward by " combining " mode, not only bulky, and need extra power-supply management system.Therefore, more and more need a kind of advantage that integrates ultracapacitor and lithium ion battery, both are realized obtaining to have concurrently the novel energy-storing device of high-energy-density and high power density in conjunction with (i.e. " interior combination ") from device inside.Super capacitance cell is a kind of existing electric double layer capacitance energy storage, has lithium ion to take off the device that the embedding mode is carried out energy storage again.Device inside can have different compound modes, and as lithium-ion energy storage just very, negative pole is the electric double layer energy storage; Just very electric double layer energy storage, negative pole are lithium-ion energy storage; Have lithium-ion energy storage and electric double layer capacitance energy storage on the perhaps same electrode simultaneously.Therefore, super capacitance cell is expected to substitute existing secondary cell or ultracapacitor and is used widely.
Super capacitance cell is a kind of novel energy storage system, because the electrolyte that super capacitance cell is used not only will satisfy the requirement that lithium ion is deviate to embed, also will satisfy the requirement that electric double layer discharges and recharges simultaneously, and its work characteristics requires electrolyte to have double function characteristic.
For satisfying the lithium-ion energy storage function of super capacitance cell, in the electrolyte suitable lithium salts to be arranged.Oxalic acid difluoro lithium borate (LiODFB) is a kind of novel lithium salts, contains BOB
-And BF
4 -Respectively the structure of half combines LiBF
4Advantage with LiBOB.LiODFB has good ionic conductivity in wide temperature range, low temperature and high magnification are supported the lithium ion battery high discharge capacity down; Can in the PC solvent, make graphite cathode form stable SEI film, make it exempt from destruction, obtain excellent cycle performance; And compare with LiBOB, the SEI membrane impedance that LiODFB forms is less relatively.Therefore, LiODFB is considered to a kind of and can substitutes LiPF
6, can be used for the electrolyte lithium salt of the prospect that has more under the PC based solvent system.
For satisfying the electric double layer capacitance energy-storage function of super capacitance cell, suitable ultracapacitor electrolysis matter salt to be arranged in the electrolyte.Organic system ultracapacitor electrolysis matter mainly is high conductivity to be arranged in AN or PC solvent and with absorbent charcoal material the quaternary ammonium salt of high stability is arranged.Tetraethylammonium tetrafluoroborate (TEABF
4) owing in the PC solvent, have good conductivity, advantages such as electrochemical window and temperature window wide ranges, thereby obtained using widely.But, if directly with TEABF
4Combine as the composite electrolyte salt of Difunctional electrolyte with the LiODFB lithium salts, will cause Li
+With BF
4 -Association, poor with the graphite compatibility, be difficult to form problems such as stable SEI film; Simultaneously, anion BF
4 -Under the situation that has micro-moisture to exist, can be hydrolyzed into hypertoxic HF.According to noted earlier, ODFB
-The type anionic group makes graphite cathode that good film-formation result is arranged in the PC solvent.Therefore, this invention proposition is that the super capacitance cell electrolyte is to satisfy the requirement of electric double layer capacitance energy storage with novel ammonium salt-oxalic acid difluoro tetraethylammonium borate (TEAODFB).
(CN101079511A) such as the Zhang Zhian of this seminar proposed a kind of electrolyte for super capacitance cell in 2007.A kind of electrolyte that adopts lithium salts and ammonium salt to combine, but do not mention have can with the PC solvent compatibility good contain ODFB
-The lithium salts of type anionic group and ammonium salt.
To sum up, this invention is on lithium ion battery and electrolytic solution for super capacitor research and development basis, proposition is solvent with PC, with TEAODFB and these two kinds of materials of LiODFB is electrolytic salt, preparation (LiODFB+TEAODFB)/PC base electrolyte, with its Difunctional electrolyte as super capacitance cell, this New-type bifunctional electrolyte also can satisfy the application of lithium ion battery and ultracapacitor simultaneously.
