CN100550240C - Addition agent of non-aqueous electrolyte, nonaqueous electrolytic solution and double electric layer capacitor - Google Patents
Addition agent of non-aqueous electrolyte, nonaqueous electrolytic solution and double electric layer capacitor Download PDFInfo
- Publication number
- CN100550240C CN100550240C CNB2005800131897A CN200580013189A CN100550240C CN 100550240 C CN100550240 C CN 100550240C CN B2005800131897 A CNB2005800131897 A CN B2005800131897A CN 200580013189 A CN200580013189 A CN 200580013189A CN 100550240 C CN100550240 C CN 100550240C
- Authority
- CN
- China
- Prior art keywords
- layer capacitor
- electric layer
- double electric
- electrolytic solution
- nonaqueous electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of addition agent of non-aqueous electrolyte that the burning inhibiting substances discharges the double electric layer capacitor of compound that contains, described compound can discharge when burning has the burning inhibiting substances that excellent burning suppresses effect, be particularly related to a kind of addition agent of non-aqueous electrolyte that the burning inhibiting substances that discharges the burning inhibiting substances when burning discharges the double electric layer capacitor of compound that contains, it is characterized by described burning inhibiting substances is to have P-F key and/or P-NH in the molecule
2The phosphine oxide compound of key.
Description
Technical field
The present invention relates to a kind of double electric layer capacitor addition agent of non-aqueous electrolyte, contain this additive double electric layer capacitor with nonaqueous electrolytic solution and use the nonaqueous electrolytic solution double electric layer capacitor of this nonaqueous electrolytic solution, particularly a kind of have an addition agent of non-aqueous electrolyte that excellent burning suppresses the double electric layer capacitor of effect.
Background technology
Double electric layer capacitor is the capacitor that utilizes the electric double layer that forms between electrode and electrolyte, its charge and discharge cycles is the circulation at electrode surface electric adion from electrolyte, from this respect, it is different from the battery that charge and discharge cycles circulates for the redox reaction that moves with material.So double electric layer capacitor is compared with battery has excellent moment charge-discharge characteristic, without chemical reaction, even therefore repeated charge, moment charge-discharge characteristic can deterioration yet.In addition, in double electric layer capacitor, owing to do not discharge and recharge overvoltage when discharging and recharging, so simple and cheap circuit can meet the demands.And, compare with battery and to have lot of advantages, as knowing remaining capacity easily, under-30～90 ℃ wide region temperature conditions, having temperature wear properties, non-pollution etc., therefore, in recent years as a kind of novel energy storage goods of the excellence that is beneficial to environmental protection and show one's promises.The capacitor of electric double layer is owing to have an above-mentioned feature, the power supply during also gradually as the energy regeneration of electric automobile, fuel-cell vehicle or hybrid electric automobile or engine start.
Above-mentioned double electric layer capacitor is for having positive and negative electrode and electrolytical energy stowage arrangement, and on electrode and electrolytical contact-making surface, positive and negative charge minimum distance is at interval arranged relatively, forms electric double layer.Because electrolyte plays a role as the ion source that is used to form electric double layer, therefore identical with electrode, be the important substance of control double electric layer capacitor fundamental characteristics.As this electrolyte, present known have aqueous electrolyte, nonaqueous electrolytic solution and solid electrolyte etc., but from the aspect of the energy density that can improve double electric layer capacitor, the nonaqueous electrolytic solution that can set high working voltage is noticeable especially, has entered the practicability stage.As this nonaqueous electrolytic solution, for example, dissolving (C in the non-proton organic solvent of high-ks such as carbonic ester (ethylene carbonate, propylene carbonate etc.), gamma-butyrolacton
2H
5)
4PBF
4Or (C
2H
5)
4NBF
4Deng the mixed liquor of solute (supporting electrolyte) practicability.
Yet because above-mentioned non-proton organic solvent flash-point (flash point) is low, therefore, because double electric layer capacitor heating etc. when on fire, it is dangerous high to ignite.In addition, this non-proton organic solvent is along with double electric layer capacitor generates heat, and the gas that produces gas or generation and thermal conductance are decomposed in gasification, and to cause the double electric layer capacitor danger on fire of breaking also higher.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of addition agent of non-aqueous electrolyte of double electric layer capacitor, this additive can discharge the burning inhibiting substances with excellent burning inhibition effect when containing burning burning inhibiting substances discharges compound.In addition, the present invention also aims to provide a kind of double electric layer capacitor that contains above-mentioned addition agent of non-aqueous electrolyte and have an excellent fail safe with nonaqueous electrolytic solution and use the safe nonaqueous electrolytic solution double electric layer capacitor of this nonaqueous electrolytic solution.
The inventor etc. concentrate on studies for achieving the above object, found that, a kind of burning inhibiting substances of ad hoc structure has excellent burning and suppresses effect, discharging compound by the burning inhibiting substances that can discharge this burning inhibiting substances joins in the nonaqueous electrolytic solution, can improve nonaqueous electrolytic solution significantly and use the fail safe of the nonaqueous electrolytic solution double electric layer capacitor of this nonaqueous electrolytic solution, thereby finish the present invention.
That is, the addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention can discharge the burning inhibiting substances when containing burning burning inhibiting substances discharges compound, and being characterized as of described burning inhibiting substances is to have P-F key and/or P-NH in the molecule
2The phosphine oxide compound of key.
