CN101490893A - Electrochemical device - Google Patents

Electrochemical device Download PDF

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Publication number
CN101490893A
CN101490893A CNA200780026598XA CN200780026598A CN101490893A CN 101490893 A CN101490893 A CN 101490893A CN A200780026598X A CNA200780026598X A CN A200780026598XA CN 200780026598 A CN200780026598 A CN 200780026598A CN 101490893 A CN101490893 A CN 101490893A
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Prior art keywords
electrolyte
fluorine
volume
carbonate
solvent
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Inventor
高明天
坂田英郎
中泽瞳
田中米基璐
山内昭佳
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides an electrochemical device having an electrolyte solution comprising: (I) a solvent for dissolving an electrolyte salt, which comprises (A) a fluorinated ether represented by the formula (1), (B) a cyclic carbonate and (C) a linear carbonate compatible with both the fluronated ether (A) and the cyclic carbonate (B); and (II) the electrolyte salt, wherein the solvent (I) contains the fluorinated ether (A) in an amount of 30 to 60% by volume, the cyclic carbonate (B) in an amount of 3 to 40% by volume and the linear carbonate (C) in an amount of 10 to 67% by volume relative to the total volume of the solvent (I). Rf<1>-O-Rf<2> (1) wherein Rf<1> and Rf2 independently represent a fluorinated alkyl group having 3 to 6 carbon atoms. The electrochemical device hardly causes phase-separation even at lower temperatures, and has excellent flame retardancy and heat resistance, can highly dissolve an electrolyte salt, has a high discharge capacity, and is excellent in charge/discharge cycle property.

Description

Electrochemical device
Technical field
The present invention relates to have the electrochemical device of following electrolyte, and above-mentioned electrolyte is combined with specific fluorine-containing ether, stable at low temperatures and excellent in flame retardance.
Background technology
As the solvent for dissolving electrolyte salt of secondary lithium batteries, commonly used have carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate.But, because the flash-point of these hydro carbons carbonates is low, flammability is high, overcharge, cross the large-scale lithium secondary battery that danger, particularly mixed type (power) automobile is used and decentralized power s is used that heating causes spark, blast so have, in order to ensure fail safe, this is an important problem.
The blast means that prevent as electrolyte, proposed in electrolyte, to cooperate the motion (Japanese patent laid-open 11-233141 communique, Japanese patent laid-open 11-283669 communique, the Japan Patent spy opens 2002-280061 communique and Japanese patent laid-open 09-293533 communique) as additive such as fluoroalkane, phosphate, phosphide.
But, in adding the system of fluoroalkane and since fluoroalkane self with mix hardly as the necessary carbonates of bath composition, so can separate by genetic horizon, battery performance is worsened.
In addition, in the system of adding phosphate, phosphide, though suppressed the flammability of electrolyte, because viscosity increased, conductance descends easily, causes the deterioration that is produced by charge and discharge cycles easily.
In order not reduce performance as electrolyte, and improve its noninflammability and anti-flammability, also proposed to add the motion (Japanese patent laid-open 08-037024 communique, Japanese patent laid-open 09-097627 communique, Japanese patent laid-open 11-026015 communique, Japan Patent 2000-294281 communique, Japan Patent spy open 2001-052737 communique and Japanese patent laid-open 11-307123 communique) of fluorine-containing ether.
In Japanese patent laid-open 08-037024 communique, the high power capacity that is added with fluorine-containing ether, the secondary cell electrolyte of cyclical stability excellence have been put down in writing, as fluorine-containing ether, it can be chain, it also can be ring-type, as the concrete example of the fluorine-containing ether of chain, put down in writing the material of carbon number below 2 as an alkyl.
But the content of also having put down in writing fluorine-containing ether is below the 30 volume %, and when surpassing 30 volume %, the discharge capacity of this system will reduce.
In Japanese patent laid-open 09-097627 communique, put down in writing in order not use cyclic carbonate to modulate electrolyte with solvent as electrolyte dissolution, except the non-annularity carbonic ester, also use to surpass 30 volume % below 90 volume %, with R 1-O-R 2(R 1Be the alkyl of carbon number below 2 or the alkyl of halogen replacement, R 2The expression carbon number alkyl that the halogen below 10 replaces more than 2) motion of the fluorine-containing ether of expression.And, though also hinted it is not necessary, cooperate the cyclic carbonate that is preferably below the 30 volume % can improve the discharge capacity at initial stage.
But, in this system, R 1Carbon number be 3 when above, the solubility of electrolytic salt descends, and can not obtain the battery behavior of target.
Open the 2000-294281 communique and the Japan Patent spy opens in the 2001-052737 communique Japanese patent laid-open 11-026015 communique, Japan Patent spy, proposed to use the organic group that contains ether oxygen to be-CH 2The fluorine-containing ether of-O-, the motion of the intermiscibility of improvement and other solvents, the stability of oxidation Decomposition and noninflammability etc. has specifically been put down in writing and HCF 2CF 2CH 2OCF 2CF 2Organic group of the conduct that the ether oxygen of H etc. combines is the fluorine-containing ether of carbon number below 2.But in general boiling point is low, low with the intermiscibility of other solvents, and dissolving electrolyte salt is low, as the solvent of secondary cell with electrolyte, is further improving under the situation of thermal endurance and oxidative resistance, not necessarily can be fully satisfied.
In Japanese patent laid-open 11-307123 communique, record by with C mF 2m+1-O-C nH 2n+1Shown fluorine-containing ether mixes with the carbonic ester of chain, and the motion of the electrolyte of capacity sustainment rate and excellent in stability is provided thus.But the dissolving of the electrolytic salt of this mixed solvent system can be low, can not dissolve as the general LiPF of high-quality electrolytic salt 6And LiBF 4,, have to use the LiN (O of metal protection as electrolytic salt 2SCF 3) 2And, because the viscosity height, so lag characteristic is poor.
Like this, present present situation be do not develop noninflammability and excellent in flame retardance, the have sufficient battery behavior electrolyte for lithium secondary batteries of (charge, discharge capacity etc.).
Summary of the invention
The present invention will solve above-mentioned existing problem points and the invention that produces, its purpose is that dissolubility height, discharge capacity that phase decomposition and anti-flammability and excellent heat resistance, electrolytic salt do not take place at low temperatures yet are big, the electrochemical device of excellent charge even provide.
That is, the present invention relates to a kind of electrochemical device, it has electrolyte, and described electrolyte contains:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1-O-Rf 2Shown fluorine-containing ether, in the formula, Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3～6;
(B) cyclic carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and cyclic carbonate (B),
Solvent for dissolving electrolyte salt (I) with respect to whole solvents (I), contains: fluorine-containing ether (A) 30～60 volume %, cyclic carbonate (B) 3～40 volume % and linear carbonate (C) 10～67 volume %.
The fluorine-containing rate of the fluorine-containing ether (A) shown in the formula (1) is 55～74 quality %, in the formula (1), and Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3 or 4, the balance of noninflammability and intermiscibility is excellent especially, and is under the situation for this carbon number, more favourable and preferred aspect boiling point, lag characteristic (viscosity).
Above-mentioned cyclic carbonate (B) is preferably ethylene carbonate and/or vinylene carbonate.
Particularly solvent for dissolving electrolyte salt (I) contains the electrolyte of fluorine-containing ether (A) 40～60 volume %, cyclic carbonate (B) 5～25 volume % and linear carbonate (C) 15～55 volume % with respect to whole solvents (I), at electrolytic salinity is that 0.5 mol is when above, as liquid, at low temperatures and at high temperature all very stable, it is also excellent to have a characteristic of electrochemical device of this electrolyte.
In addition, preferred above-mentioned electrochemical device is a battery.
In addition, the present invention relates to a kind of electrolyte, contain:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1-O-Rf 2Shown fluorine-containing ether, in the formula, Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3～6;
(B) cyclic carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and cyclic carbonate (B),
Solvent for dissolving electrolyte salt (I) with respect to whole solvents (I), contains: fluorine-containing ether (A) 30～60 volume %, cyclic carbonate (B) 3～40 volume % and linear carbonate (C) 10～67 volume %.
In addition, a kind of electrolyte for lithium secondary batteries of the present invention, contain:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1-O-Rf 2Shown fluorine-containing ether, in the formula, Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3 or 4;
(B) ethylene carbonate and/or vinylene carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and ethylene carbonate and/or vinylene carbonate (B),
Solvent for dissolving electrolyte salt (I) contains fluorine-containing ether (A) 40～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 3～20 volume % and linear carbonate (C) 20～57 volume % with respect to whole solvents (I), and electrolytic salt (II) is LiPF 6Or LiBF 4, the concentration of electrolytic salt is more than 0.8 mol.
