CN107706463A - The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery - Google Patents
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery Download PDFInfo
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Abstract
The invention discloses a kind of nitroso of lithium battery to be grafted carbonic ester electrolyte and preparation method, by nitrite to ethylene carbonate and propene carbonate mixed processing, while adds a small amount of fluoro ethers, borate as auxiliary agent, low temperature（40‑50℃）Heating water bath simultaneously quickly stirs, while adjusts PH to alkalescent, makes NO after nitrite ion decomposition2 ‑With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate, the antioxygenic property of carbonic ester is improved by fluoro ethers and nitroso collective effect, small molecule group grafting simultaneously can reduce solution overall viscosity, part nitrogen-atoms causes fault of construction in a manner of displacement into carbochain, reduces the combination energy of nitroso group.
Description
Technical field
The present invention relates to field of lithium, and in particular to lithium battery electrolytes, more particularly to a kind of nitrous of lithium battery
Base is grafted carbonic ester electrolyte and preparation method.
Background technology
Lithium battery electrolytes are the carriers of battery intermediate ion transmission.Typically it is made up of lithium salts and organic solvent.Electrolyte exists
Play a part of conducting ion between lithium battery both positive and negative polarity, be the guarantee for the advantages that lithium ion battery obtains high voltage, high specific energy.
Electrolyte is typically by raw materials such as the organic solvent of high-purity, electrolyte lithium salt, necessary additives, under certain condition, by one
What certainty ratio was formulated.The main component of lithium battery point solution liquid generally comprises following seven kinds：1. ethylene carbonate, propylene carbonate
Ester, diethyl carbonate, dimethyl carbonate (dimethyl carbonate, DMC), methyl ethyl carbonate, lithium hexafluoro phosphate, five fluorine
Change phosphorus；Wherein ethylene carbonate, molecular formula:C3H4O3, clear colorless liquid (>35 DEG C), it is polyacrylonitrile, polyvinyl chloride
Good solvent.It can be used as the liquid that reels off raw silk from cocoons in weaving；Also can be directly as the solvent of removing sour gas and the additive of concrete；
It can be used as the component and raw material of pharmacy in medicine；Also act as the stabilizer of plastics blowing agent and synthetic lubricant fluid；In battery
Industrially, can be as the fine solvent of lithium battery electrolytes.Propene carbonate molecular formula:C4H6O3, colourless odorlessness, or it is light
Yellow transparent liquid, water and carbon tetrachloride are dissolved in, it is miscible with ether, acetone, benzene etc..It is a kind of excellent polar solvent.This production
Product are mainly used in high score subjob, gas separating technology and electrochemistry.Particularly it is used for absorbing natural gas, petrochemical plant synthesis ammonia original
Expect carbon dioxide therein, also act as plasticizer, spin solvent, alkene and aromatic hydrocarbons extraction agent etc..
For now, the electrolyte that lithium battery mainly uses has lithium perchlorate, lithium hexafluoro phosphate etc..But use lithium perchlorate
Manufactured battery cryogenic effect is bad, there is the danger of blast, and Japan and the U.S. have prohibitted the use of.It is and electric made of fluorine-containing lithium salts
Pond performance is good, no explosion danger, strong applicability, the battery particularly made of lithium hexafluoro phosphate, in addition to the above-described advantages, useless in the future
The processing work of rechargeable batteries is relatively easy, and to eco-friendly, therefore the electrolytelike market prospects are quite varied.In lithium
While ion battery application is extensive all the more, the attention rate of its security, cycle performance and cryogenic property on 3C batteries is more very
In its energy density and capacity.Current lithium battery electrolytes solvent is mainly carbonic ether, carboxylic acid esters, and cyclic carbonates are situated between
Electric constant is high, but viscosity is higher simultaneously, and linear carbonates class viscosity is relatively low, and dielectric constant is relatively low.Current carbonates are molten
Agent can not meet demand of both dielectric constant and viscosity separately as electrolyte solvent, and for inoxidizability and safety
Property is poor, therefore is of great practical significance for the study on the modification of electrolyte.