Summary of the invention
The objective of the invention is to overcome the defective that electrolyte that ultracapacitor and lithium ion battery use does not have versatility, a kind of wide temperature range charge-discharge performance and high conductivity of having concurrently is provided, when satisfying super capacitance cell and have high energy density, the electrolyte that also has high power density, high current charge-discharge and the characteristics in good circulation life-span.It meets the electrolyte of lithium ion battery energy storage requirement and ultracapacitor energy storage requirement, and especially this electrolyte can satisfy the requirement that super capacitance cell has lithium-ion energy storage and electric double layer capacitance energy storage simultaneously.
The objective of the invention is to realize in the following manner.
A kind of Difunctional electrolyte is to have the TEAODFB of structure shown in the LiODFB of structure shown in the formula 1 and the formula 2, and additive is dissolved in the solution that PC base non-aqueous organic solvent forms.
Formula 1 formula 2
Described LiODFB and the TEAODFB mass percent in electrolyte is 14%-25%; The mol ratio of LiODFB and TEAODFB is not less than 5: 1.
Described PC base non-aqueous organic solvent is a kind of propene carbonate that contains at least, also contains one or more the dicyandiamide solution in ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, Ethyl formate, methyl acetate, ethyl acetate, ethylene sulfite, propylene sulfite, acetonitrile, the gamma-butyrolacton.
Propene carbonate mass content in the described PC base non-aqueous organic solvent is not less than 20%, the ethylene carbonate mass content is not higher than 20%, the dimethyl carbonate mass content is not higher than 30%, the acetonitrile mass content is not higher than 30%, the methyl ethyl carbonate mass content is not higher than 40%, and Ethyl formate content is not higher than 40%.
Additive is one or more in oxolane, diethylene glycol dimethyl ether, methyl-sulfoxide or the sulfolane; The mass percent of additive in electrolyte is 0.1-6%.
The preparation method of described electrolyte: LiODFB is dissolved in the PC base non-aqueous organic solvent, adds TEAODFB again, after the dissolving, add additive at last fully, shelve 24h, promptly obtain described electrolyte.
The present invention has overcome in the conventional art TEABF
4Combine as the composite electrolyte salt of Difunctional electrolyte with the LiODFB lithium salts, will cause Li
+With BF
4 -Association, poor with the graphite compatibility, be difficult to form problems such as stable SEI film; Simultaneously, anion BF
4 -Under the situation that has micro-moisture to exist, can be hydrolyzed into hypertoxic HF.Select for use LiODFB and TEAODFB salt to combine first, the common ODFB that it contains
-Type anion and PC solvent have good compatibility, can fully satisfy the requirement of super capacitance cell energy storage.
In addition, described Difunctional electrolyte is by the physical-chemical parameters such as molten boiling point, viscosity, dielectric constant of research electrolyte, the proportioning of optimization LiODFB and TEAODFB salt and solvent, components of additives, ratio obtain to have high conductivity, the electrolyte system of wide operating temperature range.Propene carbonate itself just has low fusing point, high boiling point and higher dielectric constant, but viscosity is bigger.Therefore select for use to have good electrical conductivity at low temperatures, mobile and molten, boiling point is low, the linear carbonates that viscosity is low is as dimethyl carbonate (DMC), methyl ethyl carbonate (EMC).Select additive such as methyl-sulfoxide (DMSO), diethylene glycol dimethyl ether (DG) etc. for use with higher, develop a kind of good high and low temperature charge-discharge performance and high conductivity of having concurrently, when satisfying super capacitance cell and have high energy density, also have high power density, high current charge-discharge and the characteristics in good circulation life-span.
Embodiment
Below in conjunction with execution mode and embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.The present invention can realize by described any mode of summary of the invention.