In the preference of the addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention, above-mentioned burning inhibiting substances is at least a kind of in self-extinguishment material, flame retardancy material and the incombustible.
In other preferences of the addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention, above-mentioned phosphine oxide compound shown in following formula (I),
O＝PR
1 3····(I)
(in the formula, R
1Be expressed as the substituting group or the halogen atom of monovalence respectively independently, at least one R
1Be fluorine atom or amino).Herein, the more preferably R in the formula (I)
1Be independently selected from fluorine atom, amino, alkyl and alkoxyl and at least one R respectively
1Be fluorine atom or amino phosphine oxide compound.In addition, at least one R in the special preferred formula (I)
1Be at least one R in fluorine atom and the formula (I)
1Be the phosphine oxide compound of amino, and two above R in the formula (I)
1Be fluorine atom or amino phosphine oxide compound.
In other preferences of the addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention, above-mentioned burning inhibiting substances discharges in the compound molecule and contains phosphorus and fluorine atom and/or nitrogen-atoms.This burning inhibiting substances discharges compound and more preferably contains phosphorus-to-nitrogen bonds in the molecule.In addition, above-mentioned burning inhibiting substances discharges in the preferred molecule of compound and contains phosphorus-fluorine bond.Discharge compound as above-mentioned burning inhibiting substances, can preferably enumerate positive phosphine compound.
In addition, double electric layer capacitor of the present invention is characterized as with nonaqueous electrolytic solution, contains the addition agent of non-aqueous electrolyte and the supporting electrolyte of above-mentioned double electric layer capacitor.
Double electric layer capacitor nonaqueous electrolytic solution of the present invention preferably also contains non-proton organic solvent.As this non-proton organic solvent, preferred nitrile compound, ring-type and the ester compounds of chain and the ether compound of chain.
Double electric layer capacitor nonaqueous electrolytic solution of the present invention, the nonaqueous electrolytic solution of the above-mentioned double electric layer capacitor of every 1L can discharge the above burning inhibiting substances of 0.03mol during preferred burn.
Double electric layer capacitor nonaqueous electrolytic solution of the present invention preferably contains the above above-mentioned burning inhibiting substances of 3 volume % and discharges compound, more preferably contains more than the 5 volume %.
Being characterized as of nonaqueous electrolytic solution double electric layer capacitor of the present invention comprises above-mentioned double electric layer capacitor nonaqueous electrolytic solution, positive pole and negative pole.
According to the present invention, a kind of addition agent of non-aqueous electrolyte of double electric layer capacitor can be provided, this additive contains burning and the time can discharge in the molecule as the burning inhibiting substances and have P-F key and/or P-NH
2The burning inhibiting substances of the phosphine oxide compound of key discharges compound, and can reduce the flammability of nonaqueous electrolytic solution significantly.In addition, providing a kind of contains above-mentioned additive and can suppress the dangerous double electric layer capacitor nonaqueous electrolytic solution of igniting on fire significantly.A kind of nonaqueous electrolytic solution double electric layer capacitor this nonaqueous electrolytic solution, that can significantly improve fail safe that uses also is provided.
Embodiment
The addition agent of non-aqueous electrolyte of＜double electric layer capacitor 〉
Below describe the addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention in detail.The addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention, the burning inhibiting substances that can discharge the burning inhibiting substances when containing burning discharges compound, it is characterized by, and described burning inhibiting substances is to have P-F key and/or P-NH in the molecule
2The phosphine oxide compound of key can also contain other compositions as required.Have P-F key and/or P-NH in the molecule
2The phosphine oxide compound of key has the combustible effect that suppresses the non-proton organic solvent that contains usually in the electrolyte significantly.Therefore, can discharge by will burn the time in the molecule as the burning inhibiting substances and have P-F key and/or P-NH
2The burning inhibiting substances of the phosphine oxide compound of key discharges compound adds in the nonaqueous electrolytic solution, can suppress the flammability of nonaqueous electrolytic solution significantly.
Above-mentioned burning inhibiting substances, as long as the time can suppress the flame of nonaqueous electrolytic solution after on fire in burning, do not have special qualification, but preferably can give nonaqueous electrolytic solution from putting out characteristic, flame retardancy or non-flame properties material, i.e. self-extinguishment material, flame retardancy material and incombustible.Herein, UL94HB method according to UL (Underwriting Laboratory) standard, to putting out characteristic certainly, flame retardancy and noninflammability define, particularly, make 1.0ml electrolyte infiltrate the noninflammability quartz fibre, the test film of preparation 127mm * 12.7mm, this test film is in atmospheric environment when on fire, flame after on fire between 25～100mm line, extinguish and from net the material that falls also confirm when not on fire for having " putting out characteristic certainly ", flame after on fire do not reach the 25mm line of device and from net the material that falls also confirm when not on fire for having " flame retardancy ", confirm that (burning length is 0mm) is for having " noninflammability " when not on fire.
