CN100486009C - Nonaqueous electrolyte, and nonaqueous electrolyte battery having same - Google Patents
Nonaqueous electrolyte, and nonaqueous electrolyte battery having same Download PDFInfo
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- CN100486009C CN100486009C CNB2005800390321A CN200580039032A CN100486009C CN 100486009 C CN100486009 C CN 100486009C CN B2005800390321 A CNB2005800390321 A CN B2005800390321A CN 200580039032 A CN200580039032 A CN 200580039032A CN 100486009 C CN100486009 C CN 100486009C
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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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Abstract
This invention relates to a non-aqueous electrolyte exhibiting a non-combustibility even under a condition having a higher oxygen concentration, and more particularly to a non-aqueous electrolyte characterized by comprising a non-aqueous solvent containing a cyclic phosphazene compound represented by the following general formula (I): (NPR 1 2 ) n ... (I) [wherein R 1 s are independently a halogen element or a monovalent substituent; and n is 3-4] and a fluorophosphate compound represented by the following general formula (II): [wherein R 2 s are independently a halogen element, an alkoxy group or an aryloxy group, and at least one of the two R 2 s is the alkoxy group or the aryloxy group], and a support salt.
Description
Technical field
The present invention relates to nonaqueous electrolyte and the nonaqueous electrolyte battery that comprises this nonaqueous electrolyte, the nonaqueous electrolyte battery that relates more particularly to have high non-flame properties nonaqueous electrolyte He have good battery performance.
Background technology
With the electrolyte of nonaqueous electrolyte as lithium battery, lithium rechargeable battery, double electric layer capacitor etc., and these equipment have high voltage and high-energy-density, thereby they are widely used as the driving power of PC, mobile phone etc.In addition, normally used as nonaqueous electrolyte is by with supporting electrolyte such as LiPF
6Or analog is dissolved in those that obtain in aprotic organic solvent such as ester compounds, ether compound or the analog.Yet,, when leaking in its slave unit, might catch fire-burn, and have the problem of fail safe aspect because aprotic organic solvent is flammable.
For this problem, studied the method for giving the nonaqueous electrolyte anti-flammability.For example, suggestion is used for phosphate such as trimethyl phosphate or analog the method for nonaqueous electrolyte, phosphate is added the method (seeing JP-A-H4-184870, JP-A-H8-22839 and JP-A-2000-182669) of aprotic organic solvent.Yet, by discharging repeatedly-recharge, phosphate reduce gradually at negative pole-decompose so that the performance that highly worsens battery as discharging-recharge efficient, cycle performance etc., cause its addition limited.
For this problem, attempted to suppress compound that phosphate decomposes and further joined in the nonaqueous electrolyte or the methods such as molecular structure (seeing JP-A-H11-67267, JP-A-H10-189040 and JP-A-2003-109659) of design phosphate self.Yet even in this case, the anti-flammability that exist to add quantitative limitation and phosphate itself also worsens etc., causes electrolyte only to obtain self-extinguishment, can not fully guarantee electrolytical fail safe.
In addition, JP-A-H06-13108 discloses phosphazene compound has been joined nonaqueous electrolyte to give the method for nonaqueous electrolyte anti-flammability.Some phosphazene compounds show high noninflammability, and with its increase that joins the amount of nonaqueous electrolyte, have the trend that improves the nonaqueous electrolyte anti-flammability.Yet owing to show that the dissolubility and the dielectric constant of the general supporting electrolyte of high non-flame properties phosphazene compound are low, along with addition increases, the precipitation and the conductivity that cause supporting electrolyte reduce, thereby can make the discharge capacity reduction of battery that discharge-recyclability is worsened.Therefore, when add showing high non-flame properties phosphazene compound, there is the limited problem of addition.
On the other hand, for main power source or the accessory power supply as motor vehicle and fuel-cell vehicle, latest developments increase battery size and further improve its energy density, require battery to have the fail safe higher than traditional battery.In traditional non-aqueous secondary batteries, if emergency as overcharge, big electric current acutely flows and battery produces unusual heat when external short circuit or its similar phenomenon, is used for anodal metal oxide and decomposes, and produces a large amount of oxygen.Thereby inside battery is in than oxygen concentration state much higher in atmosphere and is exposed to and can be very easy to cause under the condition of lighting-catching fire.
When battery explosion or catch fire by the gas that in this condition, produces and heat or during the spark ignition that produces by in short circuit the time, as if it is very big that the infringement that is produced becomes.Therefore, it is desirable to nonaqueous electrolyte not only is non-flame properties in standard atmospheric pressure but also under the condition with higher oxygen concentration.Also think to have so higher non-flame properties nonaqueous electrolyte, can reduce the fail safe of lighting-catching fire the dangerous of battery and improving battery considerably widely by use.Yet in the conventional method of adding above-mentioned phosphate or phosphazene compound, the raising of anti-flammability is limited.
Summary of the invention
Therefore, also show non-flame properties nonaqueous electrolyte under the condition of hyperoxia concentration more and comprise such nonaqueous electrolyte and have the nonaqueous electrolyte battery of good battery performance even the objective of the invention is to solve the problem of above-mentioned conventional art and provide having.
In order to achieve the above object, the inventor has carried out various researchs, and the noninflammability of finding nonaqueous electrolyte can improve greatly by use the nonaqueous solvents that contains specific phosphazene compound and specific phosphate compound in nonaqueous electrolyte, keep using battery performance such as discharge capacity, the cycle performance etc. of so electrolytical nonaqueous electrolyte battery simultaneously, the result has finished the present invention.
That is, nonaqueous electrolyte according to the present invention is characterised in that and comprises and containing by the cyclic phosphazene compound of following general formula (I) expression with by the nonaqueous solvents and the supporting electrolyte of the fluorophosphoric acid ester compounds of following general formula (II) expression:
(NPR
1 2)
n…(I)
[R wherein
1Be halogen element or unit price substituting group independently; N is 3-4]:
[R wherein
2Be halogen, alkoxyl or aryloxy group independently, two R
2In at least one be alkoxyl or aryloxy group].
In nonaqueous electrolyte according to the present invention, as preferred two R wherein of fluorophosphoric acid ester compounds
2In one be fluorine, another is the compound of the general formula (II) of alkoxyl or aryloxy group.
In nonaqueous electrolyte according to the present invention, as cyclic phosphazene compound, preferred R wherein
1Be compound and at least three R wherein of the general formula (I) of fluorine, alkoxyl or aryloxy group independently
1Compound for the general formula (I) of fluorine.
In preferred embodiment according to nonaqueous electrolyte of the present invention, by the cyclic phosphazene compound of general formula (I) expression with by the volume ratio of the fluorophosphoric acid ester compounds of general formula (II) expression in the scope of 30/70-70/30.