Application No. CN201210481362.8 discloses a kind of electrolyte for Li-S batteries, and it is mainly by electrolyte
Salt and organic solvent composition, electrolytic salt include polysulfide lithium, and the molecular formula of the polysulfide lithium is Li2Sn.The preparation side of the electrolyte
Method is：Lithium metal or Li2S are added in organic solvent in molar ratio with elemental sulfur, entered under normal temperature and inert atmosphere protection
Row reaction can obtain electrolyte, alternative addition lithium salts, shuttle inhibitor etc. in the electrolyte；Also disclose comprising foregoing
The Li-S batteries of electrolyte, its negative active core-shell material are lithium metal or lithium alloys；Its positive electrode active materials is sulphur simple substance, organic
At least one of sulfide, carbon-sulfur polymer, and positive electrode active materials, conductive agent and adhesive are by certain mass proportioning composition
Positive pole；The dosage that wherein every milligram of sulphur corresponds to electrolyte is about 0.04mL；Above-mentioned organic solvent be ethanol, acetonitrile, hexamethylene,
Cyclohexanone, isopropanol, tetrahydrofuran, 2- methyltetrahydrofurans, ethylene carbonate, propene carbonate, butylene, carbonic acid two
Methyl esters, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl formate, Ethyl formate, methyl acetate, ethyl acetate, second
It is propyl propionate, methyl propionate, ethyl propionate, ethyl butyrate, dimethoxy-ethane, 1,3- dioxolanes, glycol dimethyl ether, two sweet
At least one of diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, sulfolane, two methylene sulfones, dimethyl sulfone；Should
Although patent proposes is carried out as electrolyte using a variety of organic solvents, and but still unresolved electrolyte solvent is for dielectric constant
With viscosity both sides demand.
The content of the invention
For disadvantages described above, it is an object of the invention to provide a kind of nitroso of lithium battery to be grafted carbonic ester electrolyte and system
Preparation Method, make NO after nitrite ion decomposition2 -With EC/PC alkane alkenyl and Carbonyl addition, pass through fluoro ethers and nitroso
Collective effect improves the antioxygenic property of carbonic ester, while the grafting of small molecule group can reduce solution overall viscosity, so as to solve
The problem of certainly existing in terms of electrolyte organic solvent dielectric constant and viscosity.
In order to solve the above technical problems,
The preparation method of the nitroso grafting carbonic ester electrolyte of a kind of lithium battery, it is characterised in that comprise the following steps：
S01：By nitrous acid lithium salts to organic solvent ethylene carbonate and propene carbonate mixed processing, while add auxiliary agent；
S02：Heating water bath and quickly stirred under 40 DEG C~50 DEG C of cryogenic conditions；
S03：PH value is adjusted during heating water bath to alkalescent, makes NO after nitrite ion decomposition2 -With ethylene carbonate
The alkane alkenyl and Carbonyl addition of ester and propene carbonate；
S04：Kept for 10~30 minutes reaction time completed the preparation of electrolyte.
As the further improvement of this programme, the pH value is 7~8.5.
NO in the nitrous acid lithium salts2 -The ratio of ion and alkane alkenyl and carbonyl molal quantity sum is 1：（1~
3）；
As the further improvement of this programme, the NO2 -The ratio of ion and alkane alkenyl and carbonyl molal quantity sum is 1：1, survey
The viscosity data for obtaining electrolyte is represented and is recorded in table 1 with D1.It is the NO decomposited using nitrite in the present invention2 -Ion
With alkane alkenyl and Carbonyl addition so that the grafting of small molecule group reduces the overall viscosity of solution, therefore in order that small molecule group
Grafting completely so that the quantity of point solution liquid small molecular group is reduced, NO2 -Ion and alkane alkenyl and carbonyl molal quantity sum are most
Ratio of greater inequality example should be 1：1, that is to say, that NO2 -Number of ions=alkane alkenyl number+carbonyl number, so that three can be reacted completely,
So that single NO is not present in electrolyte2 -, alkane alkenyl, carbonyl；So that the viscosity of electrolyte is minimum.
As the further improvement of this programme, the organic solvent is that the mixing of ethylene carbonate and propene carbonate is molten
Agent, the NO2 -The ratio of ion and alkane alkenyl and carbonyl molal quantity sum is 1：2, measure the viscosity data D2 tables of electrolyte
Show and be recorded in table 1.