As long as above-mentioned burning inhibiting substances is for having P-F key and/or P-NH in the molecule
2The phosphine oxide compound of key gets final product, and does not have special qualification.In described phosphine oxide compound, the phosphine oxide compound of preferred above-mentioned formula (I) expression.In formula (I), R
1Be monovalence substituting group or halogen atom independently respectively, and at least one R
1Be fluorine atom or amino., can preferably enumerate fluorine atom, chlorine atom, bromine atoms etc. herein, wherein preferred especially fluorine atom as halogen atom.On the other hand,, can enumerate amino, alkoxyl, alkyl, carboxyl, acyl group, aryl etc., wherein, consider from the superiority aspect that reduces the electrolyte dangerous effect of igniting on fire as the monovalence substituting group, preferred amino.In addition; as above-mentioned alkoxyl; can enumerate methoxyl group, ethyoxyl, methoxy ethoxy, propoxyl group, phenoxy group etc.; as abovementioned alkyl; methyl, ethyl, propyl group, butyl, amyl group etc. can be enumerated,, formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl etc. can be enumerated as above-mentioned acyl group; as above-mentioned aryl, can enumerate phenyl, tolyl, naphthyl etc.Preferably replace hydrogen atom in the above-mentioned monovalence substituting group,, can preferably enumerate fluorine atom, chlorine atom, bromine atoms etc. as halogen atom with halogen atom, fluorine atom most preferably, the chlorine atom takes second place.
Being halogen atom more than the 10 quality % in the preferred molecule of above-mentioned phosphine oxide compound, is halogen atom more than the 15 quality % in the molecule more preferably.In addition, be fluorine atom more than the 7 quality % in the preferred molecule of this phosphine oxide compound, be fluorine atom more than the 10 quality % in the molecule more preferably.Being the phosphine oxide compound of halogen atom more than the 10 quality % in the molecule, suppressing nonaqueous electrolytic solution effect of combustion excellence, is the phosphine oxide compound of fluorine atom more than the 7 quality % in the molecule, and it is excellent especially to suppress the nonaqueous electrolytic solution effect of combustion.
As above-mentioned phosphine oxide compound, at least one R in the special preferred formula (I)
1Be at least one R in fluorine atom and the formula (I)
1Be two above R in the phosphine oxide compound of amino and the above-mentioned formula (I)
1Be fluorine atom or amino phosphine oxide compound.Above-mentioned phosphine oxide compound is because it is higher to help to suppress the fluorine atom and the amino ratio shared in molecule of electrolyte burning, so have excellent inhibition effect of combustion.
As the phosphine oxide compound of above-mentioned formula (I), can enumerate particularly: trifluoro phosphine oxide [O=PF
3], triamido phosphine oxide [O=P (NH
2)
3], amino difluoro phosphine oxide [O=PF
2NH
2], diaminourea fluorine phosphine oxide [O=PF (NH
2)
2], methyl diaminourea phosphine oxide [O=P (NH
2)
2CH
3], methylamino fluorine phosphine oxide [O=PF (NH
2) CH
3], dimethoxy fluorine phosphine oxide [O=PF (OCH
3)
2], ethyoxyl difluoro phosphine oxide [O=PF
2(OC
2H
5)], methoxyl group difluoro phosphine oxide [O=PF
2(OCH
3)], dimethyl fluorine phosphine oxide [O=PF (CH
3)
2], diethoxy fluorine phosphine oxide [O=PF (OC
2H
5)
2], methyl difluoro phosphine oxide [O=PF
2(CH
3)] etc.
The burning inhibiting substances of using in the addition agent of non-aqueous electrolyte of double electric layer capacitor of the present invention discharges compound, as long as can discharge above-mentioned burning inhibiting substances when burning, does not have special qualification, also can discharge CO
2Or other burning inhibiting substances such as phosphate.Herein, so-called " during burning " be meant in the nonaqueous electrolytic solution on fire when flame occurring.Discharge compound as this burning inhibiting substances,, contain the compound of phosphorus and fluorine atom and/or nitrogen-atoms in the preferred molecule from can suitably discharging the aspect of above-mentioned burning inhibiting substances.
When containing phosphorus and fluorine atom in the burning inhibiting substances release compound molecule, under the effect of the fluoro free radical that when above-mentioned burning inhibiting substances and burning, generates, can suppress the flammability of electrolyte more effectively.Discharge in the compound in the burning inhibiting substances, the content of above-mentioned fluorine atom is preferably in the scope of 2～80 quality %, more preferably in the scope of 2～60 quality %, further preferably in the scope of 2～50 quality %.When the content of fluorine atom was lower than 2 quality % in burning inhibiting substances release compound, it was less to suppress the combustible effect of electrolyte, when surpassing 80 quality %, and viscosity increased, the conductance of electrolyte reduces.
In addition, discharge compound, from can suitably discharge molecule, have P-NH as the burning inhibiting substances as above-mentioned burning inhibiting substances
2The aspect of the phosphine oxide compound of key is considered, contains the compound of phosphorus-to-nitrogen bonds in the preferred molecule.As the compound that contains phosphorus-to-nitrogen bonds in the molecule, can enumerate in the molecule the positive phosphine compound of directly amino and phosphorus linkage herein.