In another preferred embodiment according to nonaqueous electrolyte of the present invention, nonaqueous solvents further contains aprotic organic solvent.
In nonaqueous electrolyte according to the present invention, in nonaqueous solvents, preferably be not less than 15 volume % by the cyclic phosphazene compound of general formula (I) expression with by the total content of the fluorophosphoric acid ester compounds of general formula (II) expression, more preferably be not less than 70 volume %.
Preferably further contain by the unsaturated cyclic ester compounds of following general formula (III) expression and/or the aromatic compound of representing by following general formula (IV) according to nonaqueous electrolyte of the present invention:
[R wherein
3Be hydrogen, fluorine or the alkyl with carbon number 1-2 independently, condition is two R
3Bonding is to form ring each other]
[R wherein
4Be hydrogen, fluorine, alkoxyl, alkyl or cycloalkyl or aryl independently] with carbon number 1-6 with carbon number 1-2.
In addition, nonaqueous electrolyte battery according to the present invention is characterised in that and comprises above-mentioned nonaqueous electrolyte, positive pole and negative pole.
According to the present invention, the nonaqueous electrolyte that uses the nonaqueous solvents that contains specific phosphazene compound and specific phosphate compound can be provided, this nonaqueous electrolyte has very high noninflammability and can fully keep battery performance when being applied to nonaqueous electrolyte battery.In addition, can provide the nonaqueous electrolyte battery that comprises such nonaqueous electrolyte and have high noninflammability and good battery performance.
Embodiment
＜nonaqueous electrolyte 〉
Describe in detail according to nonaqueous electrolyte of the present invention below.Nonaqueous electrolyte according to the present invention is characterised in that and comprises and containing by the cyclic phosphazene compound of general formula (I) expression with by the nonaqueous solvents and the supporting electrolyte of the fluorophosphoric acid ester compounds of general formula (II) expression.In addition, nonaqueous solvents can contain aprotic organic solvent.So far, when each of phosphazene compound and phosphate compound is used separately, restricted aspect the noninflammability of balance nonaqueous electrolyte and battery performance, but the noninflammability of nonaqueous electrolyte and battery performance can obtain the height balance by the phosphazene compound of use formula (I) and the fluorophosphoric acid ester compounds combination of formula (II).Although reason may not be clear, but the synergy that it is believed that the fluorophosphoric acid ester compounds of the phosphazene compound of through type (I) and formula (II) forms stable coating on electrode surface, the result, make battery discharge-recharge stable in properties, even the height non-flammable gases component that reaction and thermal decomposition by phosphazene compound and fluorophosphoric acid ester compounds produce is more also forming noninflammability under the hyperoxia concentration.
Be used for representing by general formula (I) according to the cyclic phosphazene compound of nonaqueous electrolyte of the present invention.In formula (I), R
1No particular restriction, as long as it is halogen or unit price substituting group, R
1Can be identical or different.As halogen, preferred fluorine, chlorine, bromine etc.Wherein, from low viscous viewpoint, fluorine is most preferred, and chlorine is secondly preferred.
In addition, as the R of formula (I)
1In the unit price substituting group, mention alkoxyl, aryloxy group, alkyl, aryl, acyl group, replacement or non-substituted-amino, alkylthio group, arylthio etc.Wherein, from the good viewpoint of noninflammability, alkoxyl and aryloxy group are preferred.As alkoxyl, mention methoxyl group, ethyoxyl, propoxyl group, butoxy etc., contain the allyloxy of two keys etc., alkoxyl such as methoxyethoxy, methoxy (ethoxy) ethyoxyl etc. that alkoxyl replaces.As aryloxy group, mention phenoxy group, methylphenoxy, methoxyl group phenoxy group etc.As alkyl, mention methyl, ethyl, propyl group, butyl, amyl group etc.As aryl, mention phenyl, tolyl, naphthyl etc.As replacing or substituted-amino not, mention amino, methylamino, dimethylamino, ethylamino, diethylamino, aziridinyl (aziridyl group), pyrrolidinyl (pyrolidylgroup) etc.As alkylthio group, mention methyl mercapto, ethylmercapto group etc.Mention thiophenyl etc. as arylthio.In these unit price substituting groups, protium can replace and preferably replace with fluorine with halogen.
R in formula (I)
1From improving the preferred halogen of viewpoint of anti-flammability, from more preferably fluorine of low viscous viewpoint.In addition, consider balance anti-flammability and low viscosity, preferred three or more R
1Be fluorine.
In addition, the n of (I) is 3-4 in formula, considers cost and is easy to preparation, and n is preferably 3.Phosphazene compound can use separately or be used in combination with two or more.
Be used for representing by general formula (II) according to the fluorophosphoric acid ester compounds of nonaqueous electrolyte of the present invention.R in formula (II)
2Be halogen, alkoxyl or aryloxy group, two R
2In at least one be alkoxyl or aryloxy group.As halogen, preferred fluorine, chlorine, bromine etc.Wherein, from low viscous viewpoint, fluorine is most preferred.
R as formula (II)
2In alkoxyl, mention methoxyl group, ethyoxyl, propoxyl group, butoxy etc., contain the allyloxy etc. of two keys, alkoxyl such as methoxyethoxy, the methoxy (ethoxy) ethyoxyl etc. that alkoxyl replaces.In these alkoxyls, protium can replace and preferably replace with fluorine with halogen.Wherein, from good anti-flammability and low viscous viewpoint, more preferably methoxyl group, ethyoxyl, trifluoro ethoxy and propoxyl group.
R as formula (II)
2In aryloxy group, mention phenoxy group, methylphenoxy, methoxyl group phenoxy group etc.In these aryloxy group, protium can replace and preferably replace with fluorine with halogen.Wherein, from excellent flame retardancy and low viscous viewpoint, more preferably phenoxy group and fluorophenoxy.
Two R in formula (II)
2Can be identical or different, and also each other bonding to form ring.In addition, consider balance anti-flammability and low viscosity, most preferably two R wherein
2In one be fluorine, another is the difluorophosphoric acid ester of alkoxyl or aryloxy group.
