CN105047994A - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
- Publication number
- CN105047994A CN105047994A CN201510606516.5A CN201510606516A CN105047994A CN 105047994 A CN105047994 A CN 105047994A CN 201510606516 A CN201510606516 A CN 201510606516A CN 105047994 A CN105047994 A CN 105047994A
- Authority
- CN
- China
- Prior art keywords
- carbon number
- electrolyte
- alkyl
- fluoro
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/659—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having three phosphorus atoms as ring hetero atoms in the same ring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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 relates to an electrolyte and a lithium ion battery comprising the same. The electrolyte comprises a lithium salt, a solvent and addition agents. The addition agents include phosphoric acid cyclic anhydride compounds and cyclophosphazene compounds. The electrolyte comprising the phosphoric acid cyclic anhydride compounds and the cyclophosphazene compounds is applied into the lithium ion battery, so that the cycling performance of the lithium ion battery is improved, and the heat stability of the lithium ion battery at high temperature is improved.
Description
Technical field
The application relates to technical field of lithium ion, particularly a kind of electrolyte and comprise the lithium ion battery of this electrolyte.
Background technology
Lithium ion battery because of have specific energy high, have extended cycle life, the advantage such as self discharge is little, be widely used in consumer electronics product and energy storage and electrokinetic cell.Along with the extensive use of lithium ion battery, its cycle life becomes a kind of important indicator of lithium ion battery, in addition, because lithium ion battery shows unstable phenomenon after cycling, such as, the thermal stability of the lithium ion battery after circulation can be deteriorated, in order to ensure use safety, while raising cycle performance of lithium ion battery, also need to improve lithium ion battery thermal stability after cycling.As can be seen here, the security performance of lithium ion battery is also particularly important.
Lithium ion battery thermal stability is after cycling subject to the impact of factors, and wherein, electrolyte, as the important component part of lithium ion battery, has the thermal stability after its circulation and affects gravely.
Therefore, the electrolyte needing now a kind of excellent performance badly, promoting the cycle performance of lithium ion battery simultaneously, also can improve the thermal stability of lithium ion battery.
Summary of the invention
In order to solve the problem, the applicant has carried out studying with keen determination, found that: will the electrolyte of phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds be comprised, be applied to after in lithium ion battery, the cycle performance of lithium ion battery can not only be improved, and lithium ion battery at high temperature thermal stability can be improved, thus complete the application.
The object of the application is to provide a kind of electrolyte, comprises lithium salts, solvent and additive, and wherein, described additive comprises phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds.
Another object of the application is to provide a kind of lithium ion battery, comprises the electrolyte that positive plate, negative plate, lithium battery diaphragm and the application provide.
The electrolyte of what the application provided include phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds, this electrolyte is applied to after in lithium ion battery, this electrolyte can form fine and close solid electrolyte interface (SEI) film in negative terminal surface, effective minimizing electrolyte is in the decomposition of negative pole, hydrofluoric acid (HF) in all right Electolyte-absorptive, effective minimizing HF, to the corrosion of SEI film, is highly profitable to the cycle performance improving battery; In addition the passivating film impedance that formed in negative terminal surface of electrolyte is less, effectively can reduce the increase of cathode interface impedance in cyclic process.When ring phosphonitrile compounds and phosphoric acid cyclic anhydride compounds combinationally use, not only be conducive to electrolyte and form stable SEI film in negative terminal surface, the ionic conductivity of SEI film can also be increased, make the movement of lithium ion become smooth and easy, therefore also reduce the increase of membrane impedance in cyclic process.
Can learn thus, electrolyte the application provided is applied to after in lithium ion battery, the cycle performance of lithium ion battery can not only be improved, such as under the high pressure of more than 4.35V through repeatedly circulation after, still there is higher capability retention, but also lithium ion battery thermal stability at high temperature can be improved, especially, improve the thermal stability of lithium ion battery at 150 DEG C.
Embodiment
Be described in detail below by the application, the feature of the application and advantage will illustrate along with these and become more clear, clear and definite.
The object of the application is to provide a kind of electrolyte, comprises lithium salts, organic solvent and additive, and wherein, described additive comprises phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds.
Above-mentioned mentioned phosphoric acid cyclic anhydride compounds is the compound with circulus that one or more phosphoric acid are formed through intermolecular dehydrating condensation, the compound of described circulus is alternately made up of phosphorus atoms and oxygen atom, and be connected with phosphorus oxygen double bond on the phosphorus atom, in addition, the singly-bound be connected with phosphorus atoms can be connected other groups with rational situation according to the actual requirements to modify.
Preferably, one or more for being selected from the compound shown in following formula I of described phosphoric acid cyclic anhydride compounds.
In above-mentioned formula I, R
1, R
2, R
3independently of one another for be selected from carbon number be 1 ~ 20 alkyl, carbon number be one in the aryl of 6 ~ 26.
In above-mentioned formula I, R
1, R
2, R
3can be different, also can be mutually the same, or be that wherein both are identical arbitrarily.Especially, R
1, R
2, R
3be identical group.
Work as R
1, R
2, R
3independently of one another for when to be selected from carbon number be the alkyl of 1 ~ 20, the concrete kind of alkyl is not subject to concrete restriction, can select according to the actual requirements, such as chain-like alkyl and cyclic alkyl, wherein chain alkyl comprises again straight chained alkyl and branched alkyl, in addition, cyclic alkyl can there is substituting group, also can not contain substituting group.In described alkyl, in alkyl, the preferred lower limit of carbon number can be 1,3,5, and in alkyl, the preferred higher limit of carbon number can be 3,4,5,6,7,8,10,12,16.
Preferably, carbon number is selected to be the alkyl of 1 ~ 10, further preferably, selection carbon number is the chain alkyl of 1 ~ 6, carbon number is the cyclic alkane base of 3 ~ 8, still more preferably, selection carbon number is the chain alkyl of 1 ~ 4, and carbon number is the cyclic alkane base of 5 ~ 7.
As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2, 2-dimethyl propyl, 1-ethyl propyl, 1-methyl butyl, 2-methyl butyl, n-hexyl, isohesyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methyl amyl, 3-methyl amyl, 1, 1, 2-thmethylpropyl, 3, 3-dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, different heptyl, suberyl, n-octyl, ring octyl group, nonyl, decyl, hendecane alkyl, dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane alkyl, hexadecane alkyl, heptadecane alkyl, octadecane alkyl, nonadecane alkyl, eicosane alkyl.
Work as R
1, R
2, R
3independently of one another for carbon number be the aryl of 6 ~ 26 time, the not special restriction of concrete kind of aryl, can select according to the actual requirements, such as, phenyl, benzene alkyl, at least containing aryl such as xenyl, the condensed-nuclei aromatics base of a phenyl, wherein can also be connected with other substituted radicals on xenyl and condensed-nuclei aromatics base.
In aryl, the preferred higher limit of carbon number can be 7,8,9,10,12,14,16,18,20,22, and in aryl, the preferred lower limit of carbon number can be 6,7,8,9.
In a preferred embodiment, select carbon number to be the aryl of 6 ~ 16, further preferably, select carbon number to be the aryl of 6 ~ 9.