Solvent for dissolving electrolyte salt (I) particularly, with respect to whole solvents (I), contain: the electrolyte of fluorine-containing ether (A) 40～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 3～15 volume % and linear carbonate (C) 31～57 volume %, electrolytic salinity is more than 1.0 mol, as liquid at low temperatures and at high temperature all very stable, battery behavior is also excellent.
In addition, as fluorine-containing ether (A), boiling point is fluorine-containing ether high-temperature stability (thermal endurance) excellence more than 90 ℃.HCF wherein 2CF 2CH 2OCF 2CFHCF 3Boiling point be more than 100 ℃, and with the intermiscibility of other solvents and the favorable solubility of electrolytic salt, very excellent from this point.
Electrolyte flame-retardant excellence of the present invention, in order further to give its noninflammability (non-ignitable character), also can in solvent for dissolving electrolyte salt (I), add below the 3 volume %, be preferably the phosphate (D) below the 1 volume %, wherein can add fluorine-containing alkyl phosphate.
In addition, the present invention relates to a kind of electrolyte for lithium secondary batteries, contain:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1-O-Rf 2Shown fluorine-containing ether, in the formula, Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3～6;
(B) ethylene carbonate and/or vinylene carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and ethylene carbonate and/or vinylene carbonate (B),
Solvent for dissolving electrolyte salt (I), with respect to whole solvents (I), contain: fluorine-containing ether (A) 30～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 3～40 volume % and linear carbonate (C) 10～67 volume %, electrolytic salt (II) contain at least and are selected from LiN (SO 2CF 3) 2And LiN (SO 2C 2F 5) 2In electrolytic salt (IIa), and the concentration of electrolytic salt (II) is more than 0.5 mol.
The fluorine-containing rate of the fluorine-containing ether (A) shown in the formula (1) is below the above 74 quality % of 55 quality %, in formula (1), and Rf 1With Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3 or 4.The balance of noninflammability and intermiscibility is excellent especially, and is under the situation for this carbon number, more favourable so preferred aspect boiling point, lag characteristic (viscosity).
In addition, electrolytic salt (II) is except electrolytic salt (IIa), also contains to be selected from LiPF 6And LiBF 4In electrolytic salt (IIb), the concentration of this electrolytic salt (IIb) is more than 0.1 mol.
Wherein, the concentration of electrolytic salt (IIa) is 0.4～1.3 mol, the concentration of electrolytic salt (IIb) is 0.1～0.5 mol, and the concentration of electrolytic salt (IIb)/(concentration of the concentration+electrolytic salt (IIb) of electrolytic salt (IIa)) is more than 0.1 below 0.4.Especially, from the viewpoint of lag characteristic, preferred electrolyte salt (IIb) is LiPF 6In addition, be LiN (SO at electrolytic salt (IIa) 2CF 3) 2Situation under, preferably with LiPF 6And use.Moreover, in this case, from the etch-proof viewpoint of aluminium collector body, preferred LiPF 6Concentration/(LiPF 6+ LiN (SO 2CF 3) 2Concentration) be 0.2～0.35.
Particularly solvent for dissolving electrolyte salt (I) contains the electrolyte of fluorine-containing ether (A) 40～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 5～25 volume % and linear carbonate (C) 15～55 volume % with respect to whole solvents (I), the concentration of electrolytic salt is more than 0.5 mol, as liquid at low temperatures and at high temperature all very stable, battery behavior is also excellent.
In addition, as fluorine-containing ether (A), boiling point is fluorine-containing ether high-temperature stability (thermal endurance) excellence more than 80 ℃.Wherein be selected from HCF 2CF 2CH 2OCF 2CFHCF 3And CF 3CF 2CH 2OCF 2CFHCF 3Fluorine-containing ether (A) boiling point be more than 100 ℃ and good with the solubility of the intermiscibility of other solvents and electrolytic salt, very excellent.
Electrolyte flame-retardant excellence of the present invention, in order further to give its noninflammability (non-ignitable character), also can in solvent for dissolving electrolyte salt (I), add below the 10 volume %, be preferably the phosphate (D) below the 5 volume %, wherein can add fluorine-containing alkyl phosphate.
Also have, in this manual, so-called " anti-flammability " is meant in flame retardant test described later the character that does not produce spark, breaks, and so-called " noninflammability " is meant non-ignitable character in ignitability test described later.
Embodiment
Electrochemical device of the present invention has electrolyte, and this electrolyte comprises the solvent for dissolving electrolyte salt (I) and the electrolytic salt (II) of specific composition.
In first mode of the present invention, electrochemical device of the present invention has electrolyte, and this electrolyte comprises the solvent for dissolving electrolyte salt (Ia) and the electrolytic salt (IIa) of specific composition.
At first solvent for dissolving electrolyte salt (Ia) is described.
(Aa) fluorine-containing ether is by the fluorine-containing ether shown in the formula (1a),
Formula (1a): Rf 1a-O-Rf 2a
Rf in the formula 1aWith Rf 2aIdentical or different, be the fluoroalkyl that contains of carbon number 3 or 4.
Particularly, can enumerate Rf 1aAnd Rf 2aBe HCF 2CF 2CH 2-, CF 3CF 2CH 2-, CF 3CF 2CH 2CH 2-, HCF 2CF 2CF 2-, HCF 2CF 2CF 2CF 2-, HCF 2CF 2CH 2CH 2-, CF 3CFHCF 2-, CF 3CFHCF 2CH 2-etc.
Wherein, as Rf 1aAnd Rf 2a, end contains HCF 2-or CF 3The material of CFH-can form the polarizability excellence, the fluorine-containing ether of boiling point height (more than 90 ℃, particularly more than 100 ℃).As preferred example, can enumerate HCF 2CF 2CH 2OCF 2CFHCF 3, HCF 2CF 2CH 2OCH 2CF 2CF 2H, CF 3CFHCF 2CH 2OCF 2CFHCF 3Deng in a kind of or more than 2 kinds, particularly from higher boiling point, favourable with the aspects such as favorable solubility of the intermiscibility of other solvents, electrolytic salt, preferred HCF 2CF 2CH 2OCF 2CFHCF 3(106 ℃ of boiling points).
The use level of fluorine-containing ether (Aa) is 40～60 volume % with respect to the content of whole solvents (Ia).The decreased solubility of electrolytic salt in the time of too much, but also can cause that layer separates, and low-temperature characteristics (low-temperature stability) descends when very few, anti-flammability also descends, and all can destroy the balance of characteristics of liquids and battery behavior.From with the viewpoint of the favorable solubility of the intermiscibility of other solvents and electrolytic salt, preferred upper limit is 55 volume %, from the viewpoint of keeping with anti-flammability kept of low-temperature characteristics, preferred lower limit is 45 volume %.
In addition, also can replace below the 50 volume % of fluorine-containing ether (Aa) by other fluorine-containing ether.As other fluorine-containing ether, for example be preferably carbon number and add up to 4～5 the fluorine-containing ether of chain, the wherein preferred high HCF of boiling point 2CF 2CH 2OCF 2CF 2H (93 ℃ of boiling points).
(Ba) cyclic carbonate:
As cyclic carbonate (Ba), can enumerate fluorine-free cyclic carbonate and fluorine-containing cyclic carbonate.
In the fluorine-free cyclic carbonate, the dielectric constant height of ethylene carbonate and/or vinylene carbonate, and the dissolubility of electrolytic salt is excellent especially, and therefore preferred in electrolyte of the present invention.And, using under the situation of graphite type material as negative pole, can on negative pole, form stable overlay film.
The use level of cyclic carbonate (Ba) is 3～20 volume % with respect to the content of whole solvents (Ia).In the system of solvent used in the present invention (Ia), cyclic carbonate (Ba) is too much the time, and under the lower-temperature atmosphere such as room temperature of the outside air temperature in winter and refrigerator (for example-30 ℃～-20 ℃), fluorine-containing ether (Aa) can separate by genetic horizon.From this viewpoint, preferred upper limit is 15 volume %, more preferably 9 volume %.On the other hand, the decreased solubility of the electrolytic salt of solvent (IIa) when very few can not reach desirable electrolyte concentration (more than 0.8 mol).
Preferred cyclic carbonate (Ba) cooperates with amount identical with linear carbonate (Ca) or that be less than it.Cyclic carbonate (Ba) than linear carbonate (Ca) for a long time, the intermiscibility between solvent has the tendency of decline.When cyclic carbonate (Ba) cooperates with amount identical with linear carbonate (Ca) or that be less than it, can form uniform electrolyte in wide temperature range, cycle characteristics also can improve.
(Ca) linear carbonate that can mix with the both of fluorine-containing ether (Aa) and cyclic carbonate (Ba):
Because the intermiscibility of fluorine-containing ether (Aa) and cyclic carbonate (Ba) is low, so only be difficult to form uniform solvent by them.Therefore, the cooperation linear carbonate (Ca) that can mix with the both of fluorine-containing ether (Aa) and cyclic carbonate (Ba).
