CN108539269A - A kind of lithium-ion battery electrolytes - Google Patents
A kind of lithium-ion battery electrolytes Download PDFInfo
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- CN108539269A CN108539269A CN201810324218.0A CN201810324218A CN108539269A CN 108539269 A CN108539269 A CN 108539269A CN 201810324218 A CN201810324218 A CN 201810324218A CN 108539269 A CN108539269 A CN 108539269A
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- 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
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- 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
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- 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
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- H01M10/0568—Liquid materials characterised by the solutes
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- 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
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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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
To overcome the problems, such as that electrolyte is difficult to take into account the chemical properties such as flame retardant property and cycle in the prior art, the present invention provides a kind of lithium-ion battery electrolytes, including lithium salts, organic solvent and additive, the additive includes phosphazene compound and perfluor hexanone.Lithium-ion battery electrolytes provided by the invention have good cycle performance and flame-retarding, using its lithium ion battery at room temperature and 45 DEG C stable cycle performance, not inflatable is stored in 60 DEG C of hot tanks, internal resistance variation is small, and keeps good storage performance and cycle performance.
Description
Technical field
The invention belongs to the technical fields of lithium-ion battery electrolytes, and in particular to one kind is added comprising two kinds of anti-flammabilitys
The lithium-ion battery electrolytes of agent.
Background technology
Lithium ion battery is made of the part such as anode, cathode, diaphragm and electrolyte, and wherein lithium-ion battery electrolytes exist
Play the role of receiving and conduction ion between the positive and negative anodes of battery, is the advantages that lithium ion battery obtains high voltage, high specific energy
Guarantee.Lithium-ion battery electrolytes are generally formulated by solvent, lithium salts, additive according to a certain percentage.Commodity at present
It with most ripe lithium salts is lithium hexafluoro phosphate (LiPF to change in lithium ion battery production6), solvent is mainly carbonates and lacks
Quantity carboxylic acid's esters, such as：Ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC),
Diethyl carbonate (DEC) etc., and a small amount of additive is primarily used to promote the overall performance of electrolyte, such as：Improve battery
Cycle efficieny, improve electrode filming performance, reduce battery internal resistance, improve battery safety etc..
In order to meet the increasing performance requirement of lithium ion battery, additive is currently essential important set
At ingredient.Especially for flame-retardant electrolyte, since in lithium-ion battery electrolytes, traditional primary solvent is all carbonic ester
Class, linear carbonates such as DMC, EMC, DEC belong to flammable solvent, and cyclic carbonate EC, PC belong to combustible solvent, therefore dissolve
The lithium-ion battery electrolytes of lithium salts and conventional additives can burn, even inflammable in some cases.In order to
The fire-retardant of electrolyte is realized, in the case where using carbonates as electrolyte primary solvent, it is necessary to rely on addition and centainly contain
The fire retardant of amount could realize the flame-retarded of electrolyte, this is most important for the security performance for improving lithium ion battery.But
It is that the fire retardant of generally use must could realize good flame retardant effect under higher additive amount at present, such as phosphorous
Esters trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), dimethyl methyl phosphonate (DMMP),
Diethyl ethylphosphate (DEEP) etc. and phosphorous simultaneously, nitrogen fire retardant phosphonitrile etc..Phosphorous esters major defect
It is to be easy to decompose on cathode, cycle performance of battery is poor, therefore is not widely used in industrial circle.
Invention content
It is insufficient on cycle performance the technical problem to be solved by the present invention is to be directed to flame-retardant electrolyte in the prior art
The problem of, a kind of improved lithium-ion battery electrolytes are provided.
Technical solution is as follows used by the present invention solves above-mentioned technical problem：
A kind of lithium-ion battery electrolytes, including lithium salts, organic solvent and additive are provided, the additive includes phosphorus
Nitrile compound and perfluor hexanone.
Inventor has found that perfluor hexanone theoretically has certain help to the flame retardant property for improving electrolyte.But it is logical
It crosses experiment to find, using carbonates as in the electrolyte of primary solvent, the solubility of perfluor hexanone is very low, allows to use
Concentration be no more than 1%.And under this additive amount, the addition of perfluor hexanone to the flame retardant property improvement of electrolyte not
Obviously.The solubility that perfluor hexanone theoretically can be improved by adding surfactant or solubilizer etc. into electrolyte, but
It is that the addition of above-mentioned surfactant or solubilizer certainly will will seriously affect the chemical property of electrolyte.