As the enforcement of aryl, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, between tolyl, to ethylbenzene, between ethylbenzene, adjacent ethylbenzene, 3, 5-xylyl, 2, 6-3,5-dimethylphenyl, 3, 5-diethyl phenyl, 2, 6-diethyl phenyl, 3, 5-diisopropylbenzyl, 2, 6-diisopropylbenzyl, 3, 5-bis-n-proplbenzene base, 2, 6-bis-n-proplbenzene base, 3, 5-bis-n-butyl benzene base, 2, 6-bis-n-butyl benzene base, 3, 5-bis-isobutylphenyl, 2, 6-bis-isobutylphenyl, 3, 5-bis-2-methyl-2-phenylpropane base, 2, 6-bis-2-methyl-2-phenylpropane base, trityl, 1-naphthyl, 2-naphthyl.
As the example of phosphoric acid cyclic anhydride compounds, specifically can enumerate:
Preferably, in above-mentioned electrolyte, the content of described phosphoric acid cyclic anhydride compounds is 0.05% ~ 3% of the total weight of electrolyte.Find after deliberation, when phosphoric acid cyclic anhydride compounds content is in the electrolytic solution too low, then electrolyte can not, at complete solid electrolyte interface (SEI) film of anodic formation, make the thermal stability under the cycle performance of lithium ion battery and high temperature substantially can not get improving; And when the too high levels of phosphoric acid cyclic anhydride compounds, electrolyte forms thicker SEI film at anode surface, lithium ion mobility resistance is caused to increase, be unfavorable for the interface stability of the negative pole of battery in cyclic process, therefore, same, the thermal stability under the cycle performance of lithium ion battery and high temperature also can be made substantially to can not get improving.Further preferably, the total content of described phosphoric acid cyclic anhydride compounds is 0.1 ~ 2% of the total weight of electrolyte.
Above-mentioned mentioned ring phosphonitrile compounds is for containing
the compound of group, wherein, the singly-bound that the short-term on each phosphorus atoms is formed after all representing and losing atom or atomic group.
Preferably, one or more for being selected from the compound shown in following formula II of described ring phosphonitrile compounds.
In above-mentioned formula II, R
4, R
5, R
6, R
7, R
8, R
9be one that the alkyl being selected from hydrogen atom, halogen atom, carbon number are 1 ~ 20, the carbon number thiazolinyl that is 2 ~ 20, the carbon number aryl that is 6 ~ 20, the carbon number alkoxyl that is 1 ~ 20, the carbon number aryloxy group that is 6 ~ 20, the carbon number haloalkyl that is 1 ~ 20, the carbon number halogenated aryl that is 6 ~ 20, the carbon number halogenated alkoxy that is 1 ~ 20, carbon number are in the haloaryloxy of 6 ~ 20 independently of one another, wherein, at R
4, R
6, R
8middle at least one is oxy radical, at R
5, R
7, R
9in at least both be halogen atom, described halogen atom is F, Cl, Br, and halogen atom herein also comprises the halogen atom in halo group, and especially, halogen atom is F, Cl.
Described oxy radical is alkoxyl, aryloxy group, halogenated alkoxy and haloaryloxy.
In above-mentioned formula II, when carbon number is the alkyl of 1 ~ 20, the concrete kind of alkyl is not subject to concrete restriction, can select according to the actual requirements, such as chain-like alkyl and cyclic alkyl, wherein chain-like alkyl comprises again straight chained alkyl and branched alkyl, in addition, cyclic alkane base can there is substituting group, also can not contain substituting group.In described alkyl, in alkyl, the preferred lower limit of carbon number can be 1,3,5, and in alkyl, the preferred higher limit of carbon number can be 3,4,5,6,8,10,12,16.
Preferably, carbon number is selected to be the alkyl of 1 ~ 10, further preferably, select carbon number to be the chain-like alkyl of 1 ~ 6, carbon number is the cyclic alkyl of 3 ~ 8, still more preferably, select carbon number to be the chain-like alkyl of 1 ~ 4, carbon number is the cyclic alkyl of 5 ~ 7.
As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2, 2-dimethyl propyl, 1-ethyl propyl, 1-methyl butyl, 2-methyl butyl, n-hexyl, isohesyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methyl amyl, 3-methyl amyl, 1, 1, 2-thmethylpropyl, 3, 3-dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, different heptyl, suberyl, n-octyl, ring octyl group, nonyl, decyl, hendecane alkyl, dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane alkyl, hexadecane alkyl, heptadecane alkyl, octadecane alkyl, nonadecane alkyl, eicosane alkyl.
In above-mentioned formula II, carbon number is the thiazolinyl of 2 ~ 20, and wherein, the not special restriction in the number of double bond and the position of double bond, can select the thiazolinyl of desired structure according to actual conditions.Especially, the number of double bond can be 1,2,3 or 4, preferred mono alkenyl.Especially, double bond is positioned at the end of selected thiazolinyl, wherein, described end is the position that double bond is connected with phosphorus atoms in ring phosphonitrile compounds away from unsaturated alkyl, such as, when carbon number is more than or equal to 3, the carbon atom on unsaturated bond is not connected with phosphorus atoms.In described thiazolinyl, the preferred lower limit of the carbon number of thiazolinyl can be 2,3,4, and the preferred higher limit of the carbon number of unsaturated alkyl can be 3,4,5,6,7,8,10,12,16,18.
In a preferred embodiment, select carbon number to be the thiazolinyl of 2 ~ 10, further preferably, select carbon number to be the thiazolinyl of 2 ~ 6, still more preferably, select carbon number to be the thiazolinyl of 2 ~ 5.
As the example of thiazolinyl, specifically can enumerate: vinyl, pi-allyl, isopropenyl, 1-cyclobutenyl, 2-cyclobutenyl, 2-methyl-2-acrylic, 1-methyl-2-acrylic, 2-methylpropenyl, pentenyl, 1-hexenyl, 3,3-dimethyl-1-cyclobutenyls, heptenyl, octenyl.
In above-mentioned formula II, when carbon number is the aryl of 6 ~ 20, the not special restriction of concrete kind of aryl, can select according to the actual requirements, such as, phenyl, benzene alkyl, at least containing aryl such as xenyl, the condensed-nuclei aromatics base of a phenyl, wherein can also be connected with other groups on xenyl and condensed-nuclei aromatics base.
In aryl the preferred higher limit of carbon number can be 7,8,9,10,12,14,16,18, the preferred lower limit of carbon number can be 6,7,8,9 in aryl.
In a preferred embodiment, select carbon number to be the aryl of 6 ~ 16, further preferably, select carbon number to be the aryl of 6 ~ 14, still more preferably, select carbon number to be the aryl of 6 ~ 10.