Discharge compound as above-mentioned burning inhibiting substances, consider, contain the compound of phosphorus-fluorine bond in the preferred molecule from can suitably discharging as the aspect burning inhibiting substances, that have the phosphine oxide compound of P-F key the molecule.As the compound that contains phosphorus-fluorine bond in the molecule, be phosphine compound, the ring phosphine compound, phosphine oxide compound, ring phosphine oxide compound (cyclophosphineoxide), phosphine borine (phosphine borane) compound, sila phosphine (silaphosphane) compound, phosphorus arsenic ring silazane (phosphoarsenic cyclosilazane) compound, phosphine oxide borine (phosphoxide borane) compound, reach phosphorus-containing compounds such as positive phosphine compound, can use fluorine atom in the molecule directly and the compound of phosphorus linkage, wherein, fluorine atom is directly and the positive phosphine compound of phosphorus linkage in the preferred molecule.
Amino or fluorine atom directly and the positive phosphine compound of phosphorus linkage are represented as following formula (II) in the molecule.
(in the formula, R
2Be monovalence substituting group or halogen atom, in addition, R
3And R
4Be monovalence substituting group, halogen atom or hydrogen atom.R
2, R
3And R
4In at least one is fluorine atom or amino or amine derivative).
The R of formula (II)
2, R
3And R
4In, as halogen atom, can preferably enumerate fluorine atom, chlorine atom, bromine atoms etc., wherein preferred especially fluorine atom.On the other hand, at the R of formula (II)
2, R
3And R
4In, as the monovalence substituting group, can enumerate amino, alkoxyl, alkyl, carboxyl, acyl group, aryl etc., wherein, consider from the superiority aspect that reduces the electrolyte dangerous effect of igniting on fire, preferred amino.In addition; as above-mentioned alkoxyl; can enumerate methoxyl group, ethyoxyl, methoxy ethoxy, propoxyl group, phenoxy group etc.; as abovementioned alkyl; methyl, ethyl, propyl group, butyl, amyl group etc. can be enumerated,, formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl etc. can be enumerated as above-mentioned acyl group; as above-mentioned aryl, can enumerate phenyl, tolyl, naphthyl etc.Preferably replace hydrogen atom in the above-mentioned monovalence substituting group,, can preferably enumerate fluorine atom, chlorine atom, bromine atoms etc. as halogen atom with halogen atom, fluorine atom most preferably, the chlorine atom takes second place.
R
2, R
3And R
4In at least one is the positive phosphine compound of fluorine atom, have the P-F key in the molecule, in burning the time can suitably discharge molecule as the burning inhibiting substances, have the phosphine oxide compound of P-F key.In addition, R
2, R
3And R
4In at least one is amino positive phosphine compound, have P-NH in the molecule
2Key can suitably discharge when burning as having P-NH in burn inhibiting substances and the molecule
2The phosphine oxide compound of key.
Addition agent of non-aqueous electrolyte of the present invention except that containing above-mentioned burning inhibiting substances release compound, can also contain and not hinder the additive arbitrarily that the electrolyte burning suppresses effect.In addition, the burning inhibiting substances discharges the content of compound in addition agent of non-aqueous electrolyte, can suitably select according to the content of burning inhibiting substances release compound in the nonaqueous electrolytic solution described later.
＜double electric layer capacitor nonaqueous electrolytic solution 〉
Below describe double electric layer capacitor nonaqueous electrolytic solution of the present invention in detail.Double electric layer capacitor of the present invention contains above-mentioned addition agent of non-aqueous electrolyte and supporting electrolyte with nonaqueous electrolytic solution, can also contain non-proton organic solvent etc. as required.
As being used for double electric layer capacitor of the present invention supporting electrolyte with nonaqueous electrolytic solution, can from present known material, select, but from conductivity electrolyte etc. good aspect consider preferred quaternary ammonium salt.In nonaqueous electrolytic solution, this quaternary ammonium salt is the solute that plays a role as the ion source that is used to form electric double layer, from improving the aspect consideration of electrical characteristics such as electrolyte conductivity effectively, preferably can form the quaternary ammonium salt of multivalent ion.
As above-mentioned quaternary ammonium salt, for example can preferably enumerate (CH
3)
4NBF
4, (CH
3)
3C
2H
5NBF
4, (CH
3)
2(C
2H
5)
2NBF
4, CH
3(C
2H
5)
3NBF
4, (C
2H
5)
4NBF
4, (C
3H
7)
4NBF
4, CH
3(C
4H
9)
3NBF
4, (C
4H
9)
4NBF
4, (C
6H
13)
4NBF
4, (C
2H
5)
4NClO
4, (C
2H
5)
4NAsF
6, (C
2H
5)
4NSbF
6, (C
2H
5)
4NCF
3SO
3, (C
2H
5)
4NC
4F
9SO
3, (C
2H
5)
4N (CF
3SO
2)
2N, (C
2H
5)
4NBCH
3(C
2H
5)
3, (C
2H
5)
4NB (C
2H
5)
4, (C
2H
5)
4NB (C
4H
9)
4, (C
2H
5)
4NB (C
6H
5)
4Deng.In addition, also preferably use PF
6(for example, the BF of anion portion that replaces above-mentioned quaternary ammonium salt
4, ClO
4, AsF
6Deng) hexafluorophosphate of gained.Wherein, consider the quaternary ammonium salt of preferred different alkyl and N atomic linkage from the aspect that can improve solubility by increase polarity.As above-mentioned quaternary ammonium salt, the compound that preference is represented as shown in the formula (a)～(j) etc.Me represents methyl in formula (a)～(j), and Et represents ethyl.