Fluorophosphoric acid ester as formula (II), specifically mention the fluorophosphoric acid dimethyl ester, DFP, two (trifluoroethyl) esters of fluorophosphoric acid, the fluorophosphoric acid ethyl, the fluorophosphoric acid dipropyl, the fluorophosphoric acid diallyl, the fluorophosphoric acid dibutyl ester, the fluorophosphoric acid diphenyl ester, fluorophosphoric acid difluoro phenyl ester, chlorine fluorophosphoric acid methyl esters, chlorine fluorophosphoric acid ethyl ester, chlorine fluorophosphoric acid trifluoro ethyl ester, chlorine fluorophosphoric acid propyl ester, chlorine fluorophosphoric acid allyl ester, chlorine fluorophosphoric acid butyl ester, chlorine fluorophosphoric acid cyclohexyl, chlorine fluorophosphoric acid methoxyl group ethyl ester, chlorine fluorophosphoric acid methoxy ethoxy ethyl ester, chlorine fluorophosphoric acid phenyl ester, chlorine fluorophosphoric acid fluorobenzene ester, the difluorophosphoric acid methyl esters, the difluorophosphoric acid ethyl ester, the difluorophosphoric acid trifluoro ethyl ester, the difluorophosphoric acid propyl ester, difluorophosphoric acid tetrafluoro propyl ester, the difluorophosphoric acid allyl ester, the difluorophosphoric acid butyl ester, the difluorophosphoric acid cyclohexyl, difluorophosphoric acid methoxyl group ethyl ester, difluorophosphoric acid methoxy ethoxy ethyl ester, the difluorophosphoric acid phenyl ester, difluorophosphoric acid fluorobenzene ester etc.Wherein, two (trifluoroethyl) esters of preferred fluorophosphoric acid, fluorophosphoric acid ethyl, difluorophosphoric acid methyl esters, difluorophosphoric acid ethyl ester, difluorophosphoric acid trifluoro ethyl ester, difluorophosphoric acid propyl ester, difluorophosphoric acid tetrafluoro propyl ester and difluorophosphoric acid phenyl ester.These fluorophosphoric acid esters can use separately or be used in combination with two or more.
In nonaqueous electrolyte according to the present invention, from balancing battery performance and non-flame properties viewpoint, the volume ratio of cyclic phosphazene compound and fluorophosphoric acid ester compounds is preferably in the scope of 5/95-95/5, more preferably in the scope of 30/70-70/30.
Preferably contain the unsaturated cyclic ester compounds of representing by general formula (III) according to nonaqueous electrolyte of the present invention.In formula (III), R
3For hydrogen, fluorine or have the alkyl of carbon number 1-2, and the protium in alkyl can replace with fluorine.In addition, two R in formula (III)
3Can be identical or different, or bonding forms ring each other, and it can also have unsaturated bond.As passing through two R of bonding
3The divalent group that forms, mention alkylidene such as trimethylene, tetramethylene, methyl trimethylene etc., alkylene group (alkenylene group) is as allylidene, butenylidene, methyl allylidene etc., and inferior alkadienyl (alkadienylene group) is as Aden's dialkylene (butadienylenegroup) etc.
Unsaturated cyclic ester compounds as formula (III), specifically mention vinylene carbonate, carbonic acid 4-fluorine vinylene, carbonic acid 4,5-vinylidene difluoride ester, carbonic acid 4-methyl vinylene, carbonic acid 4,5-dimethyl vinylene, carbonic acid 4-methyl fluoride vinylene, carbonic acid 4-difluoromethyl vinylene, carbonic acid 4-trifluoromethyl vinylene, carbonic acid 4-ethyl vinylene, carbonic acid 4,5-diethyl vinylene, carbonic acid 4-fluoro ethyl vinylene, carbonic acid 4-two fluoro ethyl vinylenes, carbonic acid 4-trifluoroethyl vinylene, carbonic acid 4,5-bis trifluoromethyl vinylene, carbonic acid catechu phenolic ester (catechol carbonate), carbonic acid tetrahydrochysene catechu phenolic ester (tetrahydro catechol carbonate) etc.Wherein, preferred vinylene carbonate, carbonic acid 4-fluorine vinylene and carbonic acid catechu phenolic ester.These unsaturated cyclic ester compounds can use separately or be used in combination with two or more.
From the viewpoint of balancing battery performance, the content of the unsaturated cyclic ester compounds of formula (III) is preferably in the scope of 0.5-10 quality %, more preferably in the scope of 1-6 quality %, based on whole nonaqueous electrolytes.
Also preferably contain the aromatic compounds of representing by general formula (IV) according to nonaqueous electrolyte of the present invention.In formula (IV), R
4Be hydrogen, fluorine, alkoxyl, alkyl or cycloalkyl or aryl with carbon number 1-6 with carbon number 1-2.In addition, three R in formula (IV)
4Can be identical or different.
As the aromatic compounds of formula (IV), specifically mention fluorobenzene, two fluorobenzene, methyl phenyl ethers anisole, fluoroanisole, difluoroanisole, fluorine veratrole (fluoroveratrole), fluorine ethoxy benzene, biphenyl, fluorine biphenyl, methoxyl biphenyl, terphenyl, cyclohexylbenzene etc.Wherein, preferred fluorobenzene, biphenyl, fluorine biphenyl, fluoroanisole, difluoroanisole and fluorine veratrole.These aromatic compounds can be used separately or be used in combination with two or more.
From the viewpoint of balancing battery performance, the content of the aromatic compounds of formula (IV) is preferably in the scope of 0.05-4 quality %, more preferably in the scope of 0.1-2 quality %, based on whole nonaqueous electrolytes.
The compound of the compound of formula (III) and formula (IV) is even also tell on when these compounds add in the nonaqueous electrolyte of the present invention separately.Yet when the compound of formula (I) used with the high-load that is not less than 30 volume % in nonaqueous electrolyte, more preferably the compound of the compound of formula (III) and formula (IV) used together.
In the scope of not damaging the object of the invention, can in nonaqueous electrolyte, add aprotic organic solvent.When the amount of added aprotic organic solvent in nonaqueous electrolyte was not more than 85 volume %, nonaqueous electrolyte can show as noninflammability, but in order to give nonaqueous electrolyte higher noninflammability, preferably this amount is not more than 30 volume %.As aprotic organic solvent, specifically mention carbonic ester such as dimethyl carbonate (DMC), diethyl carbonate (DEC), diphenyl carbonate, methyl ethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC) or the like; Ether is as 1,2-dimethoxy-ethane (DME), oxolane (THF), diethyl ether (DEE), phenyl methyl ether or the like; Carboxylate such as gamma-butyrolacton (GBL), gamma-valerolactone, methyl formate (MF) or the like; Nitrile such as acetonitrile or the like; Acid amides such as dimethyl formamide or the like; With sulfone such as methyl-sulfoxide or the like.These aprotic organic solvents can comprise unsaturated bond and halogen.In addition, these aprotic organic solvents can use separately or be used in combination with two or more.