As the enforcement of aryl, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, between tolyl, to ethylbenzene, between ethylbenzene, adjacent ethylbenzene, 3, 5-xylyl, 2, 6-3,5-dimethylphenyl, 3, 5-diethyl phenyl, 2, 6-diethyl phenyl, 3, 5-diisopropylbenzyl, 2, 6-diisopropylbenzyl, 3, 5-bis-n-proplbenzene base, 2, 6-bis-n-proplbenzene base, 3, 5-bis-n-butyl benzene base, 2, 6-bis-n-butyl benzene base, 3, 5-bis-isobutylphenyl, 2, 6-bis-isobutylphenyl, 3, 5-bis-2-methyl-2-phenylpropane base, 2, 6-bis-2-methyl-2-phenylpropane base, trityl, 1-naphthyl, 2-naphthyl.
In above-mentioned formula II, carbon number is 1 ~ 20 alkoxyl, the concrete kind of alkyl wherein in alkoxyl is not subject to concrete restriction, can select according to the actual requirements, such as chain alkyl and cyclic alkane base, wherein chain alkyl comprises again linear paraffin base and branched alkane alkyl, in addition, cyclic alkane base can there is substituting group, also can not contain substituting group.In described alkoxyl, the preferred lower limit of carbon number can be 1,3,4, and the preferred higher limit of carbon number can be 3,4,5,6,7,8,10,12,16,18.
Preferably, select carbon number be 1 ~ 10 alkoxyl, further preferably, select carbon number be 1 ~ 6 chain alkoxyl, carbon number be the cyclic alkoxy of 3 ~ 8, still more preferably, select carbon number be 1 ~ 4 chain alkoxyl, carbon number be the cyclic alkoxy of 5 ~ 7.
As an example, specifically can enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy, neopentyl oxygen, 2,3-dimethyl propoxyl group, 1-ethylpropoxy, 1-methyl butyl oxygen base, just own oxygen base, dissident's oxygen base, 1,1,2-trimethyl propoxyl group, n-heptyl oxygen base, n-octyl oxygen base, ring propoxyl group, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, ring oxygen in heptan base, ring octyloxy.
In above-mentioned formula II, carbon number is the aryloxy group of 6 ~ 20, and wherein the concrete kind of aryl is not subject to concrete restriction, can select according to the actual requirements, such as, phenyl, benzene alkyl, at least containing aryl such as xenyl, the condensed-nuclei aromatics base of a phenyl.In described aryloxy group, in aryloxy group, the preferred lower limit of carbon number can be 6,7,8,9, and in fragrant oxygen cyano group, the preferred higher limit of carbon number can be 7,8,9,10,12,14,16,18.
Preferably, select carbon number to be the aryloxy group of 6 ~ 16, further preferably, select carbon number to be the aryloxy group of 6 ~ 14, still more preferably, select carbon atom to be the aryloxy group of 6 ~ 10.
As the example of aryloxy group, specifically can enumerate: phenoxy group, benzyloxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 4-ethyl phenoxy group, 3-ethyl phenoxy group, 2-ethyl phenoxy group, 4-n-pro-pyl phenoxy group, 3-n-pro-pyl phenoxy group, 2-n-pro-pyl phenoxy group, 4-isopropyl phenoxy group, 3-isopropyl phenoxy group, 2-isopropyl phenoxy group, 4-normal-butyl phenoxy group, 3-normal-butyl phenoxy group, 2-normal-butyl phenoxy group, 4-isobutyl group phenoxy group, 3-isobutyl group phenoxy group, 2-isobutyl group phenoxy group, 4-tert-butyl group phenoxy group, 3-tert-butyl group phenoxy group, 2-tert-butyl group phenoxy group, 3,5-dimethyl phenoxy, 2,6-dimethyl phenoxy, 3,5-diethyl phenoxy group, 2,6-diethyl phenoxy group, 3,5-diη-propyl phenoxy group, positive third methylphenoxy of 2,6-, 3,5-diisopropyl phenoxy group, 2,6-diisopropyl phenoxy group, 3,5-di-n-butyl phenoxy group, 2,6-di-n-butyl phenoxy group, 4-methylbenzyloxy, 3-methylbenzyloxy, 2-methylbenzyloxy, 4-ethyl benzyloxy, 3-ethyl benzyloxy, 2-ethyl benzyloxy, 3,5-diisopropyl benzyloxy, 2,6-diisopropyl benzyloxy, 1-naphthoxy, 2-naphthoxy.
In above-mentioned formula II, carbon number is the haloalkyl of 1 ~ 20, the not special restriction of the replacement number of the halogen atom wherein in haloalkyl and the position of substitution thereof, can replace the part hydrogen atom on abovementioned alkyl or whole hydrogen atom according to the actual requirements.Such as, the number of halogen atom can be 1,2,3 or 4.When the number that halogen atom replaces is more than 2, the kind of halogen atom can be identical, also can difference completely, or be that the species partial of selected halogen atom is identical.In described alkyl, the preferred lower limit of the carbon number of alkyl can be 1,2,3, and the preferred higher limit of the carbon number of alkyl can be 3,4,5,6,8,10,12,16,18.
Preferably, select carbon number be 1 ~ 6 chain haloalkyl, carbon number be the cyclic haloalkyl of 3 ~ 8, still more preferably, select carbon number be 1 ~ 4 chain haloalkyl, carbon number is the cyclic haloalkyl of 5 ~ 7.
As the example of haloalkyl, specifically can enumerate: specifically can enumerate: methyl fluoride, difluoromethyl, trifluoromethyl, 1-fluoro ethyl, 1, 2-bis-fluoro ethyl, 2-fluorine n-pro-pyl, 2, 2, 2-trifluoroethyl, 2, the fluoro-n-pro-pyl of 2-bis-, 1-fluorine isopropyl, one fluorine cyclopropyl, 1-fluorine normal-butyl, 2-fluorine isobutyl group, one fluorine cyclobutyl, 1-fluorine n-pentyl, 2-fluorine n-pentyl, 1-fluorine isopentyl, 2, 2-difluoromethyl propyl group, one fluorine cyclopenta, 3-fluoro-2, 2-dimethyl propyl, the fluoro-1-ethyl propyl of 1-, the fluoro-1-methyl butyl of 1-, the fluoro-2-methyl butyl of 2-, 2-fluorine n-hexyl, one fluorine cyclohexyl, 2-methyl fluoride amyl group, the fluoro-3-methyl amyl of 3-, 2-fluoro-1, 1, 2-thmethylpropyl, 4-fluoro-3, 3-dimethylbutyl, 2-fluorine n-heptyl.In above-mentioned enumerated example, F wherein can be replaced by Cl, Br.
In above-mentioned formula II, carbon number is the halogenated aryl of 6 ~ 20, the not special restriction of the replacement number of the halogen atom wherein in halogenated aryl and the position of substitution thereof, can according to the actual requirements to the part hydrogen atom of aryl or all hydrogen atom replace, select F, Cl to replace especially.The number of halogen atom can be 1,2,3 or 4, and when being replaced by the halogen atom of more than 2, halogen atom can be identical, also can be different.In described halogenated aryl, in halogenated aryl, the preferred lower limit of carbon number can be 6,7,8,9, and in halogenated aryl, the preferred higher limit of carbon number can be 7,8,9,10,12,14,16,18.