As linear carbonate (Ca), for example can enumerate hydro carbons linear carbonate such as diethyl carbonate, ethylmethyl carbonate, dimethyl carbonate; CF 3CH 2OCOOCH 2CF 3, CF 3CH 2OCOOCH 3, CF 3CF 2CH 2OCOOCH 3, HCF 2CF 2CH 2OCOOCH 3Etc. a kind of in hydrochlorofluorocar,ons linear carbonate etc. or more than 2 kinds.Wherein, from boiling point height, viscosity is low and low-temperature characteristics is good viewpoint, preferred diethyl carbonate, ethylmethyl carbonate, dimethyl carbonate, CF 3CH 2OCOOCH 2CF 3, CF 3CH 2OCOOCH 3, CF 3CF 2CH 2OCOOCH 3, HCF 2CF 2CH 2OCOOCH 3, particularly from the viewpoint of low-temperature characteristics excellence, preferred diethyl carbonate, ethylmethyl carbonate.
The use level of linear carbonate (Ca) particularly, is 20～57 volume % with respect to the content of whole solvents (Ia), from the viewpoint of the favorable solubility of the intermiscibility of other solvents and electrolytic salt, be preferably 31～57 volume %.
(Da) phosphate
In order to give noninflammability (non-ignitable character), also can cooperate phosphate (Da).Use level is 3 volume % when following in solvent for dissolving electrolyte salt (Ia), can prevent to catch fire.
As phosphate (Da), can enumerate fluorine-containing alkyl phosphate, fluorine-free alkyl phosphate, aryl phosphate ester etc., because fluorine-containing alkyl phosphate is big to the contribution of the not burning of electrolyte, adds just can access on a small quantity and do not fire effect, therefore preferred.
As fluorine-containing alkyl phosphate, the cyclic alkyl phosphate of putting down in writing in the fluorine-containing dialkyl phosphate of in Japanese patent laid-open 11-233141 communique, putting down in writing, the Japanese patent laid-open 11-283669 communique, also has the fluorine-containing trialkyl phosphates (D1a) shown in the formula (D1a).
Figure A200780026598D00141
Rf in the formula 3a, Rf 4aAnd Rf 5aIdentical or different, be the fluoroalkyl that contains of carbon number 1～3.
Because fluorine-containing trialkyl phosphates (D1a) gives non-flame properties ability height, and with the intermiscibility of composition (Aa)～(Ca) might as well, therefore can make addition few, even below the 2 volume %, even below the 1 volume %, also can prevent to catch fire.
As fluorine-containing trialkyl phosphates (D1a), in the formula (D1a), Rf 3a, Rf 4aAnd Rf 5aIdentical or different, all be preferably CF 3-, CF 3CF 2-, CF 3CH 2-, HCF 2CF 2-or CF 3CFHCF 2-, preferred especially Rf 3a, Rf 4aAnd Rf 5aBe CF 3CF 2-tricresyl phosphate 2,2,3,3,3-five fluoropropyl esters, Rf 3a, Rf 4aAnd Rf 5aBe HCF 2CF 2-tricresyl phosphate 2,2,3,3-tetrafluoro propyl diester.
(Ea) other additives
In the present invention, do not destroy composition (Aa)～(Ca), and the volume ratio of composition as required (Da), and do not damage in the scope of effect of the present invention, also can cooperate other additives such as high dielectric additive, cycle characteristics improver.
As high dielectric additive, for example can list propylene carbonate, butylene carbonate, ethylene thiazolinyl ethyl, sulfolane, methyl sulfolane, gamma-butyrolacton, gamma-valerolactone, acetonitrile, propionitrile etc.
Prevent agent as overcharging, for example can enumerate phenyl-hexafluoride, fluorobenzene, cyclohexyl benzene, dichloroaniline, toluene etc.
In addition, from the improvement of capacity characteristic, the improvement of lag characteristic, preferred HCF 2COOCH 3, HCF 2COOC 2H 5, CF 3COOCH 3, CF 3COOC 2H 5, C 2F 5COOCH 3, HCF 2CF 2COOCH 3Deng fluorinated ester.
In addition, as material, can enumerate following material etc. with effect same:
By formula (Ea1): Rf 6aCOO -M +Shown fluorine-containing carboxylate,
In the formula, Rf 6aBe the fluoroalkyl that contains of carbon number 1～8, M +Be the metal cation or the NH of 1 valency 4 +, be preferably alkali metal cation,
By formula (Ea2): Rf 7aSO 3 -M +Shown sulfonic fluoropolymer salt,
In the formula, Rf 7aBe the fluoroalkyl that contains of carbon number 1～8, M +Be the metal cation or the NH of 1 valency 4 +, be preferably alkali metal cation.
As the fluorine-containing carboxylate that satisfies formula (Ea1), for example can enumerate H (CF 2) 4COO -Li +, C 4F 9COO -Li +, C 5F 11COO -Li +, C 6F 13COO -Li +, C 7F 15COO -Li +, C 8F 17COO -Li +Deng.In addition, as the sulfonic fluoropolymer salt that satisfies formula (Ea2), for example can enumerate C 4F 9SO 3 -Li +, C 6F 13SO 3 -Li +, C 8F 17SO 3 -Li +Deng.
The modulation of solvent for dissolving electrolyte salt (Ia) can be by with composition (Aa)～(Ca), and composition as required (Da), (Ea) mix, make its uniform dissolution and carry out.
Then electrolytic salt (IIa) is described.The electrolytic salt that uses in the electrolyte of the present invention (a) is the LiPF that uses in the electrochemical device such as lithium secondary battery more 6Or LiBF 4
In order to ensure the Practical Performance as secondary cell, the concentration that requires electrolytic salt is more than 0.8 mol, and further requiring is more than 1.0 mol.The solvent for dissolving electrolyte salt that uses among the present invention (Ia) has and can make LiPF 6Or LiBF 4Concentration satisfy the dissolving energy of these requirements.
Then, represent the preferred prescription of electrolyte (a) that electrochemical device has in first mode of the present invention particularly, but the present invention is not limited to these examples.
(prescription a)
(Ia) solvent for dissolving electrolyte salt
(Aa) fluorine-containing ether
Kind: HCF 2CF 2CH 2OCF 2CFHCF 3
Use level: 40～60 volume % (amount in the solvent (Ia), down together)
(Ba) cyclic carbonate
Kind: ethylene carbonate and/or vinylene carbonate
Use level: 3～15 volume %
(Ca) linear carbonate
Kind: diethyl carbonate or ethylmethyl carbonate
Use level: 31～57 volume %
(Da) phosphate
Kind: fluorine-containing alkyl phosphate
Use level: 0～3 volume %
(IIa) electrolytic salt
Kind: LiPF 6Or LiBF 4
Concentration: 0.8～1.2 mol
In second mode of the present invention, electrochemical device of the present invention has electrolyte (b), and this electrolyte (b) comprises the solvent for dissolving electrolyte salt (Ib) and the electrolytic salt (IIb) of specific composition.
At first solvent for dissolving electrolyte salt (Ib) is described.
(Ab) fluorine-containing ether is by the fluorine-containing ether shown in the formula (Ib),
Formula (Ib): Rf 1b-O-Rf 2b
Rf in the formula 1bAnd Rf 2bIdentical or different, be carbon number 3～6, be preferably 3 or 4 the fluoroalkyl that contains.
If Rf 1bAnd Rf 2bCarbon number less than 3, the boiling point of fluorine-containing ether is low excessively, and carbon number surpasses at 6 o'clock, the solubility of electrolytic salt descends, and the intermiscibility with other solvents is also produced harmful effect, and because viscosity rises lag characteristic is descended.Particularly, from the viewpoint of boiling point and lag characteristic (viscosity), carbon number is 3 or was particularly advantageous in 4 o'clock.
In addition, because Rf 1bAnd Rf 2bComprise fluorine atom, improve so comprise the noninflammability of the electrolyte (b) of this fluorine-containing ether (Ab).
Further the fluorine-containing rate of preferred fluorine-containing ether (Ab) is more than the 55 quality %, more preferably 60 quality % above, more than the preferred especially 65 quality %, preferred upper limit is 74 quality %, more preferably 70 quality %.When having the fluorinated volume of this scope, the balance of noninflammability and intermiscibility is excellent especially.Fluorine-containing rate is the value by { (number of fluorine atom * 19)/molecular weight } * 100 (%) are calculated.