As the supporting electrolyte that is used for nonaqueous electrolyte of the present invention, be preferably used as the ionogenic supporting electrolyte of lithium ion.Supporting electrolyte does not have particular restriction, but preferably includes lithium salts such as LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiAsF
6, LiC
4F
9SO
3, Li (CF
3SO
2)
2N, Li (C
2F
5SO
2)
2N or the like.Wherein, consider that noninflammability is good, more preferably LiPF
6These supporting electrolytes can use separately or be used in combination with two or more.
The preferred 0.2-1.5mol/L of the concentration of the supporting electrolyte in nonaqueous electrolyte (M), more preferably 0.5-1mol/L (M).When the concentration of supporting electrolyte during less than 0.2mol/L, can not fully guarantee electrolytical conductivity, and cause the problem of battery discharge character and charging quantity aspect, and when it surpasses 1.5mol/L, electrolytical viscosity raises, can not guarantee the animal migration that lithium ion is enough, thereby can not guarantee the conductivity that electrolyte is enough, and may equally with above-mentioned situation cause the problem of battery discharge character and charging quantity aspect.
＜nonaqueous electrolyte battery 〉
Then, describe in detail according to nonaqueous electrolyte battery of the present invention.Nonaqueous electrolyte battery of the present invention comprises above-mentioned nonaqueous electrolyte, positive pole and negative pole, and if desired, and other member of being generally used for the nonaqueous electrolyte battery technical field such as barrier film etc. can be provided.In this case, nonaqueous electrolyte battery of the present invention can be configured to primary cell or secondary cell.
As the active material that is used for according to nonaqueous electrolyte battery positive pole of the present invention, preferably mention metal oxide such as V
2O
5, V
6O
13, MnO
2, MnO
3Deng; The composite oxides such as the LiCoO that contain lithium
2, LiNiO
2, LiMn
2O
4, LiFeO
2, LiFePO
4Deng; Metal sulfide such as TiS
2, MoS
2Deng; With electric conductive polymer such as polyaniline etc.Lithium-contained composite oxide can be to comprise the composite oxides that are selected from two or three transition metal in the group of being made up of Fe, Mn, Co and Ni.In this case, composite oxides are by LiFe
xCo
yNi
(1-x-y)O
2[wherein 0≤x＜1,0≤y＜1,0＜x+y≤1], LiMn
xFe
yO
2-x-yDeng expression.Wherein, especially preferred LiCoO
2, LiNiO
2And LiMn
2O
4, this is because their capacity height, safe and good to electrolytical wettability.These active material positive poles can use separately or be used in combination with two or more.
As the active material that is used for according to nonaqueous electrolyte battery negative pole of the present invention, preferably mention the graphite etc. of alloy, carbonaceous material such as the lithium doping of lithium metal itself, lithium and Al, In, Sn, Si, Pb, Zn or its similar substance.Wherein, consider that fail safe is higher and good to electrolytical wettability, preferred carbonaceous material such as graphite or its analog, especially preferred graphite.As graphite, mention native graphite, Delanium, middle phase charcoal microballon (MCMB) or the like, but further mention graphitized charcoal and non-graphitized charcoal.These active materials that are used for negative pole can use separately or be used in combination with two or more.
At traditional rechargeable nonaqueous electrolytic battery, particularly select under lithium or its alloy the situation as the traditional rechargeable nonaqueous electrolytic battery that is used for negative active core-shell material, the problem that has dendrite, wherein cause uneven electrocrystallization of lithium metal and dissolving by reignition-recharge, thereby be grown to the lithium of dendritic morphology, and resulting dendrite not only causes the reduction of battery performance, and may pass the barrier film that is positioned between positive pole and the negative pole, thereby causes battery short circuit.Yet except that above-mentioned effect, above-mentioned nonaqueous electrolyte according to the present invention has the effect that the dendrite that suppresses because reignition-recharge to cause produces.Therefore,, particularly preferred according to above-mentioned nonaqueous electrolyte of the present invention as the nonaqueous electrolyte that in negative pole, uses the secondary cell of lithium or its alloy preferably as the nonaqueous electrolyte that is used for secondary cell.
If necessary, anodal and negative pole can mix with conductive agent and adhesive.As conductive agent, mention acetylene black etc., as adhesive, mention polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) etc.These additives can be to compare compounding with compounding identical in conventional situation.
Form anodal and negative pole does not have particular restriction, but can suitably select from the well-known form as electrode.For example, mention thin slice shape, cylindricality, plate shape, spirality etc.
As other member that is used for nonaqueous electrolyte battery of the present invention, mention the barrier film that in nonaqueous electrolyte battery, inserts between positive pole and the negative pole, with the short circuit current that prevents to cause owing to interelectrode contact.Material as barrier film, preferentially mention can prevent really between electrode contact and by or flood electrolytical material such as nonwoven fabrics, film layer etc., it is made by synthetic resin such as polytetrafluoroethylene, polypropylene, polyethylene, cellulose base resin, polybutylene terephthalate (PBT), polyethylene terephthalate or its analog.They can be independent material, mixture or copolymers.Wherein, especially preferably have thickness about 20-50 μ m and microporous barrier of making by polypropylene or polyethylene and the film of making by cellulose base resin, polybutylene terephthalate (PBT), polyethylene terephthalate or analog.In the present invention, except that above-mentioned barrier film, can preferably use the various well-known member that is generally used for battery.
Form according to above-mentioned nonaqueous electrolyte battery of the present invention does not have particular restriction, but preferentially mentions various well-known form such as Coin shape, button type, paper mold, polygonal column type or helical structure or the like.Under the situation of button type, nonaqueous electrolyte battery can be made by preparing laminar positive pole and negative pole and barrier film being sandwiched between positive pole and the negative pole.Equally, under the situation of helical structure, nonaqueous electrolyte battery can be sandwiched between the current-collector, and pile up laminar negative pole thereon by the laminar positive pole of preparation, reels they or its analog then and makes.
＜embodiment 〉
Provide the following example with explanation the present invention, it is not that intention is as restriction of the present invention.
(embodiment 1)
Nonaqueous electrolyte passes through LiPF
6Be dissolved in the concentration of 1mol/L in the mixed solvent of difluorophosphoric acid ethyl ester of the cyclic phosphazene compound of formula (I) of 70 volume % and 30 volume % and prepare, in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In two be that methoxyl group (MeO) and its four are fluorine (F).The noninflammability of thus obtained nonaqueous electrolyte and limited oxygen index are by following method evaluation and measurement, thus the result shown in the acquisition table 1.