Preferably, select carbon number to be the halogenated aryl of 6 ~ 16, further preferably, select carbon number to be the halogenated aryl of 6 ~ 14, still more preferably, select carbon atom to be the halogenated aryl of 6 ~ 10.
As the example of halogenated aryl, specifically can enumerate: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-fluorophenyl, the fluoro-4-aminomethyl phenyl of 2-, the fluoro-4-aminomethyl phenyl of 3-, 2, the fluoro-4-aminomethyl phenyl of 3-bis-, 3, the fluoro-4-aminomethyl phenyl of 5-bis-, 2, the fluoro-4-aminomethyl phenyl of 6-bis-, to trifluoromethylbenzene, o-trifluoromethyl benzene, m-trifluoromethyl benzene, 2-luorobenzyl, 3-luorobenzyl, 4-luorobenzyl, 3, 5-difluorobenzyl, 2, 6-difluorobenzyl, the fluoro-4-ethylphenyl of 2-, the fluoro-4-ethylphenyl of 3-, 2-fluoro-4-n-pro-pyl phenyl, 3-fluoro-4-n-pro-pyl phenyl, the fluoro-4-isopropyl phenyl of 2-, the fluoro-4-isopropyl phenyl of 3-, 3, the fluoro-4-isopropyl phenyl of 5-bis-, 2, the fluoro-4-isopropyl phenyl of 6-bis-, the fluoro-1-naphthyl of 2-.In above-mentioned enumerated example, fluorine wherein can be replaced by Cl, Br.
In above-mentioned formula I, carbon number is the halogenated alkoxy of 1 ~ 20, the not special restriction of the replacement number of the halogen atom wherein in halogenated alkoxy and the position of substitution thereof, can according to the actual requirements to the part hydrogen atom of alkoxyl or all hydrogen atom replace, select F, Cl to replace especially.The number of halogen atom can be 1,2,3 or 4, and when being replaced by the halogen atom of more than 2, halogen atom can be identical, also can be different.In described halogenated alkoxy, in halogenated alkoxy, the preferred lower limit of carbon number can be 2,3,4, and in haloalkyl, the preferred higher limit of carbon number can be 3,4,5,6,7,8,10,12,14,16,18.
Preferably, carbon number is selected to be the halogenated alkoxy of 1 ~ 10, further preferably, selection carbon number is the chain halogenated alkoxy of 1 ~ 6, carbon number is the cyclic halo alkoxyl of 3 ~ 8, still more preferably, selection carbon number is the chain halogenated alkoxy of 1 ~ 4, and carbon number is the cyclic halo alkoxyl of 5 ~ 7.
As the example of halogenated alkoxy, specifically can enumerate: fluoro-methoxy, 1-fluorine ethyoxyl, 2, 2, 2 trifluoro ethoxies, the fluoro-positive propoxy of 2-, the fluoro-isopropoxy of 1-, the fluoro-1-methyl ethoxy of 2-, the fluoro-n-butoxy of 3-, the fluoro-n-pentyloxy of 4-, 2, 2-difluoromethyl propoxyl group, 1-methyl fluoride butoxy, the fluoro-just own oxygen base of 5-, 4-fluoro-dissident's oxygen base, 1, 1, 2-trifluoromethyl propoxyl group, 6-fluoro-n-heptyl oxygen base, 7-fluoro-n-octyl oxygen base, the fluoro-ring propoxyl group of 3-, the fluoro-cyclopentyloxy of 3-, the fluoro-2-methylcyclopentoxy of 4-, the fluoro-cyclohexyloxy of 3-, 3-fluorine ring oxygen in heptan base, 4-fluoro-2-methyl ring oxygen in heptan base, 3-fluorine ring octyloxy, the pungent oxygen of 4-fluoro-2-ethyl ring.In above-mentioned enumerated example, fluorine wherein can be replaced by Cl, Br.
In above-mentioned formula I, carbon number is the haloaryloxy of 7 ~ 20, the not special restriction of the replacement number of the halogen atom wherein in haloaryloxy and the position of substitution thereof, can according to the actual requirements to the part hydrogen atom of aryloxy group or all hydrogen atom replace, select F, Cl to replace especially.The number of halogen atom can be 1,2,3 or 4, and when being replaced by the halogen atom of more than 2, halogen atom can be identical, also can be different.In described haloaryloxy, in haloaryloxy, the preferred lower limit of carbon number can be 6,8,9, and in haloaryloxy, the preferred higher limit of carbon number can be 7,8,9,10,12,14,16,18.
Preferably, select carbon number to be the haloaryloxy of 6 ~ 16, further preferably, select carbon number to be the haloaryloxy of 6 ~ 14, still more preferably, select carbon atom to be the haloaryloxy of 6 ~ 10.Such as, 4-fluorophenoxy, 3-fluorophenoxy, 2-fluorophenoxy, 3,5-difluoro phenoxy group, 2,6-difluoro phenoxy group, 2,3-difluoro phenoxy group, 2,6-bis-fluoro-4-methylphenoxy, 3-(2-fluoro ethyl) phenoxy group, 2-(1-fluoro ethyl) phenoxy group, 3,5-difluoro benzyloxies, 2-fluorine benzyloxy, the fluoro-1-naphthoxy of 2-etc. all can be used as the example of haloalkoxy cyano group.
As the example of ring phosphonitrile compounds, specifically can enumerate: 2,4,4,6,6-five fluoro-2-ethoxy basic ring phosphonitrile (as shown in following formula 1), 2,4,4,6,6-five fluoro-2-phenoxy group ring phosphonitrile (as shown in following formula 2), the fluoro-2-of 2,4,4,6,6-five (4-fluorophenoxy) ring phosphonitrile (as shown in following formula 3), fluoro-2, the 4-diethoxy basic ring phosphonitriles of 2,4,6,6-tetra-(as shown in following formula 4), the fluoro-2-phenoxy group of 2,4,6,6-tetra--4-ethoxy basic ring phosphonitrile (as shown in following formula 5), the fluoro-2-of 2,4,4,6,6-five (2,2,2-trifluoro ethoxy) ring phosphonitrile (as shown in following formula 6), 2,4,6,6-tetra-fluoro-2,4 dimethoxy basic ring phosphonitrile (as shown in following formula 7), the fluoro-2-phenoxy group of 2,4,6,6-tetra--4-methyl ring phosphonitrile (as shown in following formula 8), 2,4,6-tri-fluoro-2-phenoxy group-4,6-diformazan basic ring phosphonitrile (as shown in following formula 9), the fluoro-2-of 2,4,4,6,6-five (1-fluorine n-pro-pyl) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (2-fluorine n-pro-pyl) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (the fluoro-2-cyclobutenyl of 1-) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (the fluoro-2-cyclobutenyl of 2-) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (the fluoro-2-cyclobutenyl of 3-) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (4-2-fluoro-2-butene base) ring phosphonitrile, 2,4,4,6,6-five fluoro-2-fluoro-methoxy ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (the fluoro-4-phenoxy group of 2-) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (2-methyl-4-fluorine normal-butyl) ring phosphonitrile, the fluoro-2-of 2,4,4,6,6-five (fluoro-3, the 5-dimethyl phenoxies of 2,6-bis-) ring phosphonitrile.