Specifically, Rf 1bAnd Rf 2b, can enumerate HCF 2CF 2CH 2-, CF 3CF 2CH 2-, CF 3CF 2CH 2CH 2-, HCF 2CF 2CF 2-, HCF 2CF 2CF 2CF 2-, HCF 2CF 2CH 2CH 2-, CF 3CFHCF 2-, CF 3CFHCF 2CH 2-, HCF 2CF 2CF 2CH 2-, HCF 2CF (CF 3) CH 2-etc.
Wherein end contains HCF 2-or CF 3The material of CFH-can provide the polarizability excellence, (more than 90 ℃, particularly more than 100 ℃) fluorine-containing ether that boiling point is high.As preferred example, for example can enumerate HCF 2CF 2CH 2OCF 2CFHCF 3, HCF 2CF 2CH 2OCH 2CF 2CF 2H, CF 3CFHCF 2CH 2OCF 2CFHCF 3, CF 2CH 2OCF 2CFHCF 3Deng in a kind of or more than 2 kinds, particularly, from higher boiling point, with the viewpoint of the favorable solubility of the intermiscibility of other solvents and electrolytic salt, preferred HCF 2CF 2CH 2OCF 2CFHCF 3(106 ℃ of boiling points) and CF 3CF 2CH 2OCF 2CFHCF 3(82 ℃ of boiling points).
The use level of fluorine-containing ether (Ab) is 30～60 volume % with respect to the content of whole solvents (Ib), is preferably 40～60 volume %.The decreased solubility of electrolytic salt also can cause to be separated in the time of too much, and low-temperature characteristics (low-temperature stability) descends when very few, and anti-flammability also descends, and all can destroy the balance of characteristics of liquids and battery behavior.From with the viewpoint of the favorable solubility of the intermiscibility of other solvents and electrolytic salt, be limited to 55 volume % on preferred, from the viewpoint of keeping with anti-flammability kept of low-temperature characteristics, preferred lower limit is 40 volume %.
In addition, also can replace below the 50 volume % of fluorine-containing ether (Ab) by other fluorine-containing ether.As other fluorine-containing ether, for example be preferably carbon number and add up to 4～5 the fluorine-containing ether of chain, the wherein preferred high HCF of boiling point 2CF 2CH 2OCF 2CF 2H (93 ℃ of boiling points).
(Bb) cyclic carbonate:
As cyclic carbonate (Bb), can enumerate fluorine-free cyclic carbonate and fluorine-containing cyclic carbonate.
In the fluorine-free cyclic carbonate, the dielectric constant height of ethylene carbonate and/or vinylene carbonate, and the dissolubility of electrolytic salt is excellent especially, and therefore preferred in electrolyte of the present invention.And, using under the situation of graphite type material as negative pole, also can on negative pole, form stable overlay film.
The use level of cyclic carbonate (Bb) is 3～40 volume % with respect to the content of whole solvents (Ib).In solvent used in the present invention (Ib) system, cyclic carbonate (B) is too much the time, and under the lower-temperature atmosphere such as room temperature of the outside air temperature in winter and refrigerator (for example-30 ℃～-20 ℃), fluorine-containing ether (Ab) can be separated, solidify.From this viewpoint, preferred upper limit is 30 volume %, more preferably 25 volume %.On the other hand, the decreased solubility of the electrolytic salt of solvent (IIb) when very few can not reach desirable electrolyte concentration (more than 0.8 mol).Lower limit is preferably 5 volume %.
More preferably cyclic carbonate (Bb) cooperates with amount identical with linear carbonate (Cb) or that be less than it.Cyclic carbonate (Bb) than linear carbonate (Cb) for a long time, intermiscibility between solvent descends.When cyclic carbonate (Bb) cooperates with amount identical with linear carbonate (Cb) or that be less than it, can form uniform electrolyte in wide temperature range, cycle characteristics also can improve.
(Cb) linear carbonate that can mix with the both of fluorine-containing ether (Ab) and cyclic carbonate (Bb):
Because fluorine-containing ether (Ab) is low with the intermiscibility of cyclic carbonate (Bb), so only be difficult to form uniform solvent by them.Therefore, the linear carbonate (Cb) that cooperates the both with fluorine-containing ether (Ab) and cyclic carbonate (Bb) to mix.
As linear carbonate (Cb), for example can enumerate hydro carbons linear carbonate such as diethyl carbonate, ethylmethyl carbonate, dimethyl carbonate, methylpropyl carbonate; CF 3CH 2OCOOCH 2CF 3, CF 3CH 2OCOOCH 3, CF 3CF 2CH 2OCOOCH 3Etc. a kind of in hydrochlorofluorocar,ons linear carbonate etc. or more than 2 kinds.Wherein from boiling point height, viscosity is low and low-temperature characteristics is good viewpoint, preferred diethyl carbonate, ethylmethyl carbonate, dimethyl carbonate, CF 3CH 2OCOOCH 2CF 3, CF 3CH 2OCOOCH 3, CF 3CF 2CH 2OCOOCH 3, particularly from the viewpoint of low-temperature characteristics excellence, preferred dimethyl carbonate, ethylmethyl carbonate.
Particularly, with respect to the content of the linear carbonate (Cb) of whole solvents (Ib), be 10～67 volume %, preferred lower limit is 15 volume %, more preferably 20 volume %, preferred upper limit is 57 volume %, more preferably 55 volume %.From with the viewpoint of the favorable solubility of the intermiscibility of other solvents and electrolytic salt, as preferred range, be 15～55 volume %.
(Db) phosphate
Can cooperate phosphate (Db) in order to give noninflammability (non-ignitable character).Use level is below the 10 volume % in solvent for dissolving electrolyte salt (Ib), is preferably 5 volume % when following, can prevent to catch fire.
As phosphate (Db), can enumerate fluorine-containing alkyl phosphate, fluorine-free alkyl phosphate, aryl phosphate ester etc., because fluorine-containing alkyl phosphate is big to the contribution of the not burning of electrolyte, adds just can access on a small quantity and do not fire effect, therefore preferred.
As fluorine-containing alkyl phosphate, the cyclic alkyl phosphate of putting down in writing in the fluorine-containing dialkyl phosphate of in Japanese patent laid-open 11-233141 communique, putting down in writing, the Japanese patent laid-open 11-283669 communique, also has the fluorine-containing trialkyl phosphates (D1b) shown in the formula (D1b).
Figure A200780026598D00191
Rf in the formula 3b, Rf 4bAnd Rf 5bIdentical or different, be the fluoroalkyl that contains of carbon number 1～3.
Because fluorine-containing trialkyl phosphates (D1b), give non-flame properties ability height, and with the intermiscibility of composition (Ab)～(Cb) might as well, so can make addition few,, even be below the 1 volume % even below 2 volumes, also can prevent to catch fire.
As fluorine-containing trialkyl phosphates (D1b), in the formula (D1b), Rf 3b, Rf 4bAnd Rf 5bIdentical or different, all be preferably CF 3-, CF 3CF 2-, CF 3CH 2-, HCF 2CF 2-or CF 3CFHCF 2-, particularly preferred Rf 3b, Rf 4bAnd Rf 5bBe CF 3CF 2-tricresyl phosphate 2,2,3,3,3-five fluoropropyl esters, Rf 3b, Rf 4bAnd Rf 5bBe HCF 2CF 2-tricresyl phosphate 2,2,3,3-tetrafluoro propyl diester.
(Eb) other additives
In the present invention, do not destroying composition (Ab)～(Cb), and the volume ratio of composition as required (Db), do not damage in the scope of effect of the present invention, also can cooperate high dielectric additive, cycle characteristics and lag characteristic improver, other additives such as preventing agent overcharge.
As high dielectric additive, for example can the example propylene carbonate, butylene carbonate, ethylene thiazolinyl ethyl, sulfolane, methyl sulfolane, gamma-butyrolacton, gamma-valerolactone, acetonitrile, propionitrile etc.
Prevent agent as overcharging, for example can enumerate phenyl-hexafluoride, fluorobenzene, cyclohexyl benzene, dichloroaniline, toluene etc.
As cycle characteristics and lag characteristic improver, can the example methyl acetate, ethyl acetate, oxolane, 1,4-diox etc.
In addition, from the improvement of capacity characteristic, the improvement of lag characteristic, preferred HCF 2COOCH 3, HCF 2COOC 2H 5, CF 3COOCH 3, CF 3COOC 2H 5, C 2F 5COOCH 3, HCF 2CF 2COOCH 3Deng fluorinated ester.
In addition, as material, can enumerate following substances etc. with effect same:
By formula (Eb1): Rf 6bCOO -M +Shown fluorine-containing carboxylate,
In the formula, Rf 6bBe the fluoroalkyl that contains of carbon number 1～8, M +Be the metal cation or the NH of 1 valency 4 +, be preferably alkali metal cation,
By formula (Eb2): Rf 7bSO 3 -M +Shown sulfonic fluoropolymer salt,
In the formula, Rf 7bBe the fluoroalkyl that contains of carbon number 1～8, M +Be the metal cation or the NH of 1 valency 4 +, be preferably alkali metal cation.