(1) electrolytical noninflammability
Measure the flame burning length and the burning time of under atmospheric environment, lighting and estimate according to the method for the layout UL94HB method of UL (Underwriting laboratory) standard.Particularly, according to the UL testing standard, by SiO with 127mm * 12.7mm
2Sheet prepares test pieces with the electrolyte-impregnated of 1.0mL and estimates.Noninflammability, anti-flammability, self-extinguishment and combustible evaluation criterion illustrate below.
The evaluation of＜noninflammability〉do not light under the situation of test pieces (burning length: 0mm), it is evaluated as has noninflammability in test flame.
The evaluation of＜anti-flammability〉the flame of lighting do not arrive the 25mm line and the object that falling in do not observe under the situation of catching fire, it be evaluated as have anti-flammability.
The evaluation of＜self-extinguishment〉the flame of lighting the 25-100mm line extinguish and the object that falling in do not observe under the situation of catching fire, it be evaluated as have self-extinguishment.
The evaluation of＜flammability〉under the flame of lighting surpasses the situation of 100mm line, it is evaluated as has flammability.
(2) electrolytical limited oxygen index
The electrolyte limited oxygen index is measured according to JIS K 7201.Limited oxygen index is big more, and electrolytical burning is difficult more.Particularly, test pieces is by strengthening the SiO of 127mm * 12.7mm with the U-shaped aluminium foil
2Thin slice (quartz filter paper, non-flame properties material) and becoming from bearing state and with 1.0mL electrolyte-impregnated SiO
2Thin slice prepares.Test pieces vertically is installed to the test pieces supporting member, so that leaving burning cylindrical shell (internal diameter: 75mm, high: 450mm, from bottom to 100 ± 5mm thickness is with the glass particle filling equally of diameter 4mm and place wire netting thereon) distance of upper part is not less than the position arrangement of 100mm.Then, oxygen (being equal to or greater than JIS K 1101) and nitrogen (be equal to or greater than JIS K1107 2 grades) flow through the burning cylindrical shell and under predetermined condition (thermal source is the Class1 No.1 of JIS K 2240) light test pieces to measure fired state.In this case, total flow is 11.4L/min in the burning cylindrical shell.With this test triplicate, its mean value is shown in table 1.Oxygen index means the value of keeping the necessary minimum oxygen concentration of material combustion and is represented by percent by volume.Limited oxygen index in the present invention by test pieces sustained combustion 3 minutes or longer or light the back sustained combustion so that keep burning length be not less than the necessary minimum oxygen flow of 50mm and this moment the minimum nitrogen flow, calculate according to following equation:
Limited oxygen index=(oxygen flow)/[(oxygen flow)+(nitrogen flow)] * 100 (volume %)
Then, 94 mass parts LiCoO
2Add 3 mass parts acetylene blacks (conductive agent) and 3 mass parts polyvinylidene fluoride (adhesive) in (positive electrode active materials) and use organic solvent (ethyl acetate of 50/50 volume % and ethanol mixed solvent) to mediate, thereafter, material that will be through mediating be applied in scraper has that the aluminium foil that thickness is 25 μ m (current-collector) is gone up and in hot blast dry (100-120 ℃), have the positive wafer thin of thickness 80 μ m with preparation.Equally, add 10 mass parts polyvinylidene fluoride (adhesive) in the 90 mass parts Delaniums (negative active core-shell material) and use organic solvent (ethyl acetate of 50/50 volume % and ethanol mixed solvent) to mediate, thereafter, will material be applied in scraper through mediating have that the Copper Foil that thickness is 25 μ m (current-collector) is gone up and in hot blast (100-120 ℃) drying, have the negative pole thin slice of thickness 80 μ m with preparation.
The negative pole thin slice is stacked on (microporous barrier: made by polypropylene) and coiling on the positive wafer thin by the barrier film with thickness 25 μ m, with preparation column type electrode.Anodal length in the column type electrode is about 260mm.Above-mentioned electrolyte is injected column type electrode and the sealing lithium battery (rechargeable nonaqueous electrolytic battery) with preparation size AA.Measure the initial discharge capacity and the cycle performance of thus obtained battery by following method, obtain to be shown in the result of table 1.
(3) initial discharge capacity of battery and cycle performance evaluation
Under the condition of upper voltage limit 4.3V, lower voltage limit 3.0V, discharging current 50mA and recharge current 50mA, in 20 ℃ atmosphere with battery charge and discharge, the discharge capacity of measuring this moment is divided by the weight of known electrodes, to determine initial discharge capacity (mAh/g).In addition, in same discharge-recharge under the condition, nearly 50 circulations of reignition-recharge to be measuring the discharge capacity after the circulation 50 times, and the remaining proportion S of capacity calculates according to following equation and as the sign of cycle performance of battery:
Discharge capacity/initial discharge capacity * 100 (%) after S=50 the circulation of capacity remaining proportion
(embodiment 2)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of the cyclic phosphazene compound of 50 volume % formulas (I) and 50 volume % difluorophosphoric acid methyl esters to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In two be that chlorine (Cl), its 4 are fluorine (F), estimate and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 3)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of the cyclic phosphazene compound of 30 volume % formulas (I) and 70 volume % difluorophosphoric acid propyl ester to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be ethyoxyl (EtO), its five is fluorine (F), estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 4)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of difluorophosphoric acid methyl esters, 10 volume % ethylene carbonates and 20 volume % methyl ethyl carbonates of cyclic phosphazene compound, the 30 volume % of 40 volume % formulas (I) to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be trifluoro ethoxy (TFEO), its five is fluorine (F), estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 5)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of cyclic phosphazene compound, 30 volume % fluorophosphoric acid dimethyl esters, 10 volume % ethylene carbonates, 5 volume % vinylene carbonates and the 15 volume % diethyl carbonates of 40 volume % formulas (I) to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 4, all R
1Be fluorine (F), estimate and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 6)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of cyclic phosphazene compound, 5 volume % difluorophosphoric acid phenyl esters, 28 volume % ethylene carbonates and the 57 volume % dimethyl carbonates of 10 volume % formulas (I) to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 4, all R
1In one be methoxyl group (MeO), its seven is fluorine (F), estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 7)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is 1.0 quality %4-fluoroanisoles are further joined in embodiment 3 mixed solvent that is used for " nonaqueous electrolyte preparation ", estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 8)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of the cyclic phosphazene compound of 30 volume % formulas (I) and the two trifluoro ethyl esters of 70 volume % fluorophosphoric acid to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be methoxyl group (MeO), its 5 is fluorine (F), estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(embodiment 9)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is 2 quality % carbonic acid 3-fluorine vinylenes and 0.5 quality %4-fluorine veratrole are further joined among the embodiment 8 mixed solvent that is used for " nonaqueous electrolyte preparation ", estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(comparative example 1)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of 33 volume % ethylene carbonates and 67 volume % methyl ethyl carbonates to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", estimates and the noninflammability and the limited oxygen index of the nonaqueous electrolyte of measurement gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(comparative example 2)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of 30 volume % trimethyl phosphates, 23 volume % ethylene carbonates and 47 volume % methyl ethyl carbonates to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", estimates and the noninflammability and the limited oxygen index of the nonaqueous electrolyte of measurement gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(comparative example 3)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of 30 volume % difluorophosphoric acid phenyl esters, 23 volume % ethylene carbonates and 47 volume % methyl ethyl carbonates to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", estimates and the noninflammability and the limited oxygen index of the nonaqueous electrolyte of measurement gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(comparative example 4)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of cyclic phosphazene compound, 27 volume % ethylene carbonates and the 55 volume % diethyl carbonates of 18 volume % formulas (I) to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be phenoxy group (PhO), its five is fluorine (F), estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
(comparative example 5)
Prepare nonaqueous electrolyte in the mode identical with embodiment 1, difference is to use the mixed solvent of the cyclic phosphazene compound of 50 volume % formulas (I) and 50 volume % triethyl phosphates to replace being used among the embodiment 1 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be phenoxy group (PhO), its five is fluorine (F), estimates and measure the noninflammability and the limited oxygen index of the nonaqueous electrolyte of gained.Equally, with embodiment 1 in identical mode make rechargeable nonaqueous electrolytic battery, and measure and estimate initial discharge capacity and cycle performance.The results are shown in table 1.