As the further improvement of this programme, the mixing molar ratio of the ethylene carbonate and propene carbonate is 1：
（0.5~1）, the mixing molar ratio of preferable ethylene carbonate and propene carbonate is 1：0.5, the NO2 -Ion and alkane alkene
The ratio of base and carbonyl molal quantity sum is 1：1, the viscosity data for measuring electrolyte is represented and is recorded in table 1 with D3.It is based on
The chemical property of ethylene carbonate and propene carbonate, ethylene carbonate have higher stability compared to propene carbonate,
Ethylene carbonate and propene carbonate are that a kind of polar solvent can provide NO simultaneously2 -Alkane alkenyl and carbonyl needed for grafting, carbon
The difference of vinyl acetate and propene carbonate is that ethylene carbonate has higher performance as electrolyte, therefore in the present invention
The ratio of middle ethylene carbonate in the electrolytic solution is more than propene carbonate.
As the further improvement of this programme, the auxiliary agent is fluoro ethers, the mol ratio of the auxiliary agent and organic solvent
It is（0.1~0.5）：1, the mol ratio that auxiliary agent and organic solvent are selected in preferable this programme is 0.2:1, measure the viscous of electrolyte
Degrees of data is represented and is recorded in table 1 with D4.In order to strengthen the antioxygenic property of electrolyte, by add auxiliary agent fluoro ethers and
Nitroso collective effect improves the antioxygenic property of ethylene carbonate and propene carbonate, and part nitrogen-atoms is entered in a manner of displacement
Carbochain causes fault of construction, reduces the combination energy of nitroso group.
As the further improvement of this programme, the auxiliary agent is fluoro ethers and borate by 1：0.3 mixing, it is described to help
The mol ratio of agent and organic solvent is（0.1~0.5）：1, fluoro ethers in preferable this programme, borate and organic solvent
Mol ratio is 0.2:0.06:1, the viscosity data for measuring electrolyte is represented and is recorded in table 1 with D5.Borate has stronger
Alkalescence, a small amount of borate is added in the electrolytic solution and is used to adjust electrolyte to alkalescent, is catalyzed NO2 -With ethylene carbonate and carbon
The alkane alkenyl and Carbonyl addition of acid propylene ester, so as to reduce the combination energy of nitroso group, to prevent the alkaline too strong of electrolyte,
The mol ratio of preferable auxiliary agent and organic solvent is 0.1：1, in other words it is exactly that the mol ratio of borate and solvent is about equal to
0.025:1。
Table 1, viscosity measurement data：
The present invention is by nitrite to ethylene carbonate（EC）And propene carbonate（PC）Mixed processing, while add a small amount of fluorine
For ethers, borate as auxiliary agent, NO after nitrite ion decomposes2 -With EC/PC alkane alkenyl and Carbonyl addition, pass through fluoro
Ethers and nitroso collective effect improve the antioxygenic property of carbonic ester, while the grafting of small molecule group can reduce solution entirety
Viscosity, part nitrogen-atoms cause fault of construction in a manner of displacement into carbochain, reduce the combination energy of nitroso group.
A kind of nitroso grafting carbonic ester electrolyte for the lithium battery being prepared by the above method.
By the optimization to above-mentioned different schemes, and Binding experiment data can be drawn, NO is catalyzed in electrolyte2 -Number alkane alkene
In the case that base and carbonyl number sum are equal, the viscosity of electrolyte is optimal, once alkane alkenyl and carbonyl number are more than NO2 -Number
Mesh, the viscosity of electrolyte are increased slightly；Ethylene carbonate and the single carbon of the mixed organic solvent ratio of propene carbonate simultaneously
In the case that vinyl acetate or propene carbonate are as organic solvent, the viscosity of electrolyte is lower；And fluorine is added in the electrolytic solution
After adjusting pH value to alkalescent for ethers, the viscosity of electrolyte is greatly lowered, therefore can be concluded that fluorine
A viscosity of solution is effectively reduced for ethers, while adding borate can be such that effect further strengthens.