As the fluorine-containing carboxylate that satisfies formula (Eb1), for example can enumerate H (CF 2) 4COO -Li +, C 4F 9COO -Li +, C 5F 11COO -Li +, C 6F 13COO -Li +, C 7F 15COO -Li +, C 8F 17COO -Li +Deng.In addition, as the sulfonic fluoropolymer salt that satisfies formula (Eb2), for example can enumerate C 4F 9SO 3 -Li +, C 6F 13SO 3 -Li +, C 8F 17SO 3 -Li +Deng.
The modulation of solvent for dissolving electrolyte salt (Ib) can be by with composition (Ab)～(Cb), and composition as required (Db), (Eb) mix, and makes its uniform dissolution and carries out.
Then electrolytic salt (IIb) is described.The electrolytic salt (IIb) that uses in the electrolyte of the present invention (b) is to comprise at least to be selected from LiN (SO 2CF 3) 2And LiN (SO 2C 2F 5) 2In electrolytic salt (IIb-1).
In electrolyte of the present invention, the concentration of electrolytic salt (IIb) is more than 0.5 mol, is preferably more than 0.6 mol, more preferably more than 0.8 mol.The upper limit is generally 1.5 mol.
Electrolytic salt (IIb-1), in the disassociation of electrolytic salt, particularly to the dissolubility aspect of fluorine-containing ether (Ab) excellence, the concentration in the electrolyte (b) is more than 0.4 mol, is preferably more than 0.5 mol, more preferably more than 0.6 mol.By containing this electrolytic salt (IIb-1), can improve the ionic conductivity of electrolyte (b).The upper limit is generally 1.3 mol.
In the present invention, electrolytic salt (IIb-1) can cooperate separately, but be selected from LiPF6 and LiBF 4In electrolytic salt (IIb-2) and time spent, can further obtain the effect of corroding of preventing to aluminium collector body and assembly of elements metal.And the situation of usefulness under, electrolytic salt (IIb-2) concentration is more than 0.1 mol, is preferably more than 0.15 mol, more preferably more than 0.2 mol.
Moreover, and the situation of usefulness under, the concentration of electrolytic salt (IIb-1) is 0.4～1.3 mol, 0.5～1.2 mol more preferably, the concentration of electrolytic salt (IIb-2) is 0.1～0.5 mol, more preferably 0.15～0.4 mol.The concentration of electrolytic salt (IIb-2)/(concentration of the concentration+electrolytic salt (IIb-2) of electrolytic salt (IIb-1)) is more than 0.1, below 0.4, further be more than 0.15, below 0.35, the effect of improving based on the cycle characteristics that prevents corrosion of metals, coulombic efficiency, the ionic conductivity excellence, therefore preferred.
Then, represent the preferred prescription of electrolyte (b) that electrochemical device has in second mode of the present invention particularly, but the present invention is not limited to these examples.
(prescription b1)
(Ib) solvent for dissolving electrolyte salt
(Ab) fluorine-containing ether
Kind: HCF 2CF 2CH 2OCF 2CFHCF 3Or CF 3CF 2CH 2OCF 2CFHCF 3
Use level: 30～60 volume % (amount in the solvent (I), down together)
Fluorine-containing rate: 65～70 quality %
(Bb) cyclic carbonate
Kind: ethylene carbonate and/or vinylene carbonate
Use level: 3～40 volume %
(Cb) linear carbonate
Kind: diethyl carbonate or ethylmethyl carbonate
Use level: 10～67 volume %
(Db) phosphate
Kind: fluorine-containing alkyl phosphate
Use level: 0～10 volume %
(IIb) electrolytic salt
Electrolytic salt (IIb-1)
Kind: LiN (SO 2CF 3) 2Or LiN (SO 2CF 2CF 3) 2
Concentration: 0.5～1.3 mol
(prescription b2)
(Ib) solvent for dissolving electrolyte salt
(Ab) fluorine-containing ether
Kind: HCF 2CF 2CH 2OCF 2CFHCF 3Or CF 3CF 2CH 2OCF 2CFHCF 3
Use level: 30～60 volume %
Fluorine-containing rate: 65～70 quality %
(Bb) cyclic carbonate
Kind: ethylene carbonate and/or vinylene carbonate
Use level: 3～40 volume %
(Cb) linear carbonate
Kind: diethyl carbonate or ethylmethyl carbonate
Use level: 10～67 volume %
(Db) phosphate
Kind: fluorine-containing alkyl phosphate
Use level: 0～10 volume %
(IIb) electrolytic salt
Electrolytic salt (IIb-1)
Kind: LiN (SO 2CF 3) 2Or LiN (SO 2CF 2CF 3) 2
Concentration: 0.4～1.3 mol
Electrolytic salt (IIb-2)
Kind: LiPF 6Or LiBF 4
Concentration: 0.1～0.5 mol
(IIb-2)/{(IIb-1)+(IIb-2)}：0.1～0.4
As described above, as electrochemical device, for example can enumerate electrolytic capacitor, electric double layer capacitor, move and transducers such as solid display element, current sensor, gas sensor such as the battery of charge/discharge, electroluminescence etc. by the electric charge of ion with electrolyte (a) or electrolyte (b).
The lithium secondary battery that wherein has positive pole, negative pole, dividing plate and electrolyte (a) or electrolyte (b) is fit to, particularly, employed positive active material in the positive pole, be to form energy density height, the high secondary cell of output when being selected from least a in cobalt based composite oxide, nickel based composite oxide, manganese based composite oxide, iron based composite oxide and the vanadium based composite oxide, therefore preferred.
As cobalt based composite oxide, can example LiCoO 2As the nickel based composite oxide, can example LiNiO 2, as the manganese based composite oxide, can example LiMnO 2And, also can be LiCo xNi 1-xO 2(0＜x＜1), LiCo xMn 1-xO 2(0＜x＜1), LiNi xMn 1-xO 2(0＜x＜1), LiNi xMn 2-xO 4(0＜x＜2), LiNi 1-x-yCo xMn yO 2CoNi, CoMn shown in (0＜x＜1,0＜y＜1,0＜x+y＜1), composite oxides such as NiMn, NiCoMn.These contain the composite oxides of lithium, and the part of metallic elements such as Co, Ni, Mn can also be replaced by more than one metallic element such as Mg, Al, Zr, Ti, Cr.
In addition, as the iron based composite oxide, for example can example LiFeO 2, LiFePO 4, as the vanadium based composite oxide, for example can example V 2O 5
From improving the viewpoint of capacity, as positive active material, in above-mentioned composite oxides, preferred nickel based composite oxide or cobalt based composite oxide.Particularly in small-sized lithium secondary battery, aspect high from energy density and fail safe is considered, preferably uses cobalt based composite oxide.
In the present invention, particularly under the situation about in the large-scale lithium secondary battery that hybrid vehicle is used, decentralized power s is used, using, because demanding output, so the particle of preferred positive active material is based on second particle, the average grain diameter of this second particle is below the 40 μ m, contains following microparticle 0.5～7.0 volume % of average primary particle diameter 1 μ m.
By containing the microparticle below the average primary particle diameter 1 μ m, can increase the contact area with electrolyte, the diffusion of the lithium ion between battery and the electrolyte is quickened, improve output performance.
Employed negative electrode active material can be enumerated material with carbon element in the negative pole of the present invention, can also enumerate the metal oxide that can insert lithium ion, metal nitride etc.As material with carbon element, can enumerate native graphite, Delanium, thermally decomposed carbon class, coke class, carbonaceous mesophase spherules (mesocarbonmicrobeads), carbon fiber, active carbon, pitch covering graphite etc., as the metal oxide that can insert lithium ion, can enumerate the metallic compound of stanniferous, silicon, for example tin oxide, silica etc.; As metal nitride, can enumerate Li 2.6Co 0.4N etc.
Employed dividing plate and without particular limitation can be enumerated microporous polyethylene film, microporous polypropylene film, microporosity ethylene-propylene copolymer film, microporous polypropylene/polyethylene two tunics, microporous polypropylene/polyethylene/polypropylene trilamellar membrane etc. among the present invention.
In addition, employed electrolyte (a) and electrolyte (b) among the present invention owing to be non-flame properties material, so as above-mentioned hybrid vehicle with or the electrolyte of the large-scale secondary lithium batteries used of decentralized power s particularly useful, in addition, can also be as small-sized nonaqueous electrolytes such as lithium ion battery.
Embodiment
Then, at first mode of the present invention, enumerate embodiment the present invention is described, but the present invention is not limited to these embodiment.