The preparation of TEAODFB salt
With chlorine-containing compound (silicon tetrachloride or aluminum trichloride (anhydrous)), contain oxalate compound (anhydrous oxalic acid) and contain tetrafluoro boric acid radical compound (tetraethylammonium tetrafluoroborate) and press the mol ratio 1: 2: 2 of chlorine, oxalate, tetrafluoroborate and mix, during reaction, tetraethylammonium tetrafluoroborate and anhydrous oxalic acid are dissolved in the reaction medium earlier, chlorine-containing compound dropwise adds in whipping process, stir 8～14h after 4～12h adds again, 0～40 ℃ of reaction does not produce to there being gas.Course of reaction obtains etamon difluoro oxalate borate by reduction vaporization or low temperature recrystallization again with at least a Buchholz protection in high-purity argon gas, the high pure nitrogen.
Reaction medium is selected from one or more in acetonitrile, propene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, the methyl ethyl carbonate.
The fusing point of the etamon difluoro oxalate borate (TEAODFB) of preparation is lower, has only 33 ℃, and has the potential window of 4.8V.The reduction vaporization optimum temperature is 35 ℃, the solvent of recrystallization is selected from acetonitrile or propene carbonate, the crystallization agent is selected from one or more in methyl alcohol, ethanol, methyl formate, methyl acetate, ethyl acetate, butyl acetate, toluene, the methyl ether, add crystallization agent and solvent ratio be 1: 100 to 1: 10, recrystallization temperature is-30 ℃～-10 ℃.
Embodiment 1
By weight the methyl-sulfoxide (DMSO) of getting 40% propene carbonate (PC), dimethyl carbonate (DMC) 30% and 3% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, to add total amount be the electrolyte lithium salt LiODFB of 1mol/L in gradation then, treat that electrolyte fully dissolves after, adding total amount is the electrolyte ammonium salt TEAODFB of 0.1mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.
The assembling of super capacitance cell is adopted business-like olivine LiFePO in the following manner
4And active carbon, mix as positive electrode active materials after taking by weighing at 2: 8 by weight.Anodal batching is according to active material: carbon black: the weight ratio of binding agent=80: 12: 8 is carried out mixed slurry, evenly is coated on the aluminum foil current collector that thickness is 25 μ m, dries at 120 ℃ and makes electrode.Adopt business-like Delanium and active carbon to mix as negative active core-shell material.Cathode blending is according to active material: carbon black: the weight ratio of binding agent=86: 8: 6 is carried out mixed slurry, and evenly being coated on thickness is on the Copper Foil collector of 15 μ m, dries at 120 ℃ and makes electrode.Proportionally be cut into a certain size pole piece then, matched group is dressed up 204468 batteries, and used barrier film is Celgard-2400.
The lithium ion battery assembling is adopted business-like olivine LiFePO in the following manner
4As positive electrode active materials.Anodal batching is according to active material: carbon black: the weight ratio of binding agent=80: 12: 8 is carried out mixed slurry, evenly is coated on the aluminum foil current collector that thickness is 25 μ m, dries at 120 ℃ and makes electrode.Adopt business-like Delanium and active carbon to mix as negative active core-shell material.Cathode blending is according to active material: carbon black: the weight ratio of binding agent=86: 8: 6 is carried out mixed slurry, and evenly being coated on thickness is on the Copper Foil collector of 15 μ m, dries at 120 ℃ and makes electrode.Proportionally be cut into a certain size pole piece then, matched group is dressed up square 063048 battery, and used barrier film is Celgard-2400.
The assembling mode of ultracapacitor adopts the commercialization active carbon as electrode active material in the following manner.Active carbon, acetylene black and binding agent are carried out mixed slurry by mass ratio at 80: 10: 10, evenly on coating and the 30 μ m aluminium collectors, in vacuum drying chamber under 100 ℃ of conditions dry 10h, proportionally be cut into a certain size pole piece then, matched group is dressed up the 5F ultracapacitor, and used barrier film is the special-purpose barrier film of TF4050 type organic system ultracapacitor.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞95%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 375mAh, and the 10C discharge capacity maintains 350mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞90.3%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.9F, after 1500 circulations, and capability retention＞98%.