Table 1
| Noninflammability is estimated | Limited oxygen index (vol%) | Initial discharge capacity (mAh/g) | 50 circulation back capacity remaining proportions (%) | |
| Embodiment 1 | Noninflammability | 40.2 | 147 | 97 |
| Embodiment 2 | Noninflammability | 79.3 | 143 | 96 |
| Embodiment 3 | Noninflammability | 43.4 | 134 | 94 |
| Embodiment 4 | Noninflammability | 34.3 | 145 | 96 |
| Embodiment 5 | Noninflammability | 38.7 | 146 | 95 |
| Embodiment 6 | Noninflammability | 25.3 | 147 | 97 |
| Embodiment 7 | Noninflammability | 43.4 | 146 | 97 |
| Embodiment 8 | Noninflammability | 39.6 | 131 | 91 |
| Embodiment 9 | Noninflammability | 39.6 | 144 | 96 |
| Comparative example 1 | Flammability | 18.0 | 147 | 97 |
| Comparative example 2 | Self-extinguishment | 21.5 | 64 | 33 |
| Comparative example 3 | Anti-flammability | 23.2 | 98 | 42 |
| Comparative example 4 | Noninflammability | 26.1 | 139 | 97 |
| Comparative example 5 | Noninflammability | 28.3 | 25 | 22 |
Seen as embodiment 1-3 from table 1, use uses the battery of this nonaqueous electrolyte to have high discharge capacity and good cycle performance equally by the cyclic phosphazene compound of general formula (I) expression with by representing general formula (II) even the nonaqueous electrolyte of the present invention of the mixed solvent that the fluorophosphoric acid ester compounds of expression is formed also has noninflammability under the higher oxygen concentration that is not less than 40 volume %.In addition, as what from embodiment 4 and 5, seen, even nonaqueous electrolyte of the present invention has the high noninflammability that when adding 30 volume % aprotic organic solvents limited oxygen index also is not less than 30 volume %.In addition, as what seen, even nonaqueous electrolyte of the present invention also has noninflammability when it contains the fluorophosphoric acid ester compounds of the cyclic phosphazene compound of the general formula (I) that adds up to 15 volume % and general formula (II) from embodiment 6.In addition, as what seen from embodiment 5,7 and 9, discharge capacity and the cycle performance unsaturated cyclic ester compounds and/or the aromatic compounds of general formula (IV) and further improving by adding a spot of general formula (III).Thereby the limited oxygen index of nonaqueous electrolyte of the present invention that contains specific phosphazene compound and specific phosphate compound is very high, uses the discharge capacity and the cycle performance of rechargeable nonaqueous electrolytic battery of the present invention of such nonaqueous electrolyte good.
On the other hand, as what seen from the comparative example 2 and 3 of table 1, when independent use phosphate compound, initial discharge capacity is compared with embodiment and is become lower, cycle performance height deterioration and with its structure-irrelevant.In the comparative example 4 of table 1, when the cyclic phosphazene compound of general formula (I) only and aprotic organic solvent (EC/EMC) when mixing, when cyclic phosphazene compound adds fashionable with the amount that is not less than 20 volume %, cyclic phosphazene compound and aprotic organic solvent (EC/EMC) are divided into two-layer (becoming inhomogeneous) and can not be with the nonaqueous electrolyte that acts on battery, so the amount that they only can about 18 volume % adds, the electrolyte of gained is nonflammable thus, but its limited oxygen index is limited to about 26 volume %.In addition, as what see from the comparative example 5 of table 1, when the phosphate compound with the fluorophosphoric acid ester compounds structure that is different from general formula (II) uses with cyclic phosphazene compound, can obtain noninflammability, but initial discharge capacity and cycle performance height deterioration.
(embodiment 10)
Nonaqueous electrolyte passes through LiPF
6Be dissolved in the concentration of 1mol/L in the mixed solvent of cyclic phosphazene compound, 5 volume % difluorophosphoric acid methyl esters, 42 volume % ethylene carbonates and 43 volume % methyl ethyl carbonates of the formula (I) of 10 volume % and prepare, in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be phenoxy group, its five is fluorine.The noninflammability of the nonaqueous electrolyte of gained is by the said method evaluation.The results are shown in table 2.
Then, lithium-manganese composite oxide (LiMn
2O
4) as positive electrode active materials, this oxide, mix with the mass ratio of 90:5:5 and be dispersed in the N-methyl pyrrolidone with the preparation slurry as the acetylene black of conductive agent with as the fluorocarbon resin of adhesive, this slurry is applied on the aluminium foil as cathode collector, dry, stamp out disc format then, to prepare positive pole with 12.5mm diameter.On the other hand, as negative pole, use lithium sheet metal with diameter 12.5mm and thickness 1.0mm.Then, pass through with the cellulosic nonwoven fabric barrier film of electrolyte-impregnated anodal and negative pole overlapping, and be contained in the stainless steel case as positive terminal, the corrosion resistant plate that is used as negative pole end has the Coin-shaped battery (lithium secondary battery) of diameter 20mm and thickness 1.6mm with preparation by the sealing of polypropylene packing ring.The initial discharge capacity of gained battery and cycle life are measured with the result shown in the acquisition table 2 by following method.