Preferably, in above-mentioned electrolyte, the content of described ring phosphonitrile compounds is 0.01% ~ 10% of the total weight of electrolyte.Find after deliberation, when ring phosphonitrile compounds content is in the electrolytic solution too low, then electrolyte can not form stable solid electrolyte interface (SEI) film, makes the thermal stability under the cycle performance of lithium ion battery and high temperature substantially can not get improving; And when the too high levels of ring phosphonitrile compounds, the viscosity of electrolyte can be increased, and reduce the migration rate of lithium ion, same, the thermal stability under the cycle performance of lithium ion battery and high temperature also can be made substantially to can not get improving.Further preferably, the total content of described ring phosphonitrile compounds is 0.1 ~ 3% of the total weight of electrolyte.
Find after deliberation, owing to including phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds in the electrolyte that the application provides, make this electrolyte can form fine and close solid electrolyte interface (SEI) film in negative terminal surface, thus effectively reduce the decomposition of electrolyte on negative pole, hydrofluoric acid simultaneously in all right Electolyte-absorptive, substantially improve the cycle performance of lithium ion battery, in addition, electrolyte can also form the less passivating film of impedance in negative terminal surface, effectively can reduce the increase of cathode interface impedance in cyclic process, also the cycle performance of lithium ion battery can greatly be improved.In addition, the electrolyte that the application provides, is applied to after in lithium ion battery, can also improve lithium ion battery thermal stability at high temperature.
In above-mentioned electrolyte, the concrete kind of described organic solvent can be selected according to the actual requirements, especially, selects non-aqueous organic solvent, and wherein non-aqueous organic solvent can be any kind, selects according to the actual requirements.Such as, carbon number can be selected to be 1 ~ 8 and containing the compound of at least one ester group as non-aqueous organic solvent.
Preferably, described organic solvent be selected from ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate one or more.Certainly being not limited only to above-mentioned mentioned concrete compound, also can be the halo derivatives of above-mentioned concrete compound.
In above-mentioned electrolyte, at least one of described lithium salts optionally in organic lithium salt or inorganic lithium salt.Especially, at least one in fluorine element, boron element, P elements is contained in described lithium salts.
Preferably, described lithium salts is for being selected from lithium hexafluoro phosphate LiPF
6, two trifluoromethanesulfonimide lithium LiN (CF
3sO
2)
2(being abbreviated as LiTFSI), two (fluorine sulphonyl) imine lithium Li (N (SO
2f)
2(being abbreviated as LiFSI), di-oxalate lithium borate LiB (C
2o
4)
2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF
2(C
2o
4) one or more in (being abbreviated as LiDFOB).
Preferably, the content of described lithium salts is 6.2 ~ 25% of the gross weight of electrolyte, and further preferably, the content of described lithium salts is 6.25 ~ 18.8% of the gross weight of electrolyte, and preferably, the content of described lithium salts is 10 ~ 15% of the gross weight of electrolyte.
In this application, electrolyte adopts conventional method to prepare, such as by each mixing of materials in electrolyte evenly.
Another object of the application is to provide a kind of lithium ion battery, comprises positive plate, negative plate, lithium battery diaphragm and electrolyte, wherein, and the electrolyte that electrolyte provides for the application.
In above-mentioned lithium ion battery, described positive plate comprises plus plate current-collecting body and is positioned at the positive-active pulp layer on described plus plate current-collecting body, and wherein, described positive-active pulp layer comprises positive electrode active materials; Described negative plate comprises negative current collector and is positioned at the negative electrode active pulp layer on described negative current collector, and wherein, described negative electrode active pulp layer comprises negative active core-shell material.Wherein, the concrete kind of positive electrode active materials, positive electrode binder, negative active core-shell material is not all subject to concrete restriction, can select according to demand.
Preferably, described positive electrode active materials is for being selected from cobalt acid lithium (LiCoO
2), lithium-nickel-manganese-cobalt ternary material, LiFePO 4 (LiFePO
4), LiMn2O4 (LiMn
2o
4) in one or more.
Preferably, described negative active core-shell material is graphite and/or silicon, such as native graphite, Delanium, mesophase spherule micro-carbon ball (referred to as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO
2, spinel structure lithiumation TiO
2-Li
4ti
5o
12, Li-Al alloy all can be used as negative active core-shell material.
Embodiment
The application is further described below by way of instantiation.But these examples are only exemplary, do not form any restriction to the protection range of the application.
In following experimental example, comparative example and test example, used material is as follows:
Organic solvent: ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), fluoroethylene carbonate (FEC).
Lithium salts: LiPF
6.
Ring phosphonitrile compounds:
2, 4, 4, 6, 6-five fluoro-2-ethoxy basic ring phosphonitrile (ring phosphonitrile 1), 2, 4, 4, 6, 6-five fluoro-2-phenoxy group ring phosphonitrile (ring phosphonitrile 2), 2, 4, 4, 6, the fluoro-2-of 6-five (4-fluorophenoxy) ring phosphonitrile (ring phosphonitrile 3), 2, 4, 6, 6-tetra-fluoro-2, 4-diethoxy basic ring phosphonitrile (ring phosphonitrile 4), 2, 4, 6, the fluoro-2-phenoxy group of 6-tetra--4-ethoxy basic ring phosphonitrile (ring phosphonitrile 5), 2, 4, 4, 6, the fluoro-2-(2 of 6-five, 2, 2-trifluoro ethoxy) ring phosphonitrile (ring phosphonitrile 6), 2, 4, 6, 6-tetra-fluoro-2, 4 dimethoxy basic ring phosphonitriles (ring phosphonitrile 7), 2, 4, 6, the fluoro-2-phenoxy group of 6-tetra--4-methyl ring phosphonitrile (ring phosphonitrile 8), 2, 4, the fluoro-2-phenoxy group-4 of 6-tri-, 6-diformazan basic ring phosphonitrile (ring phosphonitrile 9), 2, 4, 4, 6, the fluoro-2-of 6-five (1-fluorine n-pro-pyl) ring phosphonitrile (ring phosphonitrile 10), 2, 4, 4, 6, the fluoro-2-of 6-five (2-fluorine n-pro-pyl) ring phosphonitrile (ring phosphonitrile 11), 2, 4, 4, 6, the fluoro-2-of 6-five (the fluoro-2-cyclobutenyl of 1-) ring phosphonitrile (ring phosphonitrile 12), 2, 4, 4, 6, the fluoro-2-of 6-five (the fluoro-2-cyclobutenyl of 3-) ring phosphonitrile (ring phosphonitrile 13), 2, 4, 4, 6, 6-five fluoro-2-fluoro-methoxy ring phosphonitrile (ring phosphonitrile 14), 2, 4, 4, 6, the fluoro-2-of 6-five (the fluoro-4-phenoxy group of 2-) ring phosphonitrile (ring phosphonitrile 15), 2, 4, 4, 6, the fluoro-2-of 6-five (2-methyl-4-fluorine normal-butyl) ring phosphonitrile (ring phosphonitrile 16), 2, 4, 4, 6, the fluoro-2-(2 of 6-five, 6-bis-fluoro-3, 5-dimethyl phenoxy) ring phosphonitrile (ring phosphonitrile 17).