In the above-mentioned quaternary ammonium salt, consider, especially preferably can generate as cationic (CH from the aspect of guaranteeing high conductivity
3)
4N
+, or (C
2H
5)
4N
+Deng salt.In addition, preferably can generate the little anionic salt of molecular weight.Above-mentioned quaternary ammonium salt can use a kind separately, also can share more than 2 kinds.
As the concentration of double electric layer capacitor of the present invention with the supporting electrolyte in the nonaqueous electrolytic solution, preferred 0.2～2.5mol/L (M), more preferably 0.8～1.5mol/L (M).If the concentration of supporting electrolyte is lower than 0.2mol/L (M), then can not fully guarantee the electrical characteristics such as conductivity of electrolyte, if surpass 2.5mol/L (M), then the viscosity of electrolyte increases, and makes electrical characteristics reductions such as conductivity.
The non-proton organic solvent that uses in the nonaqueous electrolytic solution of the present invention can make the electrolyte lowering viscousity, can easily obtain the suitableeest ionic conductivity as double electric layer capacitor.As this non-proton organic solvent, particularly, can suitably enumerate nitrile compounds such as acetonitrile (AN), propionitrile, butyronitrile, isobutyronitrile, benzonitrile; 1,2-dimethoxy-ethane (DME), oxolane ether compounds such as (THF); Ester compounds such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), diphenyl carbonate, gamma-butyrolacton (GBL), gamma-valerolactone.Wherein, preferred propylene carbonate, gamma-butyrolacton and acetonitrile.In addition, consider that preferred cyclic ester compound in addition, is considered preferred chain ester compounds and ether compound from make the aspect of electrolyte lowering viscousity because of viscosity is low from the aspect of dielectric constant height, supporting electrolyte dissolubility excellence.Above-mentioned non-proton organic solvent can use a kind separately, also can share more than 2 kinds.
Double electric layer capacitor nonaqueous electrolytic solution of the present invention, this nonaqueous electrolytic solution of every 1L discharges the above above-mentioned burning inhibiting substances of 0.03mol during preferred burn, more preferably discharges 0.05～0.5mol.If the burst size of the inhibiting substances of burning in every 1L nonaqueous electrolytic solution during burning is lower than 0.03mol, then can not suppress the flammability of nonaqueous electrolytic solution fully.
At the containing ratio of double electric layer capacitor of the present invention, preferably more than 3 volume %, more preferably more than 5 volume % with above-mentioned burning inhibiting substances release compound in the nonaqueous electrolytic solution.Above-mentioned burning inhibiting substances discharges the containing ratio of compound in nonaqueous electrolytic solution when 3 volume % are above, can suppress nonaqueous electrolytic solution danger of igniting on fire fully.Need to prove that double electric layer capacitor nonaqueous electrolytic solution of the present invention can only contain a kind of above-mentioned burning inhibiting substances and discharge compound, also can contain two or more.
＜nonaqueous electrolytic solution double electric layer capacitor 〉
Describe nonaqueous electrolytic solution double electric layer capacitor of the present invention below in detail.Nonaqueous electrolytic solution double electric layer capacitor of the present invention has above-mentioned double electric layer capacitor nonaqueous electrolytic solution, positive pole and negative pole.As required, miscellaneous part commonly used in the double electric layer capacitor technical field such as barrier film can be set.
Positive pole and negative pole as nonaqueous electrolytic solution double electric layer capacitor of the present invention do not have special qualification, but the polar electric pole of usually preferred porous carbon class.As this electrode, usually preferably has the electrode of the big and characteristic such as bulk density big, electrochemistry is inertia, resistance is little of specific area.As above-mentioned porous carbon, can enumerate active carbon etc.
Above-mentioned electrode generally contains porous carbons such as active carbon, can also contain other compositions such as conductive agent or binding agent as required.As the raw material of the active carbon that is applicable to above-mentioned electrode, there is not special qualification, for example can preferably enumerate phenol resin, various heat-resistant resin, pitch etc.As heat-resistant resin, for example can preferably enumerate polyimides, polyamide, polyamidoimide, Polyetherimide, polyether sulfone, polyether-ketone, Bismaleimide Triazine, aromatic polyamides, fluororesin, polyphenylene, polyphenylene sulfide etc.Above-mentioned substance can use a kind separately, also can share more than 2 kinds.As the form of above-mentioned active carbon, consider forms such as preferred powder powder, fiber cloth shape from the aspect that the charging capacity of the big more nonaqueous electrolytic solution double electric layer capacitor of specific area is big more.In addition, above-mentioned active carbon is the charging capacity that further improves double electric layer capacitor, can heat-treat, extend shapings, vacuum high-temperature processing, processing such as rolling.
As the conductive agent that uses in the above-mentioned electrode, there is not special qualification, can enumerate graphite, acetylene black etc.In addition,, do not have special qualification, can enumerate Kynoar (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene ribber (SBR), carboxymethyl cellulose (CMC) etc. as the binding agent that uses in the above-mentioned electrode.Above-mentioned additive can be in using with identical in the past cooperation ratio.