(4) be used for the discharge of Coin-shaped battery-recharge test
At voltage range 4.3-3.0V and current density 2.0mA/cm
2Down, in 20 ℃ atmosphere, with the coin battery discharge with recharge, the discharge capacity of measuring this moment divided by the known quality of positive pole to determine initial discharge capacity (mAh/g).In addition, reignition under the same conditions-recharge circulation with the evaluation cycle life-span.Cycle life by can not reach when charging voltage stop value (4.3V) or when capacity less than initial discharge capacity 1% the time period illustrate.In addition, cause that when charging voltage decline fast or voltage show that it was assessed as and causes short circuit in battery when unsure state and charging voltage did not reach stop value (4.3V), the period of the measuring this moment sign that acts on inhibition dendrite effect.In addition, when capacity less than initial discharge capacity 1% the time, it is assessed as the carrying out that causes the electrolyte reduction decomposition before short circuit, the period of measuring this moment is with the sign that acts on anti-reduction in the electrolyte.
(embodiment 11)
Prepare nonaqueous electrolyte in the mode identical with embodiment 10, difference is to use the mixed solvent of cyclic phosphazene compound, 40 volume % difluorophosphoric acid propyl ester and the 40 volume % ethylene carbonates of 20 volume % formulas (I) to replace being used among the embodiment 10 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In two be ethyoxyl, its four is fluorine, estimates the noninflammability of the nonaqueous electrolyte of gained.In addition, make lithium secondary battery in the mode identical with embodiment 10, difference is that negative pole is lithium-ashbury metal thin slice, is discharging-is recharging and measuring initial discharge capacity and cycle life in the test.The results are shown in table 2.
(embodiment 12)
Prepare nonaqueous electrolyte in the mode identical with embodiment 10, difference is to use the mixed solvent of cyclic phosphazene compound, 93 volume % difluorophosphoric acid ethyl esters and the 2 volume % vinylene carbonates of 5 volume % formulas (I) to replace being used among the embodiment 10 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In one be pi-allyl, its five is fluorine, estimates the noninflammability of the nonaqueous electrolyte of gained.In addition, with embodiment 10 in identical mode make lithium secondary battery, discharging-recharging and measuring initial discharge capacity and cycle life in the test.The results are shown in table 2.
(comparative example 6)
Prepare nonaqueous electrolyte in the mode identical with embodiment 10, difference is to use the mixed solvent of 50 volume % ethylene carbonates and 50 volume % methyl ethyl carbonates to replace being used among the embodiment 10 mixed solvent of " nonaqueous electrolyte preparation ", the noninflammability of the non-aqueous solution electrolysis system matter of evaluation gained.In addition, with embodiment 10 in identical mode make lithium secondary battery, discharging-recharging and measuring initial discharge capacity and cycle life in the test.The results are shown in table 2.
(comparative example 7)
Prepare nonaqueous electrolyte in the mode identical with embodiment 10, difference is to use 15 volume % trimethyl phosphates, the mixed solvent of 42 volume % ethylene carbonates and 43 volume % methyl ethyl carbonates replaces being used among the embodiment 10 mixed solvent of " nonaqueous electrolyte preparation ", estimates the noninflammability of the non-aqueous solution electrolysis system matter of gained.In addition, with embodiment 10 in identical mode make lithium secondary battery, discharging-recharging and measuring initial discharge capacity and cycle life in the test.The results are shown in table 2.
(comparative example 8)
Prepare nonaqueous electrolyte in the mode identical with embodiment 10, difference is to use the mixed solvent of cyclic phosphazene compound, 40 volume triethyl phosphates and the 40 volume % ethylene carbonates of 20 volume % formulas (I) to replace being used among the embodiment 10 mixed solvent of " nonaqueous electrolyte preparation ", in the cyclic phosphazene compound of this formula (I), n is 3, all R
1In two be ethyoxyl, its four is fluorine, estimates the noninflammability of the non-aqueous solution electrolysis system matter of gained.In addition, make lithium secondary battery in the mode identical with embodiment 10, difference is that negative pole is lithium-ashbury metal thin slice, is discharging-is recharging and measuring initial discharge capacity and cycle life in the test.The results are shown in table 2.
Table 2
| Noninflammability is estimated | Initial discharge capacity (mAh/g) | Period (reason) | |
| Embodiment 10 | Noninflammability | 119 | 97 (short circuits) |
| Embodiment 11 | Noninflammability | 124 | 223 (short circuits) |
| Embodiment 12 | Noninflammability | 132 | 102 (short circuits) |
| Comparative example 6 | Flammability | 118 | 82 (short circuits) |
| Comparative example 7 | Self-extinguishment | 48 | 35 (decomposition) |
| Comparative example 8 | Noninflammability | 28 | 12 (decomposition) |
See as embodiment 10-12 from table 2, the nonaqueous electrolyte that contains the fluorophosphoric acid ester compounds of the cyclic phosphazene compound of general formula (I) and general formula (II) has noninflammability, use such lithium secondary battery of electrolyte to have good cycle life, have the effect that suppresses dendrite so determine the cyclic phosphazene compound of general formula (I) and the fluorophosphoric acid ester compounds of general formula (II).Thereby, confirm that nonaqueous electrolyte of the present invention has high noninflammability, by in lithium secondary battery, using such electrolyte, obtain to have excellent discharge-recharge the lithium secondary battery of cycle life, wherein on the negative pole of making by lithium or its alloy, produce dendrite hardly.
On the other hand, as what see from the comparative example 7 and 8 of table 2, even add the cyclic phosphazene compound of general formula (I), the nonaqueous electrolyte that contains common phosphotriester is also owing to the capacity reduction that the decomposition based on solvent itself causes makes cycle life deterioration greatly.
As what from The above results, see, contain by the cyclic phosphazene compound of general formula (I) expression with by the nonaqueous electrolyte of the fluorophosphoric acid ester compounds of general formula (II) expression by use, the nonaqueous electrolyte battery of balance noninflammability and good battery performance can be provided.
Claims (11)
1. nonaqueous electrolyte is characterized in that comprising and contains by the cyclic phosphazene compound of following general formula (I) expression with by the nonaqueous solvents and the supporting electrolyte of the fluorophosphoric acid ester compounds of following general formula (II) expression:
(NPR
1 2)
n…(I)
R wherein
1Be the unit price substituting group independently; N is 3-4;
R wherein
2Be halogen, alkoxyl or aryloxy group independently, two R
2In at least one be alkoxyl or aryloxy group.
2. nonaqueous electrolyte according to claim 1, wherein, this unit price substituting group is a halogen.