Compared with prior art, the nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery of the invention
Beneficial effect is：The present invention is by nitrite to ethylene carbonate（EC）And propene carbonate（PC）Mixed processing, add simultaneously
Enter a small amount of fluoro ethers, borate as auxiliary agent, low temperature（40-50℃）Heating water bath simultaneously quickly stirs, while adjusts PH to weak
Alkalescence, make NO after nitrite ion decomposition2 -With EC/PC alkane alkenyl and Carbonyl addition, it is total to by fluoro ethers and nitroso
Same-action improves the antioxygenic property of carbonic ester, while the grafting of small molecule group can reduce solution overall viscosity, and part nitrogen is former
Son causes fault of construction in a manner of displacement into carbochain, reduces the combination energy of nitroso group.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, by nitrous acid lithium salts to ethylene carbonate and carbon
Acid propylene ester mixed processing, the wherein mixed proportion of ethylene carbonate and propene carbonate are 1:0.5, while add fluoro-ether
As auxiliary agent, the ratio of fluoro ethers and borate is 1 for class, borate:0.3, electrolyte is formed, is formed in the mixed solution
The molar fraction of lithium nitrite salt is 0.435 i.e. NO in electrolyte2 -Molar fraction for 0.435, ethylene carbonate mole point
Number is 0.29, and the molar fraction of propene carbonate is 0.145；That is the molar fraction of ethylene carbonate rubbing for+propene carbonate
Your fraction is 0.435, and the molar fraction sum of alkane alkenyl and carbonyl is 0.87, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl
The ratio of the molar fraction sum of base is 1:2；The molar fraction of fluoro ethers is 0.1, the molar fraction of borate is 0.03；
Heating water bath and quickly stirred under 40 DEG C of cryogenic conditions；PH value is adjusted during heating water bath to 7.5, makes nitrite anions
NO after ion dissociation2 -With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate；Kept for 15 minutes reaction time complete
Into the preparation of electrolyte；Electrolyte anti oxidation time T1 and electrolysis fluid viscosity D1 are measured, and is recorded in table 2.
Embodiment 2
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, by nitrous acid lithium salts to ethylene carbonate and carbon
Acid propylene ester mixed processing, the wherein mixed proportion of ethylene carbonate and propene carbonate are 1:1, at the same add fluoro ethers,
For borate as auxiliary agent, the ratio of fluoro ethers and borate is 1:0.3, electrolyte is formed, in the electricity that the mixed solution is formed
The molar fraction for solving lithium nitrite salt in liquid is 0.493 i.e. NO2 -Molar fraction for 0.493, the molar fraction of ethylene carbonate
For 0.125, the molar fraction of propene carbonate is 0.125；I.e. the molar fraction of ethylene carbonate for+propene carbonate mole
Fraction is 0.25, and the molar fraction sum of alkane alkenyl and carbonyl is 0.5, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl
The ratio of molar fraction sum is 1:1；The molar fraction of fluoro ethers is 0.2, the molar fraction of borate is 0.06；At 45 DEG C
Cryogenic conditions under heating water bath and quickly stir；PH value is adjusted during heating water bath to 8.1, makes nitrite ion
NO after decomposition2 -With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate；Kept for 30 minutes reaction time completed electricity
Solve the preparation of liquid；Electrolyte anti oxidation time T2 and electrolysis fluid viscosity D2 are measured, and is recorded in table 2.
Embodiment 3
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, nitrous acid lithium salts is mixed to ethylene carbonate
Processing, at the same add fluoro ethers, borate is used as auxiliary agent, the ratio of fluoro ethers and borate is 1:0.3, form electrolysis
Liquid, the molar fraction of lithium nitrite salt is 0.435 i.e. NO in the electrolyte that the mixed solution is formed2 -Molar fraction be
0.435th, the molar fraction of ethylene carbonate is 0.435；I.e. the molar fraction of ethylene carbonate for+propene carbonate mole point
Number is 0.435, and the molar fraction sum of alkane alkenyl and carbonyl is 0.87, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl
The ratio of molar fraction sum is 1:2；The molar fraction of fluoro ethers is 0.1, the molar fraction of borate is 0.03；At 40 DEG C
Cryogenic conditions under heating water bath and quickly stir；PH value is adjusted during heating water bath to 7.5, makes nitrite ion
NO after decomposition2 -With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate；Kept for 30 minutes reaction time completed electricity
Solve the preparation of liquid；Electrolyte anti oxidation time T3 and electrolysis fluid viscosity D3 are measured, and is recorded in table 2.
Embodiment 4
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, nitrous acid lithium salts is mixed to propene carbonate
Processing, at the same add fluoro ethers, borate is used as auxiliary agent, the ratio of fluoro ethers and borate is 1:0.3, form electrolysis
Liquid, the molar fraction of lithium nitrite salt is 0.435 i.e. NO in the electrolyte that the mixed solution is formed2 -Molar fraction be
0.435th, the molar fraction of propene carbonate is 0.435；I.e. the molar fraction of ethylene carbonate for+propene carbonate mole point
Number is 0.435, and the molar fraction sum of alkane alkenyl and carbonyl is 0.87, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl
The ratio of molar fraction sum is 1:2；The molar fraction of fluoro ethers is 0.1, the molar fraction of borate is 0.03；At 40 DEG C
Cryogenic conditions under heating water bath and quickly stir；PH value is adjusted during heating water bath to 7.5, makes nitrite ion
NO after decomposition2 -With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate；Kept for 25 minutes reaction time completed electricity
Solve the preparation of liquid；Electrolyte anti oxidation time T4 and electrolysis fluid viscosity D4 are measured, and is recorded in table 2.