Nonaqueous electrolytic solution double electric layer capacitor of the present invention, the above-mentioned electrode of preferred disposition (positive pole and negative pole), nonaqueous electrolytic solution, barrier film, current-collector, container etc. can also dispose known each parts that use usually in double electric layer capacitor.Herein, barrier film is arranged between both positive and negative polarity, is used for short circuit that prevents by the nonaqueous electrolytic solution double electric layer capacitor etc.As this barrier film, there is not special qualification, preferably use the known common barrier film that uses as the barrier film of nonaqueous electrolytic solution double electric layer capacitor.As the material of barrier film, preferably enumerate microporous membrane, nonwoven fabrics, paper etc.Particularly, can preferably enumerate synthetic resin system nonwoven fabrics, films etc. such as polytetrafluoroethylene, polypropylene, polyethylene.Wherein, special preferred thickness is about polypropylene or the polyethylene microporous membrane of 20～50 μ m.
As above-mentioned current-collector, there is not special qualification, preferably use the known current-collector that is generally used for the nonaqueous electrolytic solution double electric layer capacitor.As this current-collector, preferably has the excellent low current-collector of electrochemical corrosion resistant, chemical resistance, processability, mechanical strength and cost, current collector layer such as preferred aluminium, stainless steel, electroconductive resin etc.In addition,, do not have special qualification, can preferably enumerate the known container that is generally used for the nonaqueous electrolytic solution double electric layer capacitor as said vesse.As the material of this container, preferred aluminium, stainless steel, electroconductive resin etc.
As the form of nonaqueous electrolytic solution double electric layer capacitor of the present invention, there is not special qualification, can preferably enumerate column type (cylinder type, angle type), platypelloid type known forms such as (Coin shapes).Above-mentioned nonaqueous electrolytic solution double electric layer capacitor; for example can be preferably used as the main power source or the accessory power supply of electric automobile or fuel cell car; or be used for various electronic equipments, industry with apparatus, aviation memory power-off protection with apparatus etc.; or be used for the electromagnetic compatibility (electromagnetic holding) of toy, wireless device, gas apparatus, fast water heater etc., or be used for the power supply etc. of table usefulness such as wrist-watch, clock and watch, solar watch, AGS wrist-watch.
＜embodiment 〉
Below enumerate embodiment and further describe the present invention, but the present invention is not limited to following embodiment.
(embodiment 1)
With tetraethylammonium tetrafluoroborate [Et
4NBF
4] (supporting electrolyte) be dissolved in the mixed solution that the phosphorane compd A by the expression of 90 volume % propylene carbonates (PC) and the following formulas of 10 volume % (III) constitutes, making its concentration is 1mol/L (M), the preparation nonaqueous electrolytic solution.
Estimate the fail safe of gained nonaqueous electrolytic solution according to the UL94HB method of above-mentioned UL (Underwriting laboratory) standard.Need to prove, in this test, when surpassing the 100mm line with the flame after on fire as " flammability ".The growing amount of phosphine oxide compound when in addition, measuring the limited oxygen index (limit oxygen index) of nonaqueous electrolytic solution and burning according to following method.The result is as shown in table 1.
(1) limited oxygen index of electrolyte
Measure the limited oxygen index of electrolyte according to JIS K 7201.Limited oxygen index is big more, and expression electrolyte is difficult to burning more.Particularly, strengthen 127mm * 12.7mm SiO by aluminium foil with the U font
2Thin slice (quartz filter paper, noninflammability) makes it to become the self-supporting body, the above-mentioned electrolyte of 1.0ml is contained to be immersed in this SiO again
2Make test film in the thin slice.This test film vertically is placed on the test film supporting member, make it to be positioned at apart from combustion cylinder (internal diameter: 75mm, high: 450mm, in the thickness of bottom to 100 ± 5mm, be full of the glass particle that diameter is 4mm equably, and lay wire netting thereon) the above place of upper end 100mm, then, aerating oxygen in combustion cylinder (JIS K 1101 or with its equal above oxygen) and nitrogen (2 grades of JIS K 1107 or with its nitrogen more than on an equal basis), under the oxygen concentration of regulation, light (thermal source be a kind of JIS K2240 No. 1) test film, observe its fired state.The interior total flow of combustion cylinder this moment is 11.4L/min.This test is carried out 3 times, and its mean value is as shown in table 2.Need to prove, so-called oxygen index is meant the value of keeping the necessary minimum oxygen concentration of representing with percent by volume of material combustion, among the application, according to the test film sustained combustion more than 3 minutes, or the burning length after catching fire is 50mm necessary minimum oxygen flow and nitrogen flow of this moment when above, according to following formula calculating limit oxygen index.
Limited oxygen index=(oxygen flow)/[(oxygen flow)+(nitrogen flow)] * 100
The growing amount of phosphine oxide compound when (2) burning
(in 30 * 30 * 30cm), under 800 ℃ flame temperature, light the electrolyte that is immersed in the noninflammability quartz plate, the gas that generates is collected in the gas trapping pipe (being filled with Tenax TA), analyze in the combustion chamber with TDS-GC-MS.Need to prove that (thickness: 0.25 μ m), column temperature is 40-300 ℃ (programming rate: 25 ℃/minute) for column length: 30m, internal diameter: 0.25mm, and the mass range that MS measures is 5～500 to use the DB-5 chromatographic column among the GC.