3. nonaqueous electrolyte according to claim 1 and 2, wherein, in general formula (II), two R
2In one be fluorine, another is alkoxyl or aryloxy group.
4. nonaqueous electrolyte according to claim 1 and 2, wherein, the R in general formula (I)
1Be fluorine, alkoxyl or aryloxy group independently.
5. nonaqueous electrolyte according to claim 1 and 2, wherein, in general formula (I), at least three R
1Be fluorine.
6. nonaqueous electrolyte according to claim 1 and 2, wherein, by this cyclic phosphazene compound of general formula (I) expression with by the volume ratio of the fluorophosphoric acid ester compounds of general formula (II) expression in the 30/70-70/30 scope.
7. nonaqueous electrolyte according to claim 1 and 2, wherein, this nonaqueous solvents further contains aprotic organic solvent.
8. nonaqueous electrolyte according to claim 1 and 2 wherein, in this nonaqueous solvents, is not less than 15 volume % by this cyclic phosphazene compound of general formula (I) expression with by the total content of this fluorophosphoric acid ester compounds of general formula (II) expression.
9. nonaqueous electrolyte according to claim 8 wherein, in this nonaqueous solvents, is not less than 70 volume % by this cyclic phosphazene compound of general formula (I) expression with by the total content of this fluorophosphoric acid ester compounds of general formula (II) expression.
10. nonaqueous electrolyte according to claim 1 and 2, it further contains by the unsaturated cyclic ester compounds of following general formula (III) expression and/or the aromatic compounds of being represented by following general formula (IV):
Wherein, R
3Be hydrogen, fluorine or alkyl independently with carbon number 1-2,
Wherein, R
4Be hydrogen, fluorine, alkoxyl, alkyl or cycloalkyl or aryl independently with carbon number 1-6 with carbon number 1-2.
11. a nonaqueous electrolyte battery, it comprises as each described nonaqueous electrolyte of claim 1-10, positive pole and negative pole.
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| JP292479/2004 | 2004-10-05 | ||
| JP2004292479A JP4911888B2 (en) | 2004-10-05 | 2004-10-05 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery including the same |
| JP108711/2005 | 2005-04-05 |
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| US20080254361A1 (en) * | 2005-03-31 | 2008-10-16 | Bridgestone Corporation | Non-Aqueous Electrolyte for Battery and Non-Aqueous Electrolyte Secondary Battery Comprising the Same |
| JP2008053211A (en) | 2006-07-24 | 2008-03-06 | Bridgestone Corp | Nonaqueous electrolytic solution for battery, and nonaqueous electrolytic solution battery equipped with it |
| US9048508B2 (en) | 2007-04-20 | 2015-06-02 | Mitsubishi Chemical Corporation | Nonaqueous electrolytes and nonaqueous-electrolyte secondary batteries employing the same |
| JP5645274B2 (en) | 2010-02-10 | 2014-12-24 | Ｎｅｃエナジーデバイス株式会社 | Non-aqueous electrolyte and lithium ion secondary battery comprising the same |
| JP5623199B2 (en) * | 2010-09-06 | 2014-11-12 | 株式会社Ｎｔｔファシリティーズ | Non-aqueous electrolyte battery |
| JP2012094432A (en) * | 2010-10-28 | 2012-05-17 | Nippon Chem Ind Co Ltd | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery including the same |
| EP2697453B1 (en) * | 2011-04-11 | 2018-10-10 | Shenzhen Capchem Technology Co. Ltd. | Non-aqueous electrolytic solutions and electrochemical cells comprising the same |
| US8852813B2 (en) | 2011-07-22 | 2014-10-07 | Chemtura Corporation | Electrolytes comprising polycyclic aromatic amine derivatives |
| US9406972B2 (en) * | 2012-05-04 | 2016-08-02 | Samsung Sdi Co., Ltd. | Flame retardant monosubstituted pentafluorocyclotriphosphazene electrolyte additive and electrolyte including the same and rechargeable lithium battery including the same |
| WO2015016187A1 (en) * | 2013-07-29 | 2015-02-05 | 富士フイルム株式会社 | Nonaqueous-secondary-battery electrolyte solution and nonaqueous secondary battery |
| JP6088934B2 (en) * | 2013-07-29 | 2017-03-01 | 富士フイルム株式会社 | Nonaqueous electrolyte and nonaqueous secondary battery |
| CN103762384B (en) * | 2014-01-24 | 2016-05-04 | 福建创鑫科技开发有限公司 | A kind of battery safety-type nonaqueous electrolytic solution |
| CN104218258A (en) * | 2014-09-17 | 2014-12-17 | 宜春金晖新能源材料有限公司 | Over-charging prevention flame-retardant battery electrolyte |
| KR102383073B1 (en) * | 2017-07-21 | 2022-04-04 | 삼성에스디아이 주식회사 | Electrolyte of rechargeable lithium battery and rechargeable lithium battery including same |
| CN108808085B (en) * | 2018-07-12 | 2020-09-04 | 合肥国轩高科动力能源有限公司 | Electrolyte for improving heat-resistant uncontrol performance of lithium ion battery |
| KR20210104922A (en) * | 2019-01-14 | 2021-08-25 | 바텔리 메모리얼 인스티튜트 | Topical Super-Concentrated Electrolyte for Silicon Anodes |
| CN112242562A (en) * | 2019-07-16 | 2021-01-19 | 东莞市杉杉电池材料有限公司 | Flame-retardant lithium ion battery electrolyte and lithium ion battery containing electrolyte |
| CN110911745B (en) * | 2019-11-29 | 2021-06-25 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device |
| CN111146502B (en) * | 2019-12-26 | 2020-12-18 | 合肥工业大学 | Composite flame-retardant electrolyte and lithium ion battery |
| CN111430781A (en) * | 2020-05-06 | 2020-07-17 | 杉杉新材料（衢州）有限公司 | Ternary high-voltage lithium ion battery electrolyte and lithium ion battery thereof |
| CN114230549A (en) * | 2021-11-24 | 2022-03-25 | 青岛科技大学 | Synthetic method of fluoroethylene carbonate |
| CN114614086A (en) * | 2022-03-24 | 2022-06-10 | 香河昆仑新能源材料股份有限公司 | Electrolyte containing fluorine substituted phosphorus nitrogen cyclic compound and battery composed of electrolyte |
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| US5830600A (en) * | 1996-05-24 | 1998-11-03 | Sri International | Nonflammable/self-extinguishing electrolytes for batteries |
| EP1357628A1 (en) * | 2001-01-04 | 2003-10-29 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic liquids and lithium secondary battery employing the same |
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| JP2006107910A (en) | 2006-04-20 |
| CN101057355A (en) | 2007-10-17 |
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