Embodiment 5
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, by nitrous acid lithium salts to ethylene carbonate and carbon
Acid propylene ester mixed processing, the wherein mixed proportion of ethylene carbonate and propene carbonate are 1:1, at the same add fluoro ethers,
For borate as auxiliary agent, the ratio of fluoro ethers and borate is 1:0.3, electrolyte is formed, in the electricity that the mixed solution is formed
The molar fraction for solving lithium nitrite salt in liquid is 0.41 i.e. NO2 -Molar fraction be 0.41, the molar fraction of ethylene carbonate be
0.101, the molar fraction of propene carbonate is 0.101；I.e. the molar fraction of ethylene carbonate for+propene carbonate mole point
Number is 0.202, and the molar fraction sum of alkane alkenyl and carbonyl is 0.41, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl
The ratio of molar fraction sum is 1:1；The molar fraction of fluoro ethers is 0.3, the molar fraction of borate is 0.09；At 40 DEG C
Cryogenic conditions under heating water bath and quickly stir；PH value is adjusted during heating water bath to 8.3, makes nitrite ion
NO after decomposition2 -With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate；Kept for 15 minutes reaction time completed electricity
Solve the preparation of liquid；Electrolyte anti oxidation time T5 and electrolysis fluid viscosity D5 are measured, and is recorded in table 2.
Embodiment 6
The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, by nitrous acid lithium salts to ethylene carbonate and carbon
Acid propylene ester mixed processing, the wherein mixed proportion of ethylene carbonate and propene carbonate are 1:0.5, while add fluoro-ether
As auxiliary agent, the ratio of fluoro ethers and borate is 1 for class, borate:0.3, electrolyte is formed, is formed in the mixed solution
The molar fraction of lithium nitrite salt is 0.435 i.e. NO in electrolyte2 -Molar fraction for 0.435, ethylene carbonate mole point
Number is 0.29, and the molar fraction of propene carbonate is 0.145；That is the molar fraction of ethylene carbonate rubbing for+propene carbonate
Your fraction is 0.435, and the molar fraction sum of alkane alkenyl and carbonyl is 0.87, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl
The ratio of the molar fraction sum of base is 1:2；The molar fraction of fluoro ethers is 0.15, the molar fraction of borate is 0.45；
Heating water bath and quickly stirred under 40 DEG C of cryogenic conditions；PH value is adjusted during heating water bath to 7.9, makes nitrous acid
NO after radical ion decomposes2 -With ethylene carbonate and the alkane alkenyl and Carbonyl addition of propene carbonate；Kept for 15 minutes reaction time
Complete the preparation of electrolyte；Electrolyte anti oxidation time T6 and electrolysis fluid viscosity D6 are measured, and is recorded in table 2.
Comparative example 1
A kind of lithium battery electrolytes, by nitrous acid lithium salts to ethylene carbonate and propene carbonate mixed processing, wherein ethylene
The mixed proportion of alkene ester and propene carbonate is 1:0.5 forms electrolyte, the nitrous acid in the electrolyte that the mixed solution is formed
The molar fraction of lithium salts is 0.5 i.e. NO2 -Molar fraction be 0.4, the molar fraction of ethylene carbonate be 0.333, propylene carbonate
The molar fraction of ester is 0.167；I.e. the molar fraction of ethylene carbonate is approximately equal to for 0.5 for the molar fraction of+propene carbonate,
And the molar fraction sum of alkane alkenyl and carbonyl is 1, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl molar fraction sum
Ratio is 1:2 measurement electrolyte anti oxidation time T1-1 and electrolysis fluid viscosity D1-1, and be recorded in table 2.