Wherein, each compound that uses in following embodiment and the comparative example as shown below.
Composition (Aa)
(Aa)：HCF 2CF 2CH 2OCF 2CFHCF 3
Composition (Ba)
(Ba-1): ethylene carbonate
(Ba-2): vinylene carbonate
Composition (Ca)
(Ca): diethyl carbonate
Composition (Da)
(Da): tricresyl phosphate 2,2,3,3,3-five fluoropropyl esters
Electrolytic salt (IIa)
(IIa-1)：LiPF 6
(IIa-2)：LiBF 4
Embodiment 1
Mixed HCF with 50/3/47 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 2
Mixed HCF with 50/10/40 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir, make electrolyte of the present invention at 25 ℃.
Embodiment 3
Mixed HCF with 50/3/47 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiBF in this solvent for dissolving electrolyte salt 4(IIa-2), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 4
Mixed HCF with 50/3/45/2 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca)/tricresyl phosphate 2,2,3,3,3-five fluoropropyl esters (Da), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 5
Mixed HCF with 60/5/35 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 6
Mixed HCF with 40/20/40 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 7
Mixed HCF with 40/15/45 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 8
Mixed HCF with 55/7/38 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 9
Mixed HCF with 50/3/47 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and vinylene carbonate (Ba-2)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 10
Mixed HCF with 50/10/40 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and vinylene carbonate (Ba-2)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Comparative example 1
With mixed ethylene carbonate (Ba-1)/diethyl carbonate of 10/90 volume %, modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Comparative example 2
Mixed HCF with 50/1/49 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Comparative example 3
Mixed HCF with 70/10/20 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Comparative example 4
Mixed HCF with 50/50 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Comparative example 5
Mixed HCF with 70/20/10 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Comparative example 6
Mixed HCF with 65/5/30 volume % 2CF 2CH 2OCF 2CFHCF 3(Aa)/and ethylene carbonate (Ba-1)/diethyl carbonate (Ca), modulation dissolving electrolyte salt solvent adds LiPF in this solvent for dissolving electrolyte salt 6(IIa-1), make its concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Test example 1 (dissolubility of electrolytic salt)
With the electrolyte 6ml that makes respectively in embodiment 1～10 and the comparative example 1～6, be taken to the sample bottle of 9ml volume, under 25 ℃, left standstill the state of visual observations liquid 8 hours.The results are shown in table 1.
(evaluation criterion)
Zero: be homogeneous solution
△: electrolytic salt is separated out
*: the liquid genetic horizon separates
Test example 2 (low-temperature stability)
With the electrolyte 6ml that makes respectively in embodiment 1～10 and the comparative example 1～6, be taken to the sample bottle of 9ml volume, visual observations leaves standstill the state after 8 hours in-20 ℃ freezer, the results are shown in table 1.
(evaluation criterion)
Zero: be homogeneous solution
△: electrolytic salt is separated out
*: liquid curing
Figure A200780026598D00281
Test example 3 (ionic conductance)
In the following method the ionic conductance of the electrolyte made respectively in embodiment 1,2,4,5 and the comparative example 1,2,4 is measured.The results are shown in table 2.
(test method)
By the 4 terminal methods of interchange, measure the ionic conductance under the room temperature.The SI1280B that impedance measuring instrument uses Dongyang technical (strain) to produce is 10 in frequency 4Hz～10 1The scope of Hz is carried out.
Test example 4 (charge-discharge characteristic)
Make coin shape (coin) lithium secondary battery according to the methods below.
(anodal making)
To mix LiCoO according to 85/6/9 (quality % ratio) 2, (Wu sprouts wings and learns (strain) and produce the inferior ethene (polyfluorovinylidene) of carbon black and poly-fluorine, trade name KF-1000) positive active material that obtains is scattered in the N-N-methyl-2-2-pyrrolidone N-, the slurry that obtains is coated on the positive electrode collector (thickness is the aluminium foil of 20 μ m) equably, after the drying, stamping-out is the disk of diameter 12.5mm, makes anodal.
(making of negative pole)
(Timcal company produces at the Delanium powder, trade name KS-44) adds the styrene butadiene rubbers of disperseing in by distilled water, making solid component content is 6 quality %, utilize dispersant to mix, the slurry that obtains is coated on the negative electrode collector (thickness is the aluminium foil of 18 μ m) equably, after the drying, stamping-out is the disk of diameter 12.5mm, makes negative pole.
(making of dividing plate)
With diameter is dividing plate (Celgard (strain) produces, trade name Celgard3501) impregnation the foregoing description of the polyethylene system of 14mm or the electrolyte that comparative example is made, and makes dividing plate.
(making of coin shape lithium secondary battery)
In the stainless steel tank of double as positive electrode collector, accommodate above-mentioned positive pole,, with pad the hush panel of this tank body and double as negative electrode collector is compressed sealing, making coin shape lithium secondary battery by insulation thereon across the above-mentioned negative pole of aforementioned barriers mounting.
(discharging and recharging test)
According to the following condition determination that discharges and recharges, measure the discharge capacity after 50 circulations.Evaluation is that the result with comparative example 1 is that 100 indexes that obtain carry out.The results are shown in table 2.
Charging/discharging voltage: 2.5～4.2V
Charging: 0.5C, 4.2V, keeping certain voltage is 1/10 until charging current.
Discharge: 1C
Test example 5 (flame retardant test)
Investigate the anti-flammability of electrolyte according to the methods below.The results are shown in table 2.
(modulation of sample)
The rectangle that will be cut into 50mm * 100mm respectively with the positive poles and the negative pole of test example 4 same making with the dividing plate (Celgard (strain) produce, trade name Celgard 3501) of their clampings by polyethylene system, is made laminated body.Anodal and negative pole, be impregnated in this laminated body in the electrolyte that the foregoing description or comparative example make as lead and welding afterwards by the aluminium foil of width 5mm, length 150mm, then carry out laminating seal, make laminated cell.
(test method)
Laminated cell is carried out following 3 kinds of flame retardant tests.
[test of nail thorn]
Laminated cell is charged to 4.3V, and the nail with diameter 3mm connects laminated cell afterwards, investigates laminated cell and has or not generation spark/break.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
[overcharge test]
With 10 hour rates laminated cell is carried out charging in 24 hours, investigate laminated cell and have or not the generation spark.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
[short circuit test]
Laminated cell is charged to 4.3V, make anodal and negative pole short circuit by copper cash afterwards, investigate laminated cell and have or not the generation spark.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
Table 2
Figure A200780026598D00311
Test example 6 (experiment of catching fire)
Investigate the noninflammability (non-ignitable character) of the electrolyte of making respectively in embodiment 1,4 and the comparative example 1 in the following method.The results are shown in table 3.
(making of sample)
Rectangular cellulose paper (width 15mm, length 320mm, thickness 0.04mm) be impregnated in fully in the electrolyte of the foregoing description or comparative example manufacturing, take out afterwards, obtain sample.
(test method)
Sample is fixed in metal, and the fire of an end of sample and igniter (lighter) is approaching, keeps 1 second, investigates to have or not and catches fire.Under the situation of catching fire, measure the burning length of sample.Carry out 3 tests, average.
Table 3
Figure A200780026598D00321
Then, at second mode of the present invention, the present invention will be described to enumerate embodiment, but the present invention is not limited to these examples.
Wherein, employed each compound is as shown below in following embodiment and the comparative example.
Composition (Ab)
(Ab-1)：HCF 2CF 2CH 2OCF 2CFHCF 3
(Ab-2)：CF 3CF 2CH 2OCF 2CFHCF 3
Composition (Bb)
(Bb-1): ethylene carbonate
(Bb-2): vinylene carbonate
Composition (Cb)
(Cb-1): dimethyl carbonate
(Cb-2): diethyl carbonate
(Cb-3): ethylmethyl carbonate
Composition (Db)
(Db-1): tricresyl phosphate 2,2,3,3,3-five fluoropropyl esters
(Db-2): trimethyl phosphate
Electrolytic salt (IIb-1)
(IIb-1-1)：LiN(SO 2C 2F 5) 2
(IIb-1-2)：LiN(SO 2CF 3) 2
Electrolytic salt (IIb-2)
(IIb-2-1)：LiPF 6
(IIb-2-2)：LiBF 4
Embodiment 11
With (Ab)/(Bb)/(Cb) is the HCF of the mixed of 30/3/67 volume % as composition (Ab) 2CF 2CH 2OCF 2CFHCF 3(Ab-1), as the ethylene carbonate (Bb-1) of composition (Bb), as the dimethyl carbonate (Cb-1) of composition (Cb), modulation dissolving electrolyte salt solvent, interpolation is as the LiN (SO of electrolyte (IIb-1) in this solvent for dissolving electrolyte salt 2C 2F 5) 2(IIb-1-1), make its concentration reach 1.0 mol, fully stir down, make electrolyte of the present invention at 25 ℃.