Embodiment 2
By weight the methyl-sulfoxide (DMSO) of getting 50% propene carbonate (PC), dimethyl carbonate (DMC) 20% and 1% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, to add total amount be the electrolyte lithium salt LiODFB of 1mol/L in gradation then, treat that electrolyte fully dissolves after, adding total amount is the electrolyte ammonium salt TEAODFB of 0.05mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞94%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 378mAh, and the 10C discharge capacity maintains 352mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞92%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.8F, after 1500 circulations, and capability retention＞98.5%.
Embodiment 3
By weight the diethylene glycol dimethyl ether (DG) of getting 50% propene carbonate (PC), dimethyl carbonate (DMC) 15%, methyl ethyl carbonate 10% and 4% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, gradation adding total amount is the electrolyte lithium salt LiODFB of 1mol/L then, after treating that electrolyte fully dissolves, adding total amount is the electrolyte ammonium salt TEAODFB of 0.05mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞97%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 379mAh, and the 10C discharge capacity maintains 355mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞95%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.8F, after 1500 circulations, and capability retention＞99%.
Embodiment 4
By weight the diethylene glycol dimethyl ether (DG) of getting 50% propene carbonate (PC), dimethyl carbonate (DMC) 10%, methyl ethyl carbonate 20% and 1% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, gradation adding total amount is the electrolyte lithium salt LiODFB of 1mol/L then, after treating that electrolyte fully dissolves, adding total amount is the electrolyte ammonium salt TEAODFB of 0.16mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞95.5%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 380mAh, and the 10C discharge capacity maintains 360mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞93%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.8F, after 1500 circulations, and capability retention＞98.5%.
Embodiment 5
By weight the diethylene glycol dimethyl ether (DG) of getting 30% propene carbonate (PC), dimethyl carbonate (DMC) 20%, methyl ethyl carbonate 20% and 3% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, gradation adding total amount is the electrolyte lithium salt LiODFB of 1mol/L then, after treating that electrolyte fully dissolves, adding total amount is the electrolyte ammonium salt TEAODFB of 0.02mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞93.5%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 380mAh, and the 10C discharge capacity maintains 360mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞95%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.8F, after 1500 circulations, and capability retention＞99%.
Embodiment 6
By weight the diethylene glycol dimethyl ether (DG) of getting 30% propene carbonate (PC), ethylene carbonate (EC) 10%, methyl ethyl carbonate 30% and 3% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, gradation adding total amount is the electrolyte lithium salt LiODFB of 1mol/L then, after treating that electrolyte fully dissolves, adding total amount is the electrolyte ammonium salt TEAODFB of 0.02mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞95%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 380mAh, and the 10C discharge capacity maintains 355mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞95%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.5F, after 1500 circulations, and capability retention＞98%.
Embodiment 7
By weight the diethylene glycol dimethyl ether (DG) of getting 20% propene carbonate (PC), ethylene carbonate (EC) 20%, dimethyl carbonate (DMC) 10%, Ethyl formate (EF) 20% and 1% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, gradation adding total amount is the electrolyte lithium salt LiODFB of 1mol/L then, after treating that electrolyte fully dissolves, adding total amount is the electrolyte ammonium salt TEAODFB of 0.05mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.6Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞93.5%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 380mAh, and the 10C discharge capacity maintains 350mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞99%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.7F, after 1500 circulations, and capability retention＞99%.
Embodiment 8
By weight the diethylene glycol dimethyl ether (DG) of getting 30% propene carbonate (PC), ethylene carbonate (EC) 25%, acetonitrile (AN) 5%, Ethyl formate (EF) 30% and 1% respectively, be lower than in the glove box of 1ppm (quality percentage composition) in water, oxygen content, fully mix, be mixed with electrolyte solvent, gradation adding total amount is the electrolyte lithium salt LiODFB of 1.2mol/L then, after treating that electrolyte fully dissolves, adding total amount is the electrolyte ammonium salt TEAODFB of 0.2mol/L, after treating that electrolyte fully dissolves, shelve 24h; Promptly obtain Difunctional electrolyte of the present invention.All the other are with embodiment 1.