The present invention has surprisingly found that after adding phosphazene compound and perfluor hexanone simultaneously into electrolyte, with phosphonitrile
The addition of object is closed, the solubility of perfluor hexanone is correspondingly improved, and by the synergistic effect of the two, perfluor hexanone is in electricity
The concentration that can use is considerably beyond 1% in solution liquid, it might even be possible to reach 6%, so as to so that perfluor hexanone can be in electrolyte
In give full play to its effect.In details of the words, the perfluor hexanone of 0.5-10% is added in the electrolyte containing phosphazene compound, it is excellent
After the perfluor hexanone of 1-6% is added in choosing, which can not be lighted with open fire.It is added in the electrolyte of the hexanone containing perfluor
When the phosphorus nitrile compounds of 1%-20%, preferably 5-15% can promote the dissolving of perfluor hexanone in the electrolytic solution.Another party
Face can help to inhibit electrolyte in electrode surface oxidation point since phosphazene compound has higher oxidizing potential and anti-flammability
Solution, to further improve the high-temperature behavior and security performance of battery.
Also, by being used cooperatively for phosphazene compound and perfluor hexanone, high rate performance change will not occur in electrolyte
The problems such as difference, conductivity decline and cycle life shortens, conductivity, wellability and the anti-flammability of electrolyte have significantly
It improves, so that the electrolyte has better cycle performance and flame-retarding.After the electrolyte injects battery, battery
Room temperature and high-temperature behavior be all significantly improved.
Use the lithium ion battery of the electrolyte of the present invention, the stable cycle performance at room temperature and 45 DEG C, in 60 DEG C of hot tanks
Middle to store not inflatable, internal resistance variation is small, and keeps good storage performance and cycle performance.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to solve
The present invention is released, is not intended to limit the present invention.
Lithium-ion battery electrolytes provided by the invention include lithium salts, organic solvent and additive, and the additive includes
Phosphazene compound and perfluor hexanone.
Wherein, phosphazene compound is well known in the prior art, for example, the phosphazene compound includes to be tied as shown in formula 1
The compound of structure：
Formula 1：
Wherein R1、R2、R3、R4、R5、R6Be independently selected from fluorine atom, fluorine-containing or not fluorine-containing phenoxy group, it is fluorine-containing or
Not fluorine-containing carbon atom number is the alkoxy of 1-3, and R1、R2、R3、R4、R5、R6It can be identical or different.
Under preferable case, the phosphazene compound is selected from three phosphonitrile of perfluor ring, five fluorine ring of methoxyl group, three phosphonitrile, ethyoxyl
Five fluorine rings, three phosphonitrile, five fluorine ring of positive propoxy, three phosphonitrile, five fluorine ring of isopropoxy, three phosphonitrile, three phosphonitrile of phenoxy group (five fluorine) ring,
Five fluorine ethyoxyls, five fluorine ring, three phosphonitrile, five fluorine ring of trifluoromethoxy, three phosphonitrile, five fluorine ring of trifluoro ethoxy, three phosphonitrile, bis- (trifluoros
Methoxyl group) ptfe ring three is one or more in phosphonitrile.
After the substituent group volume on phosphazene compound becomes larger with the carbon atom number rising of substituent group, phosphonitrile chemical combination
The viscosity and boiling point of object all rise therewith, can bring harmful effect to the electric conductivity of electrolyte, flame retardant effect is as wave
Hair property decline and be damaged.For above-mentioned phosphazene compound, preferred substituent R1、R2、R3、R4、R5、R6It is fluorine atom
Or the group no more than 6 carbon atoms, five fluorine ring of ethyoxyl, three phosphonitrile replaced such as ethyoxyl.
The flame retardant effect of phosphazene compound in the electrolytic solution is related with its dosage, while also related to the volatility of solvent.
When the volatility (or vapour pressure) of phosphazene compound is higher than the volatility of solvent, it is easy to form the anti-flammability gas of high concentration
Group, is advantageously implemented preferable flame retardant effect.But phosphazene compound especially cyclic phosphazene compound, due to self structure original
Cause, volatility are still not ideal enough.Therefore its flame retardant effect still has improved necessity, too low phosphonitrile chemical combination in the electrolytic solution
Object dosage is also insufficient for the improvement of flame retardant effect, it is however generally that, concentration has been difficult to observe by phosphonitrile chemical combination less than 1%
Improvement of the object for the anti-flammability of electrolyte.Therefore, amount ranges are in 1%-20%, preferably 5-15%.But it is excessively high
Phosphazene compound content the dissolubility to lithium salts can be brought unfavorable again, the advantages that cost is excessively high.