Phosphoric acid cyclic anhydride compounds:
Lithium battery diaphragm: polyethylene porous thin polymer film.
The preparation of embodiment 1 ~ 23 lithium ion battery 1 ~ 23
Lithium ion battery (abbreviation battery) 1 ~ 23 is prepared all by the following method:
(1) positive plate preparation
By cobalt acid lithium (LiCoO
2), binding agent (Kynoar), conductive agent (acetylene black) they are LiCoO according to weight ratio
2: Kynoar: acetylene black=96: mix at 2: 2, add 1-METHYLPYRROLIDONE (NMP), the system that is stirred under de-airing mixer effect becomes transparent and homogeneous shape, obtains anode sizing agent; Anode sizing agent being evenly coated on thickness is on the aluminium foil of 12 μm; Aluminium foil is transferred to after room temperature is dried 120 DEG C of oven drying 1h, then obtains positive plate through colding pressing, cutting.
(2) negative plate preparation
Be graphite by graphite, acetylene black, thickener sodium carboxymethylcellulose (CMC), binding agent butadiene-styrene rubber according to weight ratio: acetylene black: binding agent butadiene-styrene rubber: thickener sodium carboxymethylcellulose (CMC)=95: 2: 2: 1 mixes, after joining deionized water, under the stirring action that de-airing mixer stirs, obtain cathode size; Cathode size is evenly coated on Copper Foil; Copper Foil is transferred to after room temperature is dried 120 DEG C of oven drying 1h, then obtains negative plate through colding pressing, cutting.
(3) electrolyte preparation
Electrolyte 1 ~ 23 is prepared all by the following method:
In the argon gas atmosphere glove box of water content < 10ppm, EC, DEC, PC and FEC are mixed formation organic solvent, fully dry lithium salts is dissolved in above-mentioned organic solvent, then phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds is added in organic solvent, mix, obtain electrolyte.Wherein, the concentration of lithium salts is 1mol/L, EC, the weight ratio of DEC, PC, FEC is EC: DEC: PC: FEC=30: 50: 15: 5.
(4) preparation of lithium ion battery
Positive plate, lithium battery isolation membrane, negative plate are folded in order, make lithium battery isolation membrane be in the effect playing isolation between positive and negative plate, then winding obtains naked battery core; Naked battery core is placed in external packing paper tinsel, the above-mentioned electrolyte prepared is injected in dried battery, through Vacuum Package, leave standstill, change into, the operation such as shaping, obtain lithium ion battery (abbreviation battery).
In the preparation process of above-mentioned battery, the concrete kind of additive used in electrolyte selected in each battery, each electrolyte and content, as shown in Table 1 below.
In Table 1, the content of described phosphoric acid cyclic anhydride compounds is the percetage by weight obtained based on the total weight of electrolyte, and the content of described ring phosphonitrile compounds is the percetage by weight obtained based on the total weight of electrolyte.
Table 1
Comparative example 1 ~ 3 lithium ion battery 1
#~ 3
#preparation
Lithium ion battery 1
#~ 3
#be prepared all by the following method:
Repeat embodiment 1, be wherein the content of ring phosphonitrile compounds and phosphoric acid cyclic anhydride compounds, all the other conditions are all constant.
In the preparation process of above-mentioned battery, the concrete kind of additive used in electrolyte selected in each battery, each electrolyte and content, as shown in Table 2 below.
In table 2, the content of described phosphoric acid cyclic anhydride compounds is the percetage by weight obtained based on the total weight of electrolyte, and the content of described ring phosphonitrile compounds is the percetage by weight obtained based on the total weight of electrolyte.
Table 2
Note: any material is not added in "-" expression.
the cycle performance test of test one, battery
The battery prepared is carried out following test respectively:
At 25 DEG C, by battery with 1C constant current charge to 4.35V, then constant voltage charge to electric current is 0.05C, use 1C constant-current discharge to 3.0V again, now for circulate first, carry out 50 times, 100 times, 200 times, 300 times, 500 times cycle charging/electric discharges respectively according to above-mentioned cycling condition, calculate circulating battery respectively 50 times, 100 times, 200 times, 300 times, 500 times circulation after capability retention, wherein, the capability retention after circulation calculates according to the following formula.The relevant test data obtained in each battery is see table 3.
Capability retention after circulation=(discharge capacity after corresponding cycle-index/circulate first discharge capacity) × 100%
Table 3
Can learn from the related data above-mentioned table 3, compare battery 1
#, battery 1 ~ 13, respectively through after 50 times, 100 times, 200 times, 300 times, 500 times circulations, all has higher capability retention.
Can learn thus, the electrolyte including phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds the application provided, is applied to after in lithium ion battery, can improves the cycle performance of battery, especially, the cycle performance of battery under the high voltage of more than 4.35V can be improved.
thermostability test after test two, circulating battery
Battery under above-mentioned test one condition after 500 circulations is all carried out following test:
At 25 DEG C with 0.5C electric current constant current charge to 4.35V, again with 4.35V constant voltage charge to electric current for 0.025C, it is made to be in 4.35V fully charged state, then battery is placed in the high temperature furnace of 150 DEG C and keeps 1 hour, test battery change in voltage and battery core surface temperature in high temperature furnace simultaneously, and the state (often organizing each 5 batteries) of battery after observation test, result is shown in Table 4.
Table 4
| Battery is numbered | State after heat stability testing |
| Battery 1 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 2 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 3 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 4 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 5 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 6 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 7 | 5 batteries are all excellent, do not have phenomenon on fire |
| Battery 8 | 5 batteries are all excellent, do not have on fire existing |
| Battery 9 | 5 batteries are all excellent, do not have on fire existing |
| Battery 10 | 5 batteries are all excellent, do not have on fire existing |
| Battery 11 | 5 batteries are all excellent, do not have on fire existing |
| Battery 12 | 5 batteries are all excellent, do not have on fire existing |
| Battery 13 | 5 batteries are all excellent, do not have on fire existing |
| Battery 14 | 5 batteries are all excellent, do not have phenomenon on fire |
| Battery 15 | 3 batteries are all excellent, and remaining 2 batteries all have phenomenon on fire |
| Battery 16 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 17 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 18 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 19 | 3 batteries are all excellent, and remaining 2 batteries all have phenomenon on fire |
| Battery 20 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 21 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 22 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 23 | 2 batteries are all excellent, and remaining 3 batteries all have phenomenon on fire |
| Battery 1 # | 5 batteries all have phenomenon on fire |
| Battery 2 # | 1 battery stands intact, and remaining 4 batteries all have phenomenon on fire |
| Battery 3 # | 1 battery stands intact, and remaining 4 batteries all have phenomenon on fire |
Can learn from the correlated results above-mentioned table 4, compare battery 1
#~ 3
#test through thermostability the state presented and compare after carrying out 500 circulations, after battery 1 ~ 23 carries out circulating for 500 times again after the thermally-stabilised test under high temperature, cell integrated phenomenon on fire all not easily occurs.