＜nonaqueous electrolytic solution electric double-layer capacitors prepared 〉
Then with active carbon [AC, trade name: Kuractive-1500, Kurare Chemical society system], acetylene black (conductive agent) and Kynoar (PVDF) (binding agent) mix respectively, makes its mass ratio (active carbon: acetylene black: PVDF) be 8: 1: 1, obtain mixture.The mixture of weighing 100mg gained puts it in the withstand voltage carbon container made of 20mm φ, is 150kgf/cm at pressure
2, normal temperature condition under press-powder be shaped preparation positive pole and negative pole (electrode).(thickness: 0.5mm) (thickness: assembled battery 25 μ m) makes it dry fully by vacuumize with polypropylene, polyethylene plate (barrier film) for the electrode (positive pole and negative pole) of use gained, aluminium metal sheet (current-collector).With above-mentioned this battery of nonaqueous electrolytic solution impregnation, make the nonaqueous electrolytic solution double electric layer capacitor.Test electrical conductivity, cycle characteristics and the low-temperature characteristics of gained nonaqueous electrolytic solution double electric layer capacitor as follows.The result is as shown in table 1.
(3) electrical conductivity
Apply the constant current of 5mA to gained nonaqueous electrolytic solution double electric layer capacitor, adopt conductivity meter [trade name: CDM210, Radiometer Trading (strain) system] simultaneously, measure electrical conductivity.
(4) double electric layer capacitor characteristic
Reach the static capacity of measuring gained nonaqueous electrolytic solution double electric layer capacitor after the charging and discharging circulation 1000 times in the early stage, calculates the capability retention after circulating for 1000 times, the evaluation cycle characteristic.
(5) low-temperature characteristics of double electric layer capacitor
Under 20 ℃ ,-10 ℃ environment, measure the internal resistance of gained nonaqueous electrolytic solution double electric layer capacitor respectively, estimate the low-temperature characteristics of capacitor., can measure internal drag (Ω) herein, for example measure charging and discharging curve and following this moment charging to stop the method that (charge rest) or discharge stop the potential amplitude of (discharge rest) to measure by known internal resistance assay method.
(embodiment 2)
Except that the phosphorane compd B with following formula (IV) expression replaces preparing nonaqueous electrolytic solution in the same manner with embodiment 1 the phosphorane compd A of above-mentioned formula (III) expression, and the growing amount of the fail safe of this nonaqueous electrolytic solution of evaluating and measuring and phosphine oxide compound.And then, use this nonaqueous electrolytic solution, make double electric layer capacitor in the same manner with embodiment 1, and estimate the performance of this double electric layer capacitor.The result is as shown in table 1.
(embodiment 3)
Except that the phosphorane Compound C with following formula (V) expression replaces the phosphorane compd A of above-mentioned formula (III) expression, make evaluation nonaqueous electrolytic solution and double electric layer capacitor in the same manner with embodiment 1.The result is as shown in table 1.
(comparative example 1)
With tetraethylammonium tetrafluoroborate [Et
4NBF
4] (supporting electrolyte) be dissolved in the 100 volume % propylene carbonates (PC), making its concentration is 1mol/L (M), the preparation nonaqueous electrolytic solution is estimated in the same manner with embodiment 1.In addition, use this nonaqueous electrolytic solution, make double electric layer capacitor in the same manner, estimate with embodiment 1.The result is as shown in table 1.
Among the embodiment 1～3, generate the phosphine oxide compound that has P-F key and/or P-NH2 key in the molecule during nonaqueous electrolytic solution burning, can suppress the flammability of this nonaqueous electrolytic solution.In addition, the double electric layer capacitor of embodiment 1～3 has the abundant characteristic as capacitor.
Claims (17)
1, a kind of addition agent of non-aqueous electrolyte of double electric layer capacitor, described additive can discharge the burning inhibiting substances when containing burning burning inhibiting substances discharges compound, it is characterized by, and described burning inhibiting substances is to have P-F key and/or P-NH in the molecule
2The phosphine oxide compound of key.
2, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 1 is characterized by, and described burning inhibiting substances is at least a in self-extinguishment material, flame retardancy material and the incombustible.
3, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 1 is characterized by, described phosphine oxide compound shown in following formula (I),
O＝PR
1 3 ····(I)
In the formula, R
1Be monovalence substituting group or halogen atom independently respectively, at least one R
1Be fluorine atom or amino.
4, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 3 is characterized by, the R in the described formula (I)
1Be independently selected from fluorine atom, amino, alkyl and alkoxyl respectively, and at least one R
1Be fluorine atom or amino.
5, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 4 is characterized by, at least one R in the described formula (I)
1Be fluorine atom, and at least one R in the formula (I)
1Be amino.
6, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 4 is characterized by, the R in the described formula (I)
1Independent respectively is fluorine atom or amino.
7, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 1 is characterized by, and described burning inhibiting substances discharges in the compound molecule and contains phosphorus and fluorine atom and/or nitrogen-atoms.
8, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 7 is characterized by, and described burning inhibiting substances discharges in the compound molecule and has phosphorus-to-nitrogen bonds.
9, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 7 is characterized by, and described burning inhibiting substances discharges in the compound molecule and has phosphorus-fluorine bond.
10, the addition agent of non-aqueous electrolyte of double electric layer capacitor as claimed in claim 8 or 9 is characterized by, and it is positive phosphine compound that described burning inhibiting substances discharges compound.
11, a kind of double electric layer capacitor nonaqueous electrolytic solution, described nonaqueous electrolytic solution contains the addition agent of non-aqueous electrolyte and the supporting electrolyte of each described double electric layer capacitor in the claim 1～10.