The present inventor has found a kind of new additive agent perfluor hexanone (i.e. perfluor -2- methyl-propione).It is demonstrated experimentally that
Perfluor hexanone and phosphazene compound are used simultaneously in electrolyte, can be effectively improved the volatility problem of phosphazene compound, be promoted
The formation of anti-flammability air mass to improve fire retardancy, and can reduce the additive amount of phosphazene compound.Meanwhile it can improve
The infiltration of electrolyte and positive and negative anodes pole piece, electrolyte and diaphragm is conducive to the promotion of capacity and cycle performance.Its principle speculates
Absorption that may be with perfluor hexanone on positive or negative pole surface inhibits electrolyte related in the decomposition of electrode surface.
In lithium-ion battery electrolytes provided by the invention, the content range of perfluor hexanone is 0.5%-6%, works as content
When being 0.5% or less, concentration is relatively low, and perfluor hexanone is contributed smaller in the formation of anti-flammability air mass, and vapor partial pressure is relatively low,
To the improvement unobvious of electrolyte flame-retardant performance；And when more than 6%, may will produce perfluor hexanone cannot be completely molten
The phenomenon that solution, occurs in electrolyte being layered and muddy, bad to cause capacity or cycle performance.Preferably content range is
1%-3%.Within this range, perfluor hexanone has preferable steady dissolution and can play and improves flame retardant effect, improves
The wetting capacity of electrolyte and the effect for improving circulating battery ability.
Further include carbonic acid Asia second in lithium-ion battery electrolytes provided by the invention to improve the comprehensive performance of electrolyte
It is one or more in enester, 1,3- propane sultones, sulfuric acid vinyl ester, difluorophosphate.Above-mentioned various additives can root
It is selectively added according to actual conditions, in the electrolyte, on the basis of electrolyte total weight, the vinylene carbonate contains
Amount is 0%-3%, preferably 0.1%-3%.The content of 1, the 3- propane sultones is 0%-3%, preferably 0.1%-
3%.The content of the sulfuric acid vinyl ester is 0%-3%, preferably 0.1%-3%.The content of the difluorophosphate is 0%-
3%, preferably 0.1%-3%.
In the present invention, organic solvent may be used existing, and under preferable case, the organic solvent includes chain carbonic acid
It is one or more in ester, cyclic carbonate, carboxylate.
The linear carbonate in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate one
Kind is a variety of.
The one kind or more of the cyclic carbonate in ethylene carbonate, propene carbonate, fluorinated ethylene carbonate
Kind.
The carboxylate is selected from ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, propionic acid formic acid, third
It is one or more in acetoacetic ester, propionic acid n Propanoic acid, isopropyl propionate, methyl butyrate, ethyl butyrate.
In order to ensure that preferable flame retardant effect, the lower solvent of vapour pressure are preferred, the vapour pressures of cyclic carbonate
It is low, be conducive to the fire-retardant of electrolyte, ethylene carbonate, propene carbonate, fluorinated ethylene carbonate are all preferred.Chain carbon
In acid esters, diethyl carbonate is preferred.In carboxylate, n propyl propionate, isopropyl propionate, ethyl butyrate are preferred.With
On the basis of electrolyte total weight, its content of single solvent is adjustable out of 5%-50%, its content can be between different solvents
It is identical or differ.
The lithium salts is selected from lithium hexafluoro phosphate, LiBF4, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, double fluorine sulphurs
It is one or more in fluorine imide li, bis- (trifluoro methylsulfonyl) imine lithiums；In the electrolyte, it is with electrolyte total weight
Benchmark, a concentration of 0.5M-2.5M of the lithium salts, preferably 0.8M-1.5M.The most commonly used is the hexafluoro phosphorus of 1.0-1.3M
Sour lithium.Certainly, the salt can also be used as complementary lithium salts and use, and property is equivalent to additive, and dosage is in 0.1-
In 5% range, relatively common dosage is 0.5-3%.The present invention is further detailed by the following examples.
Table 1
Embodiment 1
(the moisture in the glove box of nitrogen protection<1ppm, oxygen<1ppm), by methyl ethyl carbonate (EMC), ethylene carbonate
Ester (EC), diethyl carbonate (DEC) etc. are mixed according to the mass ratio that table 1 is specified, and it is 12.5% that mass percent, which is added,
Lithium hexafluoro phosphate (LiPF6), the other additives and flame-retardant additive of table 1 regulation kind and content are added, stirring is equal
The lithium-ion battery electrolytes of embodiment 1 are obtained after even.