Through the super capacitance cell test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 4Ah, and the 10C discharge capacity maintains 3.7Ah, and 1C discharges and recharges through after 100 circulations, capability retention＞93.5%.
Through the lithium ion battery test, in resulting Difunctional electrolyte, in 2.2-3.8V voltage power supply scope, discharging current 1C capacity is 375mAh, and the 10C discharge capacity maintains 350mAh, and 1C discharges and recharges through after 100 circulations, capability retention＞92%.
Through the ultracapacitor test, in resulting Difunctional electrolyte, in 0-2.5V voltage power supply scope, charging and discharging currents 100mA capacity is 5F, and the 200mA charge/discharge capacity maintains 4.7F, after 1500 circulations, and capability retention＞98%.
Claims (10)
1, a kind of Difunctional electrolyte is characterized in that, described electrolyte is to have the TEAODFB of structure shown in the LiODFB of structure shown in the formula 1 and the formula 2, and additive is dissolved in the solution that PC base non-aqueous organic solvent forms.
Formula 1 formula 2
2, electrolyte according to claim 1 is characterized in that, described LiODFB and the TEAODFB mass percent in electrolyte is 14%-25%; The mol ratio of LiODFB and TEAODFB is not less than 5: 1.
3, electrolyte according to claim 1, it is characterized in that, described PC base non-aqueous organic solvent is a kind of propene carbonate that contains at least, also contains one or more the dicyandiamide solution in ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, Ethyl formate, methyl acetate, ethyl acetate, ethylene sulfite, propylene sulfite, acetonitrile, the gamma-butyrolacton.
4, according to claim 1 or 3 described electrolyte, it is characterized in that, propene carbonate mass content in the described PC base non-aqueous organic solvent is not less than 20%, the ethylene carbonate mass content is not higher than 20%, the dimethyl carbonate mass content is not higher than 30%, the acetonitrile mass content is not higher than 30%, and the methyl ethyl carbonate mass content is not higher than 40%, and Ethyl formate content is not higher than 40%.
5, electrolyte according to claim 1 is characterized in that, additive is one or more in oxolane, diethylene glycol dimethyl ether, methyl-sulfoxide or the sulfolane; The mass percent of additive in electrolyte is 0.1-6%.
6, the preparation method of the described electrolyte of claim 1 is characterized in that, LiODFB is dissolved in the PC base non-aqueous organic solvent, adds TEAODFB again, after the dissolving, adds additive at last fully, shelves 24h, promptly obtains described electrolyte.
7, the preparation method of electrolyte according to claim 6 is characterized in that, described LiODFB and the TEAODFB mass percent in electrolyte is 14%-25%; The mol ratio of LiODFB and TEAODFB is not less than 5: 1.
8, the preparation method of electrolyte according to claim 6, it is characterized in that, described PC base non-aqueous organic solvent is a kind of propene carbonate that contains at least, also contains one or more the dicyandiamide solution in ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, Ethyl formate, methyl acetate, ethyl acetate, ethylene sulfite, propylene sulfite, acetonitrile, the gamma-butyrolacton.
9, according to the preparation method of claim 6 or 8 described electrolyte, it is characterized in that, propene carbonate mass content in the described PC base non-aqueous organic solvent is not less than 20%, the ethylene carbonate mass content is not higher than 20%, the dimethyl carbonate mass content is not higher than 30%, the acetonitrile mass content is not higher than 30%, and the methyl ethyl carbonate mass content is not higher than 40%, and Ethyl formate content is not higher than 40%.
10, the preparation method of electrolyte according to claim 6 is characterized in that, additive is one or more in oxolane, diethylene glycol dimethyl ether, methyl-sulfoxide or the sulfolane; The mass percent of additive in electrolyte is 0.1-6%.