12, double electric layer capacitor nonaqueous electrolytic solution as claimed in claim 11 is characterized by, and also contains non-proton organic solvent in the described nonaqueous electrolytic solution.
13, double electric layer capacitor nonaqueous electrolytic solution as claimed in claim 12 is characterized by, and described non-proton organic solvent contains the ester compounds of nitrile compound, ring-type or chain or the ether compound of chain.
14, double electric layer capacitor nonaqueous electrolytic solution as claimed in claim 11 is characterized by, and the described double electric layer capacitor of every 1L discharges burning inhibiting substances more than the 0.03mol with nonaqueous electrolytic solution during burning.
15, double electric layer capacitor nonaqueous electrolytic solution as claimed in claim 11 is characterized by, and described nonaqueous electrolytic solution contains the above described burning inhibiting substances of 3 volume % and discharges compound.
16, double electric layer capacitor nonaqueous electrolytic solution as claimed in claim 15 is characterized by, and described nonaqueous electrolytic solution contains the above described burning inhibiting substances of 5 volume % and discharges compound.
17, a kind of nonaqueous electrolytic solution double electric layer capacitor, described double electric layer capacitor have comprised each described double electric layer capacitor nonaqueous electrolytic solution, positive pole and negative pole in the claim 11～16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP131151/2004 | 2004-04-27 | ||
| JP2004131151 | 2004-04-27 | ||
| JP353975/2004 | 2004-12-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1947211A CN1947211A (en) | 2007-04-11 |
| CN100550240C true CN100550240C (en) | 2009-10-14 |
Family
ID=38045549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800131897A Expired - Fee Related CN100550240C (en) | 2004-04-27 | 2005-03-29 | Addition agent of non-aqueous electrolyte, nonaqueous electrolytic solution and double electric layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100550240C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114507257B (en) * | 2021-06-07 | 2023-04-18 | 华南师范大学 | Fluorinated cyclic phosphorus-containing molecule and application thereof |
-
2005
- 2005-03-29 CN CNB2005800131897A patent/CN100550240C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1947211A (en) | 2007-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100767741B1 (en) | Additive for non-aqueous liquid electrolyte, non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor | |
| CA2422106C (en) | Additive for non-aqueous liquid electrolyte, non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor | |
| CN100380727C (en) | Additive for cell and electric double-layered capactitor | |
| US6452782B1 (en) | Non-aqueous electrolyte electric double-layer capacitor, deterioration inhibitor for non-aqueous electrolyte electric double-layer capacitor and additive for non-aqueous electrolyte electric double-layer capacitor | |
| JP5684138B2 (en) | Electric storage device and electrolyte used therefor | |
| JP5001507B2 (en) | Nonaqueous electrolyte additive, nonaqueous electrolyte secondary battery, and nonaqueous electrolyte electric double layer capacitor | |
| Nanbu et al. | Physical and electrochemical properties of quaternary ammonium bis (oxalato) borates and their application to electric double-layer capacitors | |
| EP3061148A1 (en) | Flame retardant for electrolytes for batteries | |
| KR20050088229A (en) | Additive for nonaqueous electrolytic solution of electric double layer capacitor and nonaqueous electrolyte electric double layer capacitor | |
| Nam et al. | Triethyl and tributyl phosphite as flame-retarding additives in Li-ion batteries | |
| CN105336506B (en) | A kind of nonflammable electrolytic solution for super capacitor | |
| JP2006294332A (en) | Nonaqueous electrolyte solution, nonaqueous electrolyte solution battery, nonaqueous electrolyte solution electric double-layer capacitor, and safety evaluation method of nonaqueous electrolyte solution | |
| CN100550240C (en) | Addition agent of non-aqueous electrolyte, nonaqueous electrolytic solution and double electric layer capacitor | |
| JP2008300523A (en) | Nonaqueous electrolyte for capacitor, and nonaqueous electrolyte capacitor having the nanoqueous electrolyte | |
| JP2001217156A (en) | Nonaqueous electrolytic solution electric double-layer capacitor | |
| JP2001217155A (en) | Nonaqueous electrolytic solution electric double-layer capacitor | |
| JP2001217152A (en) | Additive for nonaqueous electrolytic solution electric double-layer capacitor | |
| US20090213528A1 (en) | Additive for non-aqueous electrolyte of electric double layer capacitor, non-aqueous electrolyte for electric double layer capacitor and non-aqueous electrolyte electric double layer capacitor | |
| JP2004349273A (en) | Nonaqueous electrolyte and electric double layer capacitor provided with it | |
| JP2007012983A (en) | Nonaqueous electrolyte type electric double layer capacitor and nonaqueous electrolyte therefor | |
| JP2001217157A (en) | Nonaqueous electrolytic solution electric double-layer capacitor | |
| JP2008300525A (en) | Nonaqueous electrolyte for capacitor, and nonaqueous electrolyte capacitor having the nanoqueous electrolyte | |
| CN106410280A (en) | Composite electrolyte and ionic battery | |
| JP2001217158A (en) | Nonaquous electrolytic solution electric double-layer capacitor | |
| JP4511328B2 (en) | Non-aqueous electrolyte for electric double layer capacitor and non-aqueous electrolyte electric double layer capacitor having the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091014 Termination date: 20140329 |