Embodiment 12～70
Similarly to Example 11, mix as composition (Ab), composition (Bb), composition (Cb), electrolyte (IIb-1), as required each compound of table 4～6 records of composition (Db), electrolytic salt (IIb-2) with the amount shown in table 4～6, make electrolyte of the present invention.
Comparative example 7
Adding ingredient (Ab) with mixed ethylene carbonate (Bb-1)/dimethyl carbonate (Cb-1) of 15/85 volume %, is not modulated the dissolving electrolyte salt solvent, adds LiPF in this solvent for dissolving electrolyte salt 6(IIb-2-1), make concentration reach 1.0 mol, fully stir down, make the relatively electrolyte of usefulness at 25 ℃.
Comparative example 8～14
Similarly to Example 11, mix as composition (Ab), composition (Bb), composition (Cb), electrolyte (IIb-1), as required each compound of table 7 record of composition (Db), electrolytic salt (IIb-2) with the amount shown in the table 7, make the relatively electrolyte of usefulness.
Test example 7 (dissolubility of electrolytic salt)
With the electrolyte 6ml that makes respectively in embodiment 11～70 and the comparative example 8～14, be taken to the sample bottle of 9ml volume, under 25 ℃, left standstill the state of visual observations liquid 8 hours.The results are shown in table 4～7.
(evaluation criterion)
Zero: be homogeneous solution
△: electrolytic salt is separated out
*: the liquid genetic horizon separates
Test example 8 (low-temperature stability)
With the electrolyte 6ml that makes respectively in embodiment 11～70 and the comparative example 8～14, be taken to the sample bottle of 9ml volume, visual observations leaves standstill the state after 8 hours in-20 ℃ freezer.The results are shown in table 4～7.
(evaluation criterion)
Zero: be homogeneous solution
△: electrolytic salt is separated out
*: liquid curing
Figure A200780026598D00351
Figure A200780026598D00361
Figure A200780026598D00371
Table 7
Figure A200780026598D00381
Test example 9 (ionic conductance)
In the following method the ionic conductance of the electrolyte made respectively in embodiment 11,13,18,19,23,24,28,33,38,39,43 and the comparative example 7,9 is measured.The results are shown in table 8 and table 9.
(test method)
By the 4 terminal methods of interchange, measure the ionic conductance under the room temperature.The SI1280B that impedance measuring instrument uses Dongyang technical (strain) to produce is 10 in frequency 4Hz～10 1The scope of Hz is carried out.
Test example 10 (charge-discharge characteristic)
Make the coin shape lithium secondary battery according to the methods below.
(anodal making)
To mix LiCoO according to 85/6/9 (quality % ratio) 2, (Wu sprouts wings and learns (strain) and produce the inferior ethene of carbon black and poly-fluorine, trade name KF-1000) and positive active material be scattered in the N-N-methyl-2-2-pyrrolidone N-, the slurry that obtains is coated on the positive electrode collector (thickness is the aluminium foil of 20 μ m) equably, after the drying, stamping-out is the disk of diameter 12.5mm, makes anodal.
(making of negative pole)
(Timcal company produces at the Delanium powder, trade name KS-44) adds the styrene butadiene rubbers of disperseing in by distilled water, making solid component content is 6 quality %, utilize dispersant to mix, the slurry that obtains is coated on the negative electrode collector (thickness is the aluminium foil of 18 μ m) equably, after the drying, stamping-out is the disk of diameter 12.5mm, makes negative pole.
(making of dividing plate)
With diameter be 14mm, by the electrolyte that the dividing plate of polyethylene system (Celgard (strain) produces, trade name Celgard3501) impregnation the foregoing description or comparative example are made, make dividing plate.
(making of coin shape lithium secondary battery)
In the stainless steel tank of double as positive electrode collector, accommodate above-mentioned positive pole,, with pad the hush panel of this tank body and double as negative electrode collector is compressed sealing, making coin shape lithium secondary battery by insulation thereon across the above-mentioned negative pole of aforementioned barriers mounting.
(discharging and recharging test)
According to the following condition determination that discharges and recharges, measure the discharge capacity after 50 circulations.Evaluation is that the result with embodiment 23 is that 100 indexes that get carry out.The results are shown in table 8 and table 9.
Charging/discharging voltage: 2.5～4.2V
Charging: 0.5C, 4.2V, keeping certain voltage is 1/10 until charging current.
Discharge: 1C
Test example 11 (flame retardant test)
Investigate the anti-flammability of electrolyte according to the methods below.The results are shown in table 8 and table 9.
(modulation of sample)
The rectangle that will be cut into 50mm * 100mm respectively with the positive poles and the negative pole of test example 10 same making with the dividing plate (Celgard (strain) produce, trade name Celgard 3501) of their clampings by polyethylene system, is made laminated body.Anodal and negative pole, be impregnated in this laminated body in the electrolyte that the foregoing description or comparative example make as lead and welding afterwards by the aluminium foil of width 5mm, length 150mm, then carries out laminating seal, the making laminated cell.
(test method)
Laminated cell is carried out following 3 kinds of flame retardant tests.
[test of nail thorn]
Laminated cell is charged to 4.3V, and the nail with diameter 3mm connects laminated cell afterwards, investigates laminated cell and has or not generation spark/break.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
[overcharge test]
With 10 hour rates laminated cell is carried out charging in 24 hours, investigate laminated cell and have or not the generation spark.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
[short circuit test]
Laminated cell is charged to 4.3V, make anodal and negative pole short circuit by copper cash afterwards, investigate laminated cell and have or not the generation spark.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
Table 8
Table 9
Figure A200780026598D00411
Test example 12 (experiment of catching fire)
Investigate the noninflammability (non-ignitable character) of the electrolyte of making respectively in embodiment 43,58 and the comparative example 7 in the following method.The results are shown in table 10.
(making of sample)
Rectangular cellulose paper (width 15mm, length 320mm, thickness 0.04mm) be impregnated in fully in the electrolyte of the foregoing description or comparative example manufacturing, take out afterwards, obtain sample.
(test method)
Sample is fixed in metal, and an end of sample and the fire of igniter are approaching, keep 1 second, investigate to have or not and catch fire.Under the situation of catching fire, measure the burning length of sample.Carry out 3 tests, average.
Table 10
Figure A200780026598D00421
Test example 12 (charge-discharge characteristic)
With the test example 10 same slurries of making positive pole, negative pole, be coated on aluminium foil with cutter type coating, thickness is 50 μ m.Lead is installed respectively on these positive poles, negative pole, is rolled relatively across dividing plate afterwards, inserting with SUS304 is the outer tinning of material, seals after the vacuum impregnation electrolyte, makes diameter 18mm, the cylindrical battery of height 50mm.The safety device of safety valve etc. is not installed for the difference of clear and definite fail safe.And, according to the following condition determination that discharges and recharges, measure the discharge capacity after 50 circulations.Evaluation is that the result with comparative example 7 is that 100 indexes that get carry out.The results are shown in table 11.
Charging/discharging voltage: 2.5～4.2V
Charging: 0.5C, 4.2V, keeping certain voltage is 1/10 until charging current.
Discharge: 1C
Test example 13 (flame retardant test)
For these cylinder batteries, follow closely the thorn test according to the methods below.The results are shown in table 11.
[test of nail thorn]
Laminated cell is charged to 4.3V, and the nail with diameter 3mm connects laminated cell afterwards, investigates laminated cell and has or not generation spark/break.Estimate as followsly, producing in the absence of spark (breaking) is zero, produce under the situation of spark (breaking) for *.
Table 11
Figure A200780026598D00431
According to electrochemical device of the present invention, can provide that dissolubility height that phase decomposition and anti-flammability and excellent heat resistance, electrolytic salt do not take place under the low temperature yet, discharge capacity are big, the electrochemical device of excellent charge, design safety and large-scale electrochemical device easily.

Claims (22)

1. an electrochemical device is characterized in that having electrolyte,
Described electrolyte contains:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1-O-Rf 2Shown fluorine-containing ether, in the formula, Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3～6;
(B) cyclic carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and cyclic carbonate (B),
Solvent for dissolving electrolyte salt (I) with respect to whole solvents (I), contains: fluorine-containing ether (A) 30～60 volume %, cyclic carbonate (B) 3～40 volume % and linear carbonate (C) 10～67 volume %.
2. electrochemical device according to claim 1 is characterized in that:
The fluorine-containing rate of the fluorine-containing ether (A) shown in the formula (1) is 55～74 quality %, in the formula (1), and Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3 or 4.