Embodiment 2~5
Embodiment 1 under the same conditions, allocated by the ingredient of each embodiment as defined in table 1, respectively obtain reality
Apply the lithium-ion battery electrolytes of example 2~5.
Comparative example 1~3
Embodiment 1 under the same conditions, allocated, respectively obtained pair by the ingredient of each comparative example as defined in table 1
The lithium-ion battery electrolytes of ratio 1~3.
Test event 1：Dissolubility is tested
Take the electrolyte of 50mL in turbidity colorimetric cylinder respectively embodiment 1-3 and comparative example 1 lithium battery electrolytes prepared
In, observe respective electrolyte turbidity and electrolyte stand after whether there is delamination, the size by turbidity and layering
Situation, to judge the intermiscibility in electrolyte between solvent.
Test result is as shown in table 2.
Table 2
It can be obtained by the data of table 2, the turbidity of the electrolyte of embodiment 1-3 is respectively less than comparative example 1, and with addition
The content of five fluorine ring triphosphine nitrile of ethyoxyl increases, and the turbidity of electrolyte is gradually reducing, after electrolyte is stood for a long time between solvent
Lamination also gradually unobvious, further demonstrate that phosphonitrile class additive can promote perfluor hexanone in carbonate solvent
Dissolubility so that the dissolving of perfluor hexanone in the electrolytic solution is more uniform.Although added in electrolyte 6% perfluor oneself
Ketone, it is still, most of not to be dissolved in electrolyte actually.
Test event 2：Flame retardant property is tested
The electrolyte of 50mL is taken to be placed in table respectively lithium battery electrolytes prepared by embodiment 4, embodiment 5 and comparative example 2
In the ware of face, then gone to light corresponding electrolyte with open fire.It smolders by the way that whether electrolyte can be lighted by open fire, to differentiate electricity
Solve the anti-flammability of liquid.
Test result is as shown in table 3.
Table 3
The electrolyte of embodiment 4 and embodiment 5 can not be lighted with open fire, and the electrolyte of comparative example 2 be can point
Ignite fire (although being added to 5% perfluor hexanone in comparative example 2, the perfluor hexanone amount that is in fact dissolved in electrolyte
Considerably less, electrolyte flame-retardant poor performance, therefore, electrolyte can be ignited), illustrate the anti-flammability of embodiment 4 and embodiment 5
It can be better than comparative example 2, this demonstrate that when the additive of phosphorous nitrile is used in mixed way with perfluor hexanone, phosphorous nitrile additive can
To make up the deficiency of perfluor hexanone anti-flammability, the flame retardant property of electrolyte is further increased.
Battery performance test
Lithium-ion battery electrolytes difference prepared by lithium battery electrolytes and embodiment 4-5 prepared by above-mentioned comparative example 3
Inject just extremely LiNi0.5Co0.2Mn0.3O2Ternary material, cathode are in the soft-package battery of artificial graphite, and battery rated capacity is
1000mAh tests battery.
Test event 3：Normal-temperature circulating performance is tested
Battery is placed in the insulating box of 25 DEG C of constant temperature, with the electric current constant-current constant-voltage charging of 1C to 4.4V, cut-off current is
0.03C, then with the electric current constant-current discharge of 1C to 3.0V.So cycle 300 weeks, the 1st week discharge capacity and the 300th of record
The discharge capacity in week, is calculated as follows capacity retention ratio.
Capacity retention ratio (%)=(the 300th cyclic discharge capacity/1st time cyclic discharge capacity) × 100%
Test result is as shown in table 4.
Test event 4：High temperature cyclic performance is tested
Test condition is other identical as test event 3 in addition to calorstat temperature is 45 DEG C.Test result is shown in Table 4.
Table 4
With nickel cobalt manganese Ni it can be seen from the data of table 4xCoyMn(1-x-y)Ternary material is as anode, graphite conduct
In the lithium ion battery of cathode, the lithium ion battery of the lithium-ion battery electrolytes preparation of embodiment 4-5 is in normal temperature condition (25
DEG C) cycle when, capacity attenuation speed obviously slows down, and battery capacity conservation rate is obviously improved, and is substantially better than comparative example 3, card
Cycle performance, which is substantially better than, when bright phosphazene compound is mixed together with perfluor hexanone is used alone phosphazene compound additive
Effect, the capacity retention ratio of battery is significantly improved.
From test data it can be seen that：After (45 DEG C) of high temperature cycle, either comparative example or embodiment, battery
Capacity retention ratio all be higher than normal temperature circulation when data, when this may be increased with temperature electrolyte conductivity rise, infiltrate
Capability improving, caused cycle performance improve related.The capacity retention ratio of embodiment 4 and embodiment 5 remains above comparative example 3, into
One step shows that the collaboration of phosphazene compound and perfluor hexanone uses the high temperature cyclic performance for being conducive to further be promoted battery.
Test event 5：High temperature storage is tested
The lithium ion battery of the full electric state of embodiment 4, embodiment 5 and comparative example 3 is placed in 60 DEG C of baking oven and is stored
72h tests capacity, internal resistance and the thickness change of battery.
Test result is as shown in table 5.
Table 5
It can be obtained by the data of table 5, after 60 DEG C of high temperature storage 72h, use the electrolyte system of embodiment 4 and embodiment 5
After storage at high temperatures, capacity retention ratio is superior to comparative example 3 to standby lithium ion battery, and thickness increment rate and internal resistance increase rate are equal
Less than comparative example 3.This further demonstrates that phosphazene compound uses the storage for being conducive to battery capacity with cooperateing with for perfluor hexanone
Energy.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. a kind of lithium-ion battery electrolytes, which is characterized in that including lithium salts, organic solvent and additive, the additive packet
Include phosphazene compound and perfluor hexanone.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that the phosphazene compound includes such as formula 1
The compound of shown structure：
Formula 1：
Wherein R1、R2、R3、R4、R5、R6It is independently selected from fluorine atom, fluorine-containing or not fluorine-containing phenoxy group, fluorine-containing or not fluorine-containing
Carbon atom number be 1-3 alkoxy, and R1、R2、R3、R4、R5、R6It can be identical or different.
3. lithium-ion battery electrolytes according to claim 2, which is characterized in that the phosphazene compound is selected from perfluor ring
Three phosphonitriles, five fluorine ring of methoxyl group, three phosphonitrile, five fluorine ring of ethyoxyl, three phosphonitrile, five fluorine ring of positive propoxy, three phosphonitrile, isopropoxy five
Three phosphonitrile of fluorine ring, three phosphonitrile of phenoxy group (five fluorine) ring, five fluorine ethyoxyls, five fluorine ring, three phosphonitrile, five fluorine ring of trifluoromethoxy, three phosphorus
It is one or more in nitrile, five fluorine ring of trifluoro ethoxy, three phosphonitrile, bis- three phosphonitriles of (trifluoromethoxy) ptfe ring.
4. according to the lithium-ion battery electrolytes described in any one of claim 1-3, which is characterized in that the electrolyte
In, on the basis of electrolyte total weight, the content of the phosphazene compound is 1%-20%；The content of the perfluor hexanone is
0.5%-10%.
5. lithium-ion battery electrolytes according to claim 4, which is characterized in that total with electrolyte in the electrolyte
On the basis of weight, the content of the phosphazene compound is 5%-15%；The content of the perfluor hexanone is 1%-6%.
6. according to the lithium-ion battery electrolytes described in claim 1-3, any one of 5, which is characterized in that the additive
Further include one or more in vinylene carbonate, 1,3- propane sultones, sulfuric acid vinyl ester, difluorophosphate.
7. lithium-ion battery electrolytes according to claim 6, which is characterized in that total with electrolyte in the electrolyte
On the basis of weight, the content of the vinylene carbonate is 0%-3%；The content of the 1,3- propane sultones is 0%-
3%；The content of the sulfuric acid vinyl ester is 0%-3%；The content of the difluorophosphate is 0%-3%.
8. lithium-ion battery electrolytes according to claim 1, which is characterized in that the organic solvent includes chain carbonic acid
It is one or more in ester, cyclic carbonate, carboxylate；
The one kind or more of the linear carbonate in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate
Kind；
The cyclic carbonate is one or more in ethylene carbonate, propene carbonate, fluorinated ethylene carbonate；
The carboxylate is selected from ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, propionic acid formic acid, propionic acid second
It is one or more in ester, propionic acid n Propanoic acid, isopropyl propionate, methyl butyrate, ethyl butyrate.
9. lithium-ion battery electrolytes according to claim 1, which is characterized in that the lithium salts be selected from lithium hexafluoro phosphate,
LiBF4, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, double fluorine sulphur fluorine imide lis, bis- (trifluoro methylsulfonyl) imine lithiums
In it is one or more；In the electrolyte, on the basis of electrolyte total weight, a concentration of 0.5M-2.5M of the lithium salts is excellent
It is selected as 0.8M-1.5M.
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| CN201810324218.0A CN108539269B (en) | 2018-04-12 | 2018-04-12 | Lithium ion battery electrolyte |
| PCT/CN2018/117557 WO2019196417A1 (en) | 2018-04-12 | 2018-11-27 | Lithium ion battery electrolyte |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019196417A1 (en) * | 2018-04-12 | 2019-10-17 | 南通新宙邦电子材料有限公司 | Lithium ion battery electrolyte |
| CN110994026A (en) * | 2019-12-24 | 2020-04-10 | 河南省法恩莱特新能源科技有限公司 | Wide-temperature-range electrolyte for ternary manganese-doped lithium battery and preparation method thereof |
| CN111697268A (en) * | 2020-05-15 | 2020-09-22 | 湖南博信新能源科技有限公司 | High-safety electrolyte with wide temperature range for lithium battery, preparation method of electrolyte and lithium battery |
| WO2020238302A1 (en) * | 2019-05-29 | 2020-12-03 | 华为技术有限公司 | Lithium secondary battery electrolyte, preparation method therefor and lithium secondary battery |
| CN112713302A (en) * | 2020-12-31 | 2021-04-27 | 蜂巢能源科技(无锡)有限公司 | Flame-retardant polymer gel electrolyte composition, gel electrolyte, and preparation method and application thereof |
| CN113299994A (en) * | 2021-05-21 | 2021-08-24 | 上海电气集团股份有限公司 | Modified electrolyte, preparation method thereof and battery |
| CN113540564A (en) * | 2020-04-21 | 2021-10-22 | 安徽盟维新能源科技有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN113839087A (en) * | 2020-06-23 | 2021-12-24 | 浙江蓝天环保高科技股份有限公司 | Method for improving high and low temperature performance of lithium ion battery and electrolyte thereof |
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| CN108923066B (en) * | 2018-06-29 | 2020-08-18 | 南通新宙邦电子材料有限公司 | Flame-retardant electrolyte for lithium ion battery |
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| US8815453B1 (en) * | 2005-04-05 | 2014-08-26 | Quallion Llc | Flame retardant battery |
| WO2009108374A1 (en) * | 2008-02-27 | 2009-09-03 | Quallion Llc | Batteries pack having batteries in a porous medium |
| CN102516307A (en) * | 2011-12-31 | 2012-06-27 | 湖南有色郴州氟化学有限公司 | Phosphazene flame retardant and preparation method thereof, as well as lithium ion battery electrolyte |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019196417A1 (en) * | 2018-04-12 | 2019-10-17 | 南通新宙邦电子材料有限公司 | Lithium ion battery electrolyte |
| WO2020238302A1 (en) * | 2019-05-29 | 2020-12-03 | 华为技术有限公司 | Lithium secondary battery electrolyte, preparation method therefor and lithium secondary battery |
| CN110994026A (en) * | 2019-12-24 | 2020-04-10 | 河南省法恩莱特新能源科技有限公司 | Wide-temperature-range electrolyte for ternary manganese-doped lithium battery and preparation method thereof |
| CN110994026B (en) * | 2019-12-24 | 2021-03-09 | 河南省法恩莱特新能源科技有限公司 | Wide-temperature-range electrolyte for ternary manganese-doped lithium battery and preparation method thereof |
| CN113540564A (en) * | 2020-04-21 | 2021-10-22 | 安徽盟维新能源科技有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN111697268A (en) * | 2020-05-15 | 2020-09-22 | 湖南博信新能源科技有限公司 | High-safety electrolyte with wide temperature range for lithium battery, preparation method of electrolyte and lithium battery |
| CN113839087A (en) * | 2020-06-23 | 2021-12-24 | 浙江蓝天环保高科技股份有限公司 | Method for improving high and low temperature performance of lithium ion battery and electrolyte thereof |
| CN112713302A (en) * | 2020-12-31 | 2021-04-27 | 蜂巢能源科技(无锡)有限公司 | Flame-retardant polymer gel electrolyte composition, gel electrolyte, and preparation method and application thereof |
| CN113299994A (en) * | 2021-05-21 | 2021-08-24 | 上海电气集团股份有限公司 | Modified electrolyte, preparation method thereof and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019196417A1 (en) | 2019-10-17 |
| CN108539269B (en) | 2020-02-18 |
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