Can learn thus, the electrolyte of what the application provided include phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds, is applied to after in lithium ion battery, can improves the thermal stability of the lithium ion battery after repeatedly circulation.
The announcement of book according to the above description, the application those skilled in the art can also carry out suitable change and amendment to above-mentioned execution mode.Therefore, the application is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the application some modifications and changes of the application.
Claims (10)
1. an electrolyte, is characterized in that, comprises lithium salts, solvent and additive, and wherein, described additive comprises phosphoric acid cyclic anhydride compounds and ring phosphonitrile compounds.
2. electrolyte according to claim 1, is characterized in that, one or more for being selected from the compound shown in following formula I of described phosphoric acid cyclic anhydride compounds:
Wherein, R
1, R
2, R
3independently of one another for be selected from carbon number be 1 ~ 20 alkyl, carbon number be one in the aryl of 6 ~ 26.
3. electrolyte according to claim 2, is characterized in that, R
1, R
2, R
3independently of one another for be selected from carbon number be 1 ~ 10 alkyl, carbon number be one in the aryl of 6 ~ 16.
4. a kind of electrolyte according to claim 2, is characterized in that, R
1, R
2, R
3independently of one another for being selected from the chain alkyl that carbon number is 1 ~ 6, carbon number be 3 ~ 8 cyclic alkane base, carbon number be one in the aryl of 6 ~ 9.
5. electrolyte according to claim 1, is characterized in that, one or more for being selected from the compound shown in following formula II of described ring phosphonitrile compounds.
Wherein, R
4, R
5, R
6, R
7, R
8, R
9be one that the alkyl being selected from hydrogen atom, halogen atom, carbon number are 1 ~ 20, the carbon number thiazolinyl that is 2 ~ 20, the carbon number aryl that is 6 ~ 20, the carbon number alkoxyl that is 1 ~ 20, the carbon number aryloxy group that is 6 ~ 20, the carbon number haloalkyl that is 1 ~ 20, the carbon number halogenated aryl that is 6 ~ 20, the carbon number halogenated alkoxy that is 1 ~ 20, carbon number are in the haloaryloxy of 6 ~ 20 independently of one another, wherein, at R
4, R
6, R
8middle at least one is oxy radical, at R
5, R
7, R
9in at least both be halogen atom, described halogen atom is F, Cl, Br.
6. electrolyte according to claim 5, is characterized in that, R
4, R
5, R
6, R
7, R
8, R
9independently of one another for being selected from F, Cl, the carbon number alkyl that is 1 ~ 10, the carbon number thiazolinyl that is 2 ~ 10, the carbon number aryl that is 6 ~ 16, the carbon number alkoxyl that is 1 ~ 10, the carbon number aryloxy group that is 6 ~ 16, the carbon number haloalkyl that is 1 ~ 10, the carbon number halogenated aryl that is 6 ~ 16, the carbon number halogenated alkoxy that is 1 ~ 10, carbon number be one in the haloaryloxy of 6 ~ 16.
7. electrolyte according to claim 5, is characterized in that, R
4, R
5, R
6, R
7, R
8, R
9independently of one another for being selected from the chain-like alkyl that carbon number is 1 ~ 6, carbon number is the cyclic alkyl of 3 ~ 8, carbon number is the thiazolinyl of 2 ~ 6, carbon number is the aryl of 6 ~ 9, carbon number is the chain alkoxyl of 1 ~ 6, carbon number is the cyclic alkoxy of 3 ~ 8, carbon number is the aryloxy group of 6 ~ 16, carbon number is the chain haloalkyl of 1 ~ 6, carbon number is the cyclic haloalkyl of 3 ~ 8, carbon number is the halogenated aryl of 6 ~ 14, carbon number is the chain halogenated alkoxy of 1 ~ 6, carbon number is the cyclic halo alkoxyl of 3 ~ 8, carbon number is the one in the haloaryloxy of 6 ~ 14.
8. electrolyte according to claim 1, is characterized in that, the content of described phosphoric acid cyclic anhydride compounds is 0.05% ~ 3% of the total weight of electrolyte, and the content of described ring phosphonitrile compounds is 0.01% ~ 10% of the total weight of electrolyte.
9. electrolyte according to claim 1, it is characterized in that, described organic solvent be selected from ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate one or more; One or more for being selected from lithium hexafluoro phosphate, two trifluoromethanesulfonimide lithium, two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate and difluorine oxalic acid boracic acid lithium of described lithium salts.
10. a lithium ion battery, is characterized in that, comprises the electrolyte according to any one of positive plate, negative plate, lithium battery diaphragm and claim 1 ~ 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510606516.5A CN105047994B (en) | 2015-09-22 | 2015-09-22 | Electrolyte and the lithium ion battery including the electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510606516.5A CN105047994B (en) | 2015-09-22 | 2015-09-22 | Electrolyte and the lithium ion battery including the electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105047994A true CN105047994A (en) | 2015-11-11 |
| CN105047994B CN105047994B (en) | 2018-02-23 |
Family
ID=54454356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510606516.5A Active CN105047994B (en) | 2015-09-22 | 2015-09-22 | Electrolyte and the lithium ion battery including the electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105047994B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159327A (en) * | 2016-08-29 | 2016-11-23 | 凯思普科技有限责任公司 | Lithium rechargeable battery |
| CN107331893A (en) * | 2016-04-29 | 2017-11-07 | 华为技术有限公司 | A kind of high-temperature lithium-ion battery electrolyte and preparation method thereof and high temperature lithium ion battery |
| CN107516745A (en) * | 2017-08-16 | 2017-12-26 | 中节能万润股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell |
| CN107863556A (en) * | 2017-10-24 | 2018-03-30 | 湛江市金灿灿科技有限公司 | The lithium ion battery and its electrolyte that a kind of high-nickel material is positive pole, silicon carbon material is negative pole |
| CN107936062A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院福建物质结构研究所 | A kind of ring phosphazene derivative and preparation method thereof and the purposes as electrolysis additive |
| CN107946645A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院福建物质结构研究所 | A kind of high safety electrolyte and lithium battery |
| WO2018090594A1 (en) * | 2016-11-17 | 2018-05-24 | 张家港市国泰华荣化工新材料有限公司 | Lithium-ion battery electrolyte and lithium-ion battery |
| CN109309253A (en) * | 2017-07-27 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and electrochemical energy storage device |
| CN109428078A (en) * | 2017-08-25 | 2019-03-05 | 宁德时代新能源科技股份有限公司 | Battery with a battery cell |
| WO2023159797A1 (en) * | 2022-02-23 | 2023-08-31 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, non-aqueous electrolyte and lithium-ion battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021128093A1 (en) * | 2019-12-25 | 2021-07-01 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008053212A (en) * | 2006-07-24 | 2008-03-06 | Bridgestone Corp | Nonaqueous electrolytic solution for battery, and nonaqueous electrolytic solution battery equipped with it |