3. electrochemical device according to claim 1 and 2 is characterized in that:
Cyclic carbonate (B) is ethylene carbonate and/or vinylene carbonate.
4. according to each described electrochemical device in the claim 1～3, it is characterized in that:
Solvent for dissolving electrolyte salt (I) with respect to whole solvents (I), contains: fluorine-containing ether (A) 40～60 volume %, cyclic carbonate (B) 5～25 volume % and linear carbonate (C) 15～55 volume %.
5. according to each described electrochemical device in the claim 1～4, it is characterized in that:
It is a battery.
6. an electrolyte is characterized in that, contains:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1-O-Rf 2Shown fluorine-containing ether, in the formula, Rf 1And Rf 2Identical or different, be the fluoroalkyl that contains of carbon number 3～6;
(B) cyclic carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and cyclic carbonate (B),
Solvent for dissolving electrolyte salt (I) with respect to whole solvents (I), contains: fluorine-containing ether (A) 30～60 volume %, cyclic carbonate (B) 3～40 volume % and linear carbonate (C) 10～67 volume %.
7. an electrolyte for lithium secondary batteries is characterized in that, contains:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1a-O-Rf 2aShown fluorine-containing ether, in the formula, Rf 1aAnd Rf 2aIdentical or different, be the fluoroalkyl that contains of carbon number 3 or 4;
(B) ethylene carbonate and/or vinylene carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and ethylene carbonate and/or vinylene carbonate (B),
Solvent for dissolving electrolyte salt (I), with respect to whole solvents (I), contain: fluorine-containing ether (A) 40～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 3～20 volume % and linear carbonate (C) 20～57 volume %,
Electrolytic salt (II) is LiPF 6Or LiBF 4,
The concentration of electrolytic salt is more than 0.8 mol.
8. electrolyte for lithium secondary batteries according to claim 7, it is characterized in that: solvent for dissolving electrolyte salt (I), with respect to whole solvents (I), contain: fluorine-containing ether (A) 40～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 3～15 volume % and linear carbonate (C) 31～57 volume %
The concentration of electrolytic salt is more than 1.0 mol.
9. according to claim 7 or 8 described electrolyte for lithium secondary batteries, it is characterized in that:
The boiling point of fluorine-containing ether (A) is more than 90 ℃.
10. according to each described electrolyte for lithium secondary batteries in the claim 7～9, it is characterized in that:
Fluorine-containing ether (A) is HCF 2CF 2CH 2OCF 2CFHCF 3
11., it is characterized in that according to each described electrolyte for lithium secondary batteries in the claim 7～10:
Contain the following phosphate (D) of 3 volume % in the solvent for dissolving electrolyte salt (I).
12. electrolyte for lithium secondary batteries according to claim 11 is characterized in that:
Phosphate (D) is fluorine-containing alkyl phosphate.
13. an electrolyte for lithium secondary batteries is characterized in that, contains:
(I) solvent for dissolving electrolyte salt; With
(II) electrolytic salt,
Wherein, described solvent for dissolving electrolyte salt (I) contains:
(A) formula (1): Rf 1b-O-Rf 2bShown fluorine-containing ether, in the formula, Rf 1bAnd Rf 2bIdentical or different, be the fluoroalkyl that contains of carbon number 3～6;
(B) ethylene carbonate and/or vinylene carbonate; With
(C) linear carbonate that can both all mix with fluorine-containing ether (A) and ethylene carbonate and/or vinylene carbonate (B),
Solvent for dissolving electrolyte salt (I), with respect to whole solvents (I), contain: fluorine-containing ether (A) 30～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 3～40 volume % and linear carbonate (C) 10～67 volume %,
Electrolytic salt (II) contains at least and is selected from LiN (SO 2CF 3) 2And LiN (SO 2C 2F 5) 2In electrolytic salt (IIa), and the concentration of electrolytic salt (II) is more than 0.5 mol.
14. electrolyte for lithium secondary batteries according to claim 13 is characterized in that:
The fluorine-containing rate of the fluorine-containing ether (A) shown in the formula (1) is below the above 74 quality % of 55 quality %, Rf 1bWith Rf 2bIdentical or different, be the fluoroalkyl that contains of carbon number 3 or 4.
15., it is characterized in that according to claim 13 or 14 described electrolyte for lithium secondary batteries:
Also contain and be selected from LiPF 6And LiBF 4In electrolytic salt (IIb), the concentration of electrolytic salt (IIb) is more than 0.1 mol.
16. electrolyte for lithium secondary batteries according to claim 15 is characterized in that:
The concentration of electrolytic salt (IIa) is 0.4～1.3 mol, and the concentration of electrolytic salt (IIb) is 0.1～0.5 mol, and the concentration of electrolytic salt (IIb)/(concentration of the concentration+electrolytic salt (IIb) of electrolytic salt (IIa)) is more than 0.1 below 0.4.
17. electrolyte for lithium secondary batteries according to claim 16 is characterized in that:
Electrolytic salt (IIa) is LiN (SO 2CF 3) 2
18., it is characterized in that according to each described electrolyte for lithium secondary batteries in the claim 13～17:
Solvent for dissolving electrolyte salt (I) with respect to whole solvents (I), contains: fluorine-containing ether (A) 40～60 volume %, ethylene carbonate and/or vinylene carbonate (B) 5～25 volume % and linear carbonate (C) 15～55 volume %.
19., it is characterized in that according to each described electrolyte for lithium secondary batteries in the claim 13～18:
The boiling point of fluorine-containing ether (A) is more than 80 ℃.
20., it is characterized in that according to each described electrolyte for lithium secondary batteries in the right 13～19:
Fluorine-containing ether (A) is selected from HCF 2CF 2CH 2OCF 2CFHCF 3And CF 3CF 2CH 2OCF 2CFHCF 3
21., it is characterized in that according to each described electrolyte for lithium secondary batteries in the claim 13～20:
Contain the following phosphate (D) of 10 volume % in the solvent for dissolving electrolyte salt (I).
22. electrolyte for lithium secondary batteries according to claim 21 is characterized in that: phosphate (D) is fluorine-containing alkyl phosphate.
CNA200780026598XA 2006-07-13 2007-07-12 Electrochemical device Pending CN101490893A (en)

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Cited By (7)

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CN102055019A (en) * 2009-10-30 2011-05-11 三星Sdi株式会社 Electrolyte for lithium battery, lithium battery comprising same and method of operating battery
CN102074737A (en) * 2009-11-19 2011-05-25 三星Sdi株式会社 Electrolyte for lithium battery and lithium battery containing the same
CN102959787A (en) * 2010-06-25 2013-03-06 Nec能源元器件株式会社 Lithium ion secondary battery
CN105322228A (en) * 2015-01-10 2016-02-10 汕头市金光高科有限公司 High-safety and flame-retardant electrolyte of lithium ion battery
CN107293788A (en) * 2017-06-28 2017-10-24 常州市万昌化工有限公司 A kind of lithium ion battery flame-retardant electrolyte and preparation method thereof
CN114024036A (en) * 2021-11-05 2022-02-08 中南大学 Low-concentration lithium ion battery electrolyte and lithium ion battery prepared from same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102055019A (en) * 2009-10-30 2011-05-11 三星Sdi株式会社 Electrolyte for lithium battery, lithium battery comprising same and method of operating battery
CN102074737A (en) * 2009-11-19 2011-05-25 三星Sdi株式会社 Electrolyte for lithium battery and lithium battery containing the same
CN102074737B (en) * 2009-11-19 2015-05-13 三星Sdi株式会社 Electrolyte for lithium battery and lithium battery containing the same
CN102959787A (en) * 2010-06-25 2013-03-06 Nec能源元器件株式会社 Lithium ion secondary battery
CN105870494A (en) * 2010-06-25 2016-08-17 Nec能源元器件株式会社 Lithium ion secondary battery
CN105870494B (en) * 2010-06-25 2019-07-05 Nec 能源元器件株式会社 Lithium ion secondary battery
CN105322228A (en) * 2015-01-10 2016-02-10 汕头市金光高科有限公司 High-safety and flame-retardant electrolyte of lithium ion battery
CN107293788A (en) * 2017-06-28 2017-10-24 常州市万昌化工有限公司 A kind of lithium ion battery flame-retardant electrolyte and preparation method thereof
CN114024036A (en) * 2021-11-05 2022-02-08 中南大学 Low-concentration lithium ion battery electrolyte and lithium ion battery prepared from same
CN116914264A (en) * 2023-09-14 2023-10-20 泉州市博泰半导体科技有限公司 Electrolyte, preparation method thereof, battery, electrochemical device and assembly
CN116914264B (en) * 2023-09-14 2023-12-19 泉州市博泰半导体科技有限公司 Electrolyte, preparation method thereof, battery, electrochemical device and assembly

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