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| CN103943376A (en) * | 2013-01-22 | 2014-07-23 | 中国科学院大连化学物理研究所 | Electrolyte of mixed type super capacitor |
| CN104681301A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super capacitor |
| CN104701032A (en) * | 2015-01-07 | 2015-06-10 | 南昌大学 | Preparation method of boron ionic liquid containing super capacitor |
| CN105098248A (en) * | 2015-07-16 | 2015-11-25 | 湖南中大新能源科技有限公司 | Lithium ion battery electrolyte |
| WO2015196427A1 (en) * | 2014-06-26 | 2015-12-30 | 深圳新宙邦科技股份有限公司 | Electrolyte solute, electrolyte and high-voltage super-capacitor |
| CN106848401A (en) * | 2017-01-11 | 2017-06-13 | 长兴天晟能源科技有限公司 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
| CN106848402A (en) * | 2017-01-11 | 2017-06-13 | 长兴天晟能源科技有限公司 | A kind of lithium ion battery high temperature blocks electrolyte certainly |
| CN107564733A (en) * | 2017-08-23 | 2018-01-09 | 吴江佳亿电子科技有限公司 | A kind of ultracapacitor flame retardant type electrolyte, its preparation method and ultracapacitor |
| CN108242569A (en) * | 2016-12-27 | 2018-07-03 | 丰田自动车株式会社 | Non-aqueous electrolyte and lithium secondary battery |
| CN109888180A (en) * | 2019-02-01 | 2019-06-14 | 无锡凯帕德瑞科技有限公司 | Capacitor batteries |
| CN111477977A (en) * | 2019-01-23 | 2020-07-31 | 北京理工大学 | Water-ether mixed electrolyte for lithium ion battery and preparation method thereof |
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- 2009-06-19 CN CN2009100437258A patent/CN101587777B/en not_active Expired - Fee Related
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| CN103943376A (en) * | 2013-01-22 | 2014-07-23 | 中国科学院大连化学物理研究所 | Electrolyte of mixed type super capacitor |
| CN104681301A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super capacitor |
| CN104681301B (en) * | 2013-12-03 | 2018-03-20 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super-capacitor |
| US9870874B2 (en) | 2014-06-26 | 2018-01-16 | Shenzhen Capchem Technology Co., Ltd. | Electrolyte solute, electrolyte, and high-voltage supercapacitor |
| WO2015196427A1 (en) * | 2014-06-26 | 2015-12-30 | 深圳新宙邦科技股份有限公司 | Electrolyte solute, electrolyte and high-voltage super-capacitor |
| CN104701032A (en) * | 2015-01-07 | 2015-06-10 | 南昌大学 | Preparation method of boron ionic liquid containing super capacitor |
| CN105098248A (en) * | 2015-07-16 | 2015-11-25 | 湖南中大新能源科技有限公司 | Lithium ion battery electrolyte |
| CN108242569A (en) * | 2016-12-27 | 2018-07-03 | 丰田自动车株式会社 | Non-aqueous electrolyte and lithium secondary battery |
| CN108242569B (en) * | 2016-12-27 | 2021-01-12 | 丰田自动车株式会社 | Nonaqueous electrolyte solution and lithium secondary battery |
| CN106848402A (en) * | 2017-01-11 | 2017-06-13 | 长兴天晟能源科技有限公司 | A kind of lithium ion battery high temperature blocks electrolyte certainly |
| CN106848401A (en) * | 2017-01-11 | 2017-06-13 | 长兴天晟能源科技有限公司 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
| CN107564733A (en) * | 2017-08-23 | 2018-01-09 | 吴江佳亿电子科技有限公司 | A kind of ultracapacitor flame retardant type electrolyte, its preparation method and ultracapacitor |
| CN111477977A (en) * | 2019-01-23 | 2020-07-31 | 北京理工大学 | Water-ether mixed electrolyte for lithium ion battery and preparation method thereof |
| CN109888180A (en) * | 2019-02-01 | 2019-06-14 | 无锡凯帕德瑞科技有限公司 | Capacitor batteries |
| CN109888180B (en) * | 2019-02-01 | 2020-05-19 | 无锡凯帕德瑞科技有限公司 | Capacitor battery |
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