| CN102569890A (en) * | 2012-02-13 | 2012-07-11 | 东莞新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN103208653A (en) * | 2013-03-21 | 2013-07-17 | 东莞新能源科技有限公司 | Lithium ion battery with nickel-based cathode, and electrolyte therefor |
| CN103779607A (en) * | 2014-01-17 | 2014-05-07 | 中南大学 | Electrolyte solution and lithium-ion secondary battery |
| US20140342240A1 (en) * | 2013-05-14 | 2014-11-20 | Mason Kurt Harrup | Fluorinated phosphazenes for use as electrolyte additives and co-solvents in lithium ion batteries |
| CN104638293A (en) * | 2015-01-23 | 2015-05-20 | 深圳新宙邦科技股份有限公司 | High-compaction-density cathode lithium ion battery and electrolyte |
-
2015
- 2015-09-22 CN CN201510606516.5A patent/CN105047994B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008053212A (en) * | 2006-07-24 | 2008-03-06 | Bridgestone Corp | Nonaqueous electrolytic solution for battery, and nonaqueous electrolytic solution battery equipped with it |
| CN102569890A (en) * | 2012-02-13 | 2012-07-11 | 东莞新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN103208653A (en) * | 2013-03-21 | 2013-07-17 | 东莞新能源科技有限公司 | Lithium ion battery with nickel-based cathode, and electrolyte therefor |
| US20140342240A1 (en) * | 2013-05-14 | 2014-11-20 | Mason Kurt Harrup | Fluorinated phosphazenes for use as electrolyte additives and co-solvents in lithium ion batteries |
| CN103779607A (en) * | 2014-01-17 | 2014-05-07 | 中南大学 | Electrolyte solution and lithium-ion secondary battery |
| CN104638293A (en) * | 2015-01-23 | 2015-05-20 | 深圳新宙邦科技股份有限公司 | High-compaction-density cathode lithium ion battery and electrolyte |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3442071A4 (en) * | 2016-04-29 | 2019-03-20 | Huawei Technologies Co., Ltd. | High-temperature lithium-ion battery electrolyte solution and preparation method therefor and high-temperature lithium-ion battery |
| CN107331893A (en) * | 2016-04-29 | 2017-11-07 | 华为技术有限公司 | A kind of high-temperature lithium-ion battery electrolyte and preparation method thereof and high temperature lithium ion battery |
| US10862167B2 (en) | 2016-04-29 | 2020-12-08 | Huawei Technologies Co., Ltd. | High-temperature lithium-ion battery electrolyte and production method thereof, and high-temperature lithium-ion battery |
| CN107331893B (en) * | 2016-04-29 | 2020-03-10 | 华为技术有限公司 | High-temperature lithium ion battery electrolyte, preparation method thereof and high-temperature lithium ion battery |
| CN106159327B (en) * | 2016-08-29 | 2019-08-30 | 恺时浦(上海)检测技术有限公司 | Lithium ion secondary battery |
| CN106159327A (en) * | 2016-08-29 | 2016-11-23 | 凯思普科技有限责任公司 | Lithium rechargeable battery |
| CN107946645A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院福建物质结构研究所 | A kind of high safety electrolyte and lithium battery |
| CN107946645B (en) * | 2016-10-13 | 2020-11-20 | 中国科学院福建物质结构研究所 | High-safety electrolyte and lithium battery |
| CN107936062B (en) * | 2016-10-13 | 2020-02-21 | 中国科学院福建物质结构研究所 | Cyclophosphnitrile derivative, preparation method thereof and application of cyclic phosphnitrile derivative as electrolyte additive |
| CN107936062A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院福建物质结构研究所 | A kind of ring phosphazene derivative and preparation method thereof and the purposes as electrolysis additive |
| WO2018090594A1 (en) * | 2016-11-17 | 2018-05-24 | 张家港市国泰华荣化工新材料有限公司 | Lithium-ion battery electrolyte and lithium-ion battery |
| EP3544109A4 (en) * | 2016-11-17 | 2020-10-14 | Zhangjiagang Guotai-Huarong New Chemical Materials Co., Ltd | Lithium-ion battery electrolyte and lithium-ion battery |
| CN109309253A (en) * | 2017-07-27 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and electrochemical energy storage device |
| CN107516745B (en) * | 2017-08-16 | 2019-09-03 | 中节能万润股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell |
| CN107516745A (en) * | 2017-08-16 | 2017-12-26 | 中节能万润股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell |
| CN109428078A (en) * | 2017-08-25 | 2019-03-05 | 宁德时代新能源科技股份有限公司 | Battery with a battery cell |
| CN109428078B (en) * | 2017-08-25 | 2021-09-17 | 宁德时代新能源科技股份有限公司 | Battery with a battery cell |
| CN107863556A (en) * | 2017-10-24 | 2018-03-30 | 湛江市金灿灿科技有限公司 | The lithium ion battery and its electrolyte that a kind of high-nickel material is positive pole, silicon carbon material is negative pole |
| CN107863556B (en) * | 2017-10-24 | 2020-09-08 | 湛江市金灿灿科技有限公司 | Lithium ion battery with high nickel material as anode and silicon carbon material as cathode and electrolyte thereof |
| WO2023159797A1 (en) * | 2022-02-23 | 2023-08-31 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, non-aqueous electrolyte and lithium-ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105047994B (en) | 2018-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105047995B (en) | Lithium ion battery of electrolyte including the electrolyte and preparation method thereof | |
| CN105047994A (en) | Electrolyte and lithium ion battery comprising same | |
| CN105261788B (en) | Electrolyte and the lithium ion battery including the electrolyte | |
| CN107017432B (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN109728340B (en) | Lithium ion battery | |
| CN105845977A (en) | Electrolyte and lithium ion battery comprising same | |
| CN105098242A (en) | Electrolyte and lithium ion battery comprising the same | |
| CN105655641B (en) | A kind of electrolyte and its lithium ion battery | |
| CN105489934A (en) | Electrolyte and lithium-ion battery comprising same | |
| CN105489937B (en) | Nonaqueous electrolytic solution and the lithium ion battery for using the nonaqueous electrolytic solution | |
| CN105655643B (en) | Electrolyte and lithium ion battery comprising same | |
| CN107293784A (en) | Electrolyte and lithium ion battery | |
| CN107293782A (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN104934636A (en) | Electrolyte and lithium ion battery containing same | |
| CN105226321A (en) | Electrolyte and comprise the lithium ion battery of this electrolyte | |
| CN105489935A (en) | Electrolyte and lithium-ion battery comprising same | |
| CN107293776A (en) | Electrolyte and lithium ion battery | |
| CN109888384A (en) | Electrolyte and battery containing electrolyte | |
| CN110085906A (en) | Nonaqueous electrolytic solution, the lithium ion battery containing the nonaqueous electrolytic solution | |
| CN108258297A (en) | Electrolyte and lithium ion battery | |
| CN105811009B (en) | Electrolyte and lithium ion battery comprising same | |
| CN109755648A (en) | Electrolyte and battery using same | |
| CN107403950A (en) | Electrolyte and lithium ion battery | |
| CN108987802A (en) | A kind of high-voltage lithium ion batteries nonaqueous electrolytic solution | |
| CN105489936A (en) | Non-aqueous electrolyte and lithium ion battery comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |