CN109762023A - A kind of fire retardant and its preparation method and application - Google Patents
A kind of fire retardant and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of fire retardants and preparation method thereof, belong to lithium battery related fields, fire retardant provided by the present invention is the derivative of hexachlorocyclotriph,sphazene, with good flame retardant effect, and it is applied in lithium battery electrolytes, compared to conventional fire retardant, flame retardant effect becomes apparent from, preferable flame retardant effect can be realized in addition on a small quantity, and electrolysis fluid viscosity is lower, the conductivity of electrolyte is influenced smaller, moreover it is possible to have better compatibility with negative electrode material, lithium battery is made to keep higher chemical property while with preferable flame retarding function；Meanwhile the preparation method of fire retardant provided by the present invention, have the characteristics that synthesis technology is simple, at low cost, economic and environment-friendly.
Description
[technical field]
The present invention relates to the technical field of electrolyte of lithium battery, and in particular to for a kind of fire retardant and preparation method thereof, contains
The lithium battery flame-retardant electrolyte of the fire retardant and lithium battery containing the flame-retardant electrolyte.
[background technique]
Lithium battery has that specific energy is high, self-discharge rate is low, the remarkable advantages such as environmentally protective, is most widely used at present clear
Clean energy system.However, the electrolyte component that lithium battery uses at present is the mixed solvent system of inflammable ester or ether, although its
Excellent electrochemical performance, but easily burning even sets off an explosion, and causes personnel and property loss.Therefore, exploitation has non-ignitable
Or the lithium battery electrolytes of resistance to combustion have very important application value.
Currently, fire retardant is added into electrolyte and has become one of the main method for solving lithium battery security performance, often
Fire retardant has the compounds such as phosphate, phosphite ester, halogenated phosphate, halogenated acid phosphate and halogenated ether compound,
For example, patent CN103779608 makes electrolyte have certain flame retardant property by the way that tributyl phosphate (TBP) is added.But it hinders
The dosage of combustion agent addition can be only achieved certain flame retardant effect in 10%wt or more, not only increase the cost of electrolyte, also
It reduces the ionic conductivity of electrolyte, increase the viscosity of electrolyte, to reduce the chemical property of lithium battery.Cause
This, at present there is an urgent need to a kind of flame retardant effect is obvious, self stability is good, and can effectively improve lithium battery chemical property and peace
The new flame retardant of full property.
[summary of the invention]
For the above-mentioned technical problems in the prior art, the present invention provides a kind of fire retardant, which has
Good flame retardant effect, and make an addition in lithium battery electrolytes, not only flame retardant property is fabulous, viscosity is lower, conductivity is higher,
It ensure that the excellent chemical property of lithium battery, and the simple, cost with preparation process while improving lithium battery safety
Low, environmental-friendly advantage, the prospect with large-scale application.To achieve the above object, main technical schemes of the invention are such as
Under:
A kind of fire retardant, general structure are shown in formula I:
Wherein, R1-R6In, the general structure of at least one is as shown in Formula II, remaining general structure is as shown in formula III:
Wherein, R8ForIn any one, R9For C1-C4's
Alkyl, alkylene, containing any one in fluoroalkyl, Fluorine containing olefine base；
Wherein, R10For C1-C4Alkyl, alkylene, containing fluoroalkyl, Fluorine containing olefine base or phenyl ring, contain-CH3The benzene of substituent group
Any one in ring.
The present invention also provides the preparation methods of fire retardant as described above, comprising the following steps:
1. by with III structure of formula alcohol, phenol, metal alkoxide or metal phenates solution and hexachlorocyclotriph,sphazene replace
Reaction, obtains mix products A；
2. taking upper liquid, adding has the alcohol of Formula II structure or metal alkoxide molten after the mix products A centrifugation of step 1.
Liquid carries out substitution reaction, obtains mix products B；
3. to step, 2. middle mix products B carries out revolving purification, obtains the target product C with Formulas I structure；
Wherein, step 1. in III structure of formula alcohol or phenol general structure are as follows: R10- OH, the gold with III structure of formula
Belong to the general structure of alkoxide or metal phenates are as follows: R10-O-M；Step 2. in Formula II structure alcohol general structure are as follows: R9-
R8- OH, the general structure of the metal alkoxide with Formula II structure are as follows: R9-R8-O-N。
Preferably, described M, N are respectively lithium, sodium, any one in potassium element.
Further, step 1. in, the hexachlorocyclotriph,sphazene and alcohol, phenol, metal alkoxide or gold with III structure of formula
The molar ratio for belonging to phenates is 1:X, wherein X is any natural number in 1-5.
Further, step 2. in, mole of the hexachlorocyclotriph,sphazene and alcohol or metal alkoxide with Formula II structure
Than for 1:(6-X).
Further, in the metal alkoxide or metal phenates solution with III structure of formula, the gold with III structure of formula
It is 20-50% that the quality of category alkoxide or metal phenates, which accounts for solution gross mass,.
Further, in the metal alkoxide solution with Formula II structure, the matter of the metal alkoxide with Formula II structure
Amount accounts for the 20-50% of solution gross mass.
Further, the metal alkoxide solution with Formula II structure and the metal alkoxide or metal with III structure of formula
Phenate solution solvent for use is tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether and acetonitrile
One of or it is a variety of.
Further, the reaction temperature of the step 1. and 2. is 20-80 DEG C；Preferably, the reaction of step 1. and 2.
Temperature is 40-60 DEG C.
Further, the reaction time of the step 1. is 1-6h, and the reaction time of the step 2. is 2-8h；It is preferred that
, the reaction time of the step 1. is 2-3h, and the reaction time of the step 2. is 3-4h.
A kind of lithium battery flame-retardant electrolyte, by fire retardant as described above and non-aqueous organic solvent, lithium salts and additive
Composition.
Compared to the prior art, beneficial effects of the present invention are as follows:
The fire retardant synthesized in the present invention compares conventional flame retardants, and flame retardant effect becomes apparent from, addition can be realized on a small quantity compared with
Good flame retardant effect, and electrolysis fluid viscosity is lower, influences on the conductivity of electrolyte smaller, moreover it is possible to have more preferably with negative electrode material
Compatibility, so that lithium battery is also able to maintain preferable chemical property while being able to achieve flame retardant efficiency.Meanwhile the present invention proposes
Fire retardant preparation method, also have the advantages that synthesis technology is simple, cheap, economic and environment-friendly.
[specific embodiment]
The present invention provides a kind of fire retardant, general structure is shown in formula I:
Wherein, R1-R6In, the general structure of at least one is as shown in Formula II, remaining general structure is as shown in formula III:
Wherein, R8ForIn any one, R9For C1-C4's
Alkyl, alkylene, containing any one in fluoroalkyl, Fluorine containing olefine base；
Wherein, R10For C1-C4Alkyl, alkylene, containing fluoroalkyl, Fluorine containing olefine base or phenyl ring, contain-CH3The benzene of substituent group
Any one in ring.
The present invention also provides the preparation methods of fire retardant as described above, comprising the following steps:
1. alcohol or phenol, metal alkoxide or metal phenates solution and hexachlorocyclotriph,sphazene with III structure of formula are replaced
Reaction, obtains mix products A；
2. taking upper liquid, adding has the alcohol of Formula II structure or metal alkoxide molten after the mix products A centrifugation of step 1.
Liquid carries out substitution reaction, obtains mix products B；
3. to step 2. in mix products B carry out revolving purification, obtain the target product C with Formulas I structure；
Wherein, step 1. in III structure of formula alcohol or phenol general structure are as follows: R10- OH, the gold with III structure of formula
Belong to the general structure of alkoxide or metal phenates are as follows: R10-O-M；Step 2. in Formula II structure alcohol general structure are as follows: R9-
R8- OH, the general structure of the metal alkoxide with Formula II structure are as follows: R9-R8-O-N。
Further, described M, N are respectively any one in the elements such as lithium, sodium, potassium.
Further, step 1. in, the hexachlorocyclotriph,sphazene and alcohol, phenol, metal alkoxide or gold with III structure of formula
The molar ratio for belonging to phenates is 1:X, wherein X is any natural number in 1-5.
Further, step 2. in, the molar ratio of the hexachlorocyclotriph,sphazene and alcohol or alkoxide with Formula II structure is
1:(6-X).
Further, in the metal alkoxide or metal phenates solution with III structure of formula, the gold with III structure of formula
The quality of category alkoxide or metal phenates accounts for the 20-50% of solution gross mass.
Further, the metal alkoxide or metal phenates solution solvent for use with III structure of formula be tetrahydrofuran,
One of glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether and acetonitrile are a variety of.
Further, in the metal alkoxide solution with Formula II structure, the matter of the metal alkoxide with Formula II structure
Amount accounts for the 20-50% of solution gross mass.
Further, the metal alkoxide solution solvent for use with Formula II structure is tetrahydrofuran, glycol dinitrate
One of ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether and acetonitrile are a variety of.
Further, the reaction temperature of the step 1. and 2. is 20-80 DEG C；Preferably, the reaction of step 1. and 2.
Temperature is 40-60 DEG C.
Further, the reaction time of the step 1. is 1-6h, and the reaction time of the step 2. is 2-8h；It is preferred that
, the reaction time of the step 1. is 2-3h, and the reaction time of the step 2. is 3-4h.
A kind of lithium battery flame-retardant electrolyte, by fire retardant as described above and non-aqueous organic solvent, lithium salts and additive
Composition, percentage, the fire retardant, non-aqueous organic solvent, the content of lithium salts and additive are as follows:
Fire retardant: 2-30%
Non-aqueous organic solvent: 65-85%
Lithium salts: 5-20%
Additive: 0-8%
Further, the non-aqueous organic solvent includes cyclic carbonate and linear carbonate, and the linear carbonate is excellent
Be selected as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl acetate, methyl acetate, in butyl acetate
One or more combinations；The cyclic carbonate is preferably one of ethylene carbonate, propene carbonate or multiple combinations.
Further, the lithium salts is lithium hexafluoro phosphate, lithium perchlorate, LiBF4, di-oxalate lithium borate, double fluorine sulphurs
One of imide li, bis trifluoromethyl sulfimide lithium and double fluorine Lithium bis (oxalate) borates are a variety of；
Further, the additive is selected from vinylene carbonate, ethylene sulfite, fluorinated ethylene carbonate, carbonic acid
Vinylethylene, biphenyl, cyclohexyl benzene, tert-butyl benzene, succinonitrile, glutaronitrile, adiponitrile, the third sultone of 1,3-, 1,4- fourth sulphur
One of lactone, glycol sulfite, acrylic -1,3- sultones are a variety of.
The present invention also provides a kind of lithium battery, which contains lithium battery flame-retardant electrolyte as described above.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment and right
Than embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention is not intended to limit the present invention.
Embodiment 1
(1) preparation of fire retardant I
In N2Protection under, by 21.3g sodium ethoxide (structural formula are as follows: CH3-CH2- O-Na) and 120mL tetrahydrofuran at three mouthfuls
Stirring and dissolving in flask obtains content and is 20% alcohol sodium solution, then 22.5g hexachlorocyclotriph,sphazene is added to three-necked flask
Middle stirring and dissolving reacts 3h under 30 DEG C of reaction temperature, obtains mix products A.After mix products A centrifugation, upper liquid is taken,
Add the methyl glycollate (structural formula are as follows: CH of 5.4g3-O-CO-CH2OH), after reacting 3h, mix products B is obtained；To what is obtained
Mix products B rotates purification at 40 DEG C, 0.001MPa, obtains target product C, i.e. compound I (i.e. fire retardant I), purity is
99%, the structural formula of yield 97.1%, fire retardant I is as follows:
(2) preparation of anode pole piece
Nickel cobalt lithium aluminate, acetylene black, Kynoar are mixed according to mass ratio 96:2:2, N- methylpyrrole is added
Alkanone carries out high-speed stirred to mixture, obtains uniform anode sizing agent and dual coating on 12um aluminium foil, obtains after drying
It is spare after anode pole piece, roll-in and cross cutting.
(3) preparation of cathode pole piece
Graphite, acetylene black, butadiene-styrene rubber, sodium carboxymethylcellulose are mixed according to mass ratio 95:2:2:1, are added
Deionized water carries out high-speed stirred to mixture, uniform negative electrode slurry and dual coating is obtained on 8um copper foil, after drying
Obtain cathode pole piece, roll-in cross cutting after it is spare.
(4) preparation of electrolyte I
By organic solvent according to ethylene carbonate (EC) in glove box of the moisture less than 10ppm: dimethyl carbonate
(DMC): methyl ethyl carbonate (EMC): propene carbonate (PC)=3:4:2:1 mass ratio is uniformly mixed, and (organic solvent accounts for electricity
The percentage for solving liquid total weight is 77%), 15% electrolyte lithium salt (LiPF to be added6), then sequentially add 2% carbonic acid Asia
Vinyl acetate (VC), 2% fluorinated ethylene carbonate (FEC), 1% gamma-butyrolacton and 3% chemical compounds I, is thoroughly mixed
Uniformly to get arrive electrolyte I.
(5) preparation of lithium battery I
Anode pole piece, diaphragm, cathode pole piece are successively passed through into lamination in -60 DEG C of dry environments below in dew point control
Mode be fabricated to 10Ah battery core, in welding tab post package in aluminum plastic film, will preparation battery core toast after inject electrolyte
I, the processes such as aluminum plastic film sealing, chemical conversion, aging, partial volume are then carried out, lithium battery I is obtained.
Embodiment 2
(1) preparation of fire retardant II
In N2Protection under, by 8.3g ethyl alcohol (structural formula: CH3CH2OH) and 22.5g hexachlorocyclotriph,sphazene is added to three mouthfuls
Stirring and dissolving in flask reacts 4h under 70 DEG C of reaction temperature, obtains mix products A；After mix products A centrifugation, take
Layer liquid, adds the methyl glycollate of 16.2g, after reacting 3h, obtains mixture product B, to obtain mix products B 40 DEG C,
Purification is rotated under 0.001MPa, obtains target product C, i.e. compound II (i.e. fire retardant II), purity 99%, yield
96.5%, the structural formula of compound II is as follows:
(2) and (3) anode pole piece and cathode pole piece it is same as Example 1, details are not described herein.
(4) preparation of electrolyte II
By organic solvent according to ethylene carbonate (EC) in glove box of the moisture less than 10ppm: dimethyl carbonate
(DMC): methyl ethyl carbonate (EMC): propene carbonate (PC)=3:4:2:1 mass ratio is uniformly mixed, and (organic solvent accounts for electricity
The percentage for solving liquid total weight is 77%), 15% electrolyte lithium salt (LiPF to be added6), then sequentially add 2% carbonic acid Asia
Vinyl acetate (VC), 2% fluorinated ethylene carbonate (FEC), 1% gamma-butyrolacton and 3% compound II, be sufficiently stirred mixed
Close uniformly to get arrive electrolyte II.
(5) lithium battery II prepares in the same manner as in Example 1, and details are not described herein.
Embodiment 3
(1) preparation of fire retardant III
Under the protection of N2, by 16.2g sodium methoxide (structural formula are as follows: CH3- O-Na) and 80mL tetrahydrofuran in three-necked flask
Middle stirring and dissolving obtains content and is 22.5% sodium methoxide solution, then 22.5g hexachlorocyclotriph,sphazene is added in three-necked flask
Stirring and dissolving reacts 3h under 40 DEG C of reaction temperature, obtains mix products A；Mix products A is centrifuged, upper liquid is taken, is added
The hydroxy-ethyl acrylate of 7.5g obtains mix products B after reacting 3h.To obtained mix products B at 40 DEG C, 0.001MPa
Revolving purification, obtains target product C, i.e. compound III (i.e. fire retardant III), purity 99%, yield 98.5%, compound III
Structural formula it is as follows:
(2) and (3) anode pole piece and cathode pole piece it is same as Example 1, details are not described herein.
(4) preparation of electrolyte III
By organic solvent according to ethylene carbonate (EC) in glove box of the moisture less than 10ppm: dimethyl carbonate
(DMC): methyl ethyl carbonate (EMC): propene carbonate (PC)=3:4:2:1 mass ratio is uniformly mixed, and (organic solvent accounts for electricity
The percentage for solving liquid total weight is 77%), 15% electrolyte lithium salt (LiPF to be added6), then sequentially add 2% carbonic acid Asia
Vinyl acetate (VC), 2% fluorinated ethylene carbonate (FEC), 1% gamma-butyrolacton and 3% compound III, is sufficiently stirred mixed
Close uniformly to get arrive electrolyte III.
(5) lithium battery III prepares in the same manner as in Example 1, and details are not described herein.
Comparative example 1
(1) pole piece is prepared same as Example 1, and details are not described herein.
(2) preparation of electrolyte IV
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC): dimethyl carbonate
(DMC): methyl ethyl carbonate (EMC): propene carbonate (PC)=3:4:2:1 mass ratio is uniformly mixed, and (organic solvent accounts for electricity
The percentage for solving liquid total weight is 80%), 15% electrolyte lithium salt (LiPF to be added6), then sequentially add 2% carbonic acid Asia
Vinyl acetate (VC), 2% fluorinated ethylene carbonate (FEC), 1% gamma-butyrolacton are thoroughly mixed uniformly electric to get arriving
Solve liquid IV.
(3) preparation of lithium battery IV
The electrolyte that lithium battery IV uses is electrolyte IV, and lithium battery preparation process is same as Example 1.
Comparative example 2
(1) pole piece preparation embodiment 1 is identical, and details are not described herein.
(2) preparation of electrolyte V
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC): dimethyl carbonate
(DMC): methyl ethyl carbonate (EMC): propene carbonate (PC)=3:4:2:1 mass ratio is uniformly mixed, and (organic solvent accounts for electricity
The percentage for solving liquid total weight is 77%), 15% electrolyte lithium salt (LiPF to be added6), then sequentially add 2% carbonic acid Asia
Vinyl acetate (VC), 2% fluorinated ethylene carbonate (FEC), 1% gamma-butyrolacton and 3% trimethyl phosphate, is sufficiently stirred
It is uniformly mixed to get electrolyte V is arrived.
(3) preparation of lithium battery V
The electrolyte that lithium battery V uses is electrolyte V, and lithium battery preparation process is same as Example 1.
Comparative example 3
(1) pole piece preparation embodiment 1 is identical, and details are not described herein.
(2) preparation of electrolyte VI
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC): dimethyl carbonate
(DMC): methyl ethyl carbonate (EMC): propene carbonate (PC)=3:4:2:1 mass ratio is uniformly mixed, and (organic solvent accounts for electricity
The percentage for solving liquid total weight is 77%), 15% electrolyte lithium salt (LiPF to be added6), then sequentially add 2% carbonic acid Asia
Vinyl acetate (VC), 2% fluorinated ethylene carbonate (FEC), 1% gamma-butyrolacton and 3% three phosphonitrile of hexafluoro ring, sufficiently stir
It mixes and is uniformly mixed to get electrolyte VI is arrived.
(3) preparation of lithium battery VI
The electrolyte that lithium battery VI uses is electrolyte VI, and lithium battery preparation process is same as Example 1.
By electrolyte prepared by embodiment 1-3 and comparative example 1-3 and lithium battery carry out anti-flammability, viscosity, conductivity and
The test of the correlated performances such as capacity retention ratio, specific test mode and test result is as follows:
Test case 1: electrolyte flame-retardant test
The electrolyte that embodiment 1-3 and comparative example 1-3 is prepared carries out self-extinguishing time test, and self-extinguishing time is tested raw material and used
Mineral wool is prepared into the sphere that a collection of radius is about 5mm.Its quality is weighed, and is recorded.Then, it puts it into electrolyte
It impregnates, then weighs, impregnating front and back of poor quality, identical (impregnating the of poor quality of front and back is glass cotton balls Electolyte-absorptive
Quality).Then the cotton balls is placed on the circle iron wire of front, is lighted using gas igniter, and recorded used in extinguishing
Time, the average value for extinguishing the time used is calculated, test result is as shown in table 1.
Test case 2: electrolysis fluid viscosity and conductivity are tested
It tests the viscosity and conductivity of each electrolyte sample respectively using rotational viscometer and desk-top conductivity measurement, surveys
Trying temperature is 25 DEG C, and test result is the average value measured three times, and test result is as shown in table 1.
Test case 3: cycle performance test of the lithium battery at 25 DEG C
Soft-package battery after partial volume is connect under 25 DEG C of environment with charge-discharge test instrument, battery is set with the electricity of 0.5C
Stream carries out constant-current constant-voltage charging, and blanking voltage 4.2V, cut-off current 0.01C shelve 10min, then permanent with the electric current of 0.5C
Stream is discharged to 2.75V, shelves 10min, so circulation 50 weeks.Capacity retention ratio when calculating its 50 weeks, test result such as 1 institute of table
Show.
The performance test results of electrolyte prepared by table 1 embodiment 1-3 and comparative example 1-3
Such as table 1, according to embodiment 1-3 and not plus from the point of view of the self-gravitation time data comparison of the comparative example 1 of fire retardant, use
After fire retardant prepared by the present invention, electrolyte self-extinguishing time is in 10s hereinafter, illustrating fire retardant provided by the present invention with excellent
Flame retardant effect；Embodiment 1-3 and the comparative example 2,3 using general fire retardant (three phosphonitrile of trimethyl phosphate and hexafluoro ring) are seen again
The self-gravitation time data comparison, illustrate that the flame retardant effect of fire retardant prepared by embodiment 1-3 is better than comparative example 2 and right
The general electrolyte flame-retardant agent that ratio 3 uses；According to being added to the embodiment 1-3 of fire retardant provided by the present invention and be not added with
Viscosity, the test result of conductivity of the comparative example 1 of fire retardant, are added to after fire retardant provided by the present invention, electrolyte
Viscosity do not obviously increase, illustrate that fire retardant provided by the present invention is smaller to the viscosity influence of electrolyte, and electrolyte
Conductivity also without being substantially reduced.According to all discharge capacities of the head of embodiment 1-3 and 1 battery of comparative example for being not added with fire retardant
The initial discharge capacity of test result, the initial capacity and comparative example 1 of embodiment 1-3 battery is not much different, and illustrates institute of the present invention
The flame-retardant electrolyte of offer is preferable to the compatibility of cathode.From the point of view of 50 weeks capacity retention ratios, the capacity of embodiment 1-3 is protected
Holdup is respectively 94%, 94% and 93%, still there is higher capacity retention ratio, higher than pair for using general electrolysis additive
The capacity retention ratio of ratio 2 and 3.
It is seen through properties test result data, fire retardant provided by the present invention is applied in electrolyte, has fine
Flame retardant effect, and electrolyte can be made to be able to maintain good chemical property while with flame retardant property.
The above content is combine specific optimal technical scheme further detailed description of the invention, and it cannot be said that
Specific implementation of the invention is only limited to these instructions, and can not be considered limitations on the claims.For belonging to the present invention
For the professional technician of technical field, without departing from the inventive concept of the premise, several simple deductions can also be made
Or replacement, it all shall be regarded as belonging to protection scope of the present invention.
Claims (10)
1. a kind of fire retardant, which is characterized in that its general structure is shown in formula I:
Wherein, R1-R6In, the general structure of at least one is as shown in Formula II, remaining general structure is as shown in formula III:
Wherein, R8ForIn any one, R9For C1-C4Alkyl,
Alkylene, containing any one in fluoroalkyl, Fluorine containing olefine base；
Wherein, R10For C1-C4Alkyl, alkylene, containing fluoroalkyl, Fluorine containing olefine base or phenyl ring, contain-CH3In the phenyl ring of substituent group
Any one.
2. fire retardant according to claim 1, which is characterized in that preparation method includes the following steps:
1. by with III structure of formula alcohol, phenol, metal alkoxide or metal phenates solution and hexachlorocyclotriph,sphazene carry out substitution reaction,
Obtain mix products A；
2. take upper liquid after the mix products A centrifugation of step 1., add the alcohol with Formula II structure or metal alkoxide solution into
Row substitution reaction obtains mix products B；
3. to step 2. in mix products B carry out revolving purification, obtain the target product C with Formulas I structure；Wherein, step
The general structure of alcohol or phenol in 1. with III structure of formula are as follows: R10- OH, metal alkoxide or metal phenates with III structure of formula
General structure are as follows: R10-O-M；Step 2. in Formula II structure alcohol general structure are as follows: R9-R8- OH has Formula II structure
Metal alkoxide general structure are as follows: R9-R8-O-N。
3. fire retardant according to claim 2, which is characterized in that described M, N be respectively lithium, sodium, any in potassium element
It is a kind of.
4. fire retardant according to claim 2, which is characterized in that step 1. in, the hexachlorocyclotriph,sphazene and have formula
The alcohol of III structure, phenol, metal alkoxide or phenates molar ratio be 1:X, wherein X is any natural number in 1-5.
5. fire retardant according to claim 4, which is characterized in that step 2. in, the hexachlorocyclotriph,sphazene and have formula
The molar ratio of the alcohol of II structure is 1:(6-X).
6. fire retardant according to claim 2, which is characterized in that the metal alkoxide solution with Formula II structure, tool
Have in the metal alkoxide or metal phenates solution of III structure of formula, the metal alkoxide with Formula II structure, the gold with III structure of formula
The quality of category alkoxide or metal phenates accounts for the 20-50% of its solution gross mass respectively.
7. fire retardant according to claim 2, which is characterized in that the metal alkoxide solution and tool with Formula II structure
There is the metal alkoxide of III structure of formula or phenate solution solvent for use is tetrahydrofuran, glycol dimethyl ether, diethylene glycol diformazan
One of ether, diethylene glycol monomethyl ether and acetonitrile are a variety of.
8. fire retardant according to claim 2, which is characterized in that the reaction temperature of the step 1. and 2. is 20-80
℃。
9. fire retardant according to claim 2, which is characterized in that the reaction time of the step 1. is 1-6h, the step
Suddenly the reaction time 2. is 2-8h.
10. a kind of lithium battery flame-retardant electrolyte, which is characterized in that by described in any item fire retardants of claim 1-9 and non-
Aqueous organic solvent, lithium salts and additive composition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698586A (en) * | 2019-10-14 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | Lithium battery positive electrode additive and preparation method thereof |
| CN112189278A (en) * | 2020-01-11 | 2021-01-05 | 山东理工大学 | Preparation method of flame-retardant lithium ion battery electrolyte easy to dissolve in organic solvent |
| CN113130996A (en) * | 2019-12-31 | 2021-07-16 | 北京卫蓝新能源科技有限公司 | Lithium battery electrolyte additive and preparation method and application thereof |
| CN113363579A (en) * | 2021-06-08 | 2021-09-07 | 清华大学深圳国际研究生院 | Flame-retardant electrolyte, preparation method and lithium metal battery |
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| CN113363579A (en) * | 2021-06-08 | 2021-09-07 | 清华大学深圳国际研究生院 | Flame-retardant electrolyte, preparation method and lithium metal battery |
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Inventor after: Gao Peng Inventor after: Huang Jie Inventor after: Li Qun Inventor before: Li Qun Inventor before: Huang Jie Inventor before: Gao Peng |
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Application publication date: 20190517 |