Comparative example 2
A kind of lithium battery electrolytes, by nitrous acid lithium salts to ethylene carbonate and propene carbonate mixed processing, wherein ethylene
The mixed proportion of alkene ester and propene carbonate is 1:1, while fluoro ethers is added, electrolyte is formed, is formed in the mixed solution
Electrolyte in lithium nitrite salt molar fraction for 0.533 i.e. NO2 -Molar fraction for 0.533, mole of ethylene carbonate
Fraction is 0.133, and the molar fraction of propene carbonate is 0.133；I.e. the molar fraction of ethylene carbonate is+propene carbonate
Molar fraction is 0.267, and the molar fraction sum of alkane alkenyl and carbonyl is 0.533, i.e. NO2 -Molar fraction and alkane alkenyl and
The ratio of the molar fraction sum of carbonyl is 1:1；The molar fraction of fluoro ethers is the 0.2, water-bath under 45 DEG C of cryogenic conditions
Heat and quickly stir；Electrolyte anti oxidation time T2-1 and electrolysis fluid viscosity D2-1 are measured, and is recorded in table 2.
Comparative example 3
A kind of lithium battery electrolytes, nitrous acid lithium salts is formed into electrolysis to ethylene carbonate mixed processing, borate as auxiliary agent
Liquid, the molar fraction of lithium nitrite salt is 0.435 i.e. NO in the electrolyte that the mixed solution is formed2 -Molar fraction be
0.485th, the molar fraction of ethylene carbonate is 0.485；And the molar fraction sum of alkane alkenyl and carbonyl is 0.97, i.e. NO2 -'s
The ratio of molar fraction and the molar fraction sum of alkane alkenyl and carbonyl is 1:2；The molar fraction of borate is 0.03；At 40 DEG C
Cryogenic conditions under heating water bath and quickly stir；9 keep the preparation of 30 minutes reaction time completion electrolyte；Measure electrolyte
Anti oxidation time T3-1 and electrolysis fluid viscosity D3-1, and be recorded in table 2.
Comparative example 4
A kind of lithium battery electrolytes, the nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery, by lithium nitrite
Salt forms electrolyte, mole of lithium nitrite salt in the electrolyte that the mixed solution is formed to propene carbonate mixed processing
Fraction is 0.5 i.e. NO2 -Molar fraction be 0.5, the molar fraction of propene carbonate be 0.5；And mole of alkane alkenyl and carbonyl
Fraction sum is 1, i.e. NO2 -Molar fraction and the molar fraction sum of alkane alkenyl and carbonyl ratio be 1:2；It is low at 40 DEG C
Heating water bath and quickly stirred under the conditions of temperature；Kept for 25 minutes reaction time completed the preparation of electrolyte；Measure electrolyte antioxygen
Change time T4-1 and electrolysis fluid viscosity D4-1, and be recorded in table 2.
Comparative example 5
A kind of lithium battery electrolytes, by nitrous acid lithium salts to ethylene carbonate and propene carbonate mixed processing, wherein ethylene
The mixed proportion of alkene ester and propene carbonate is 1:1, while fluoro ethers is added, electrolyte is formed, is formed in the mixed solution
Electrolyte in lithium nitrite salt molar fraction for 0.6 i.e. NO2 -Molar fraction for 0.41, the molar fraction of ethylene carbonate
For 0.15, the molar fraction of propene carbonate is 0.15；I.e. the molar fraction of ethylene carbonate for+propene carbonate mole point
Number is 0.3, and the molar fraction sum of alkane alkenyl and carbonyl is 0.6, i.e. NO2 -Molar fraction and alkane alkenyl and carbonyl mole
The ratio of fraction sum is 1:1；The molar fraction of fluoro ethers is 0.1 system for keeping 15 minutes reaction time completion electrolyte
It is standby；Electrolyte anti oxidation time T5-1 and electrolysis fluid viscosity D5-1 are measured, and is recorded in table 2..
Comparative example 6
A kind of lithium battery electrolytes, by nitrous acid lithium salts to ethylene carbonate and propene carbonate mixed processing, wherein ethylene
The mixed proportion of alkene ester and propene carbonate is 1:1, while fluoro ethers, borate are added as auxiliary agent, fluoro ethers and boron
The ratio of hydrochlorate is 1:0.3, electrolyte is formed, the molar fraction of lithium nitrite salt is in the electrolyte that the mixed solution is formed
0.4 i.e. NO2 -Molar fraction be 0.4, the molar fraction of ethylene carbonate be 0.05, the molar fraction of propene carbonate is
0.05；I.e. the molar fraction of ethylene carbonate is 0.1 for the molar fraction of+propene carbonate, and mole of alkane alkenyl and carbonyl
Fraction sum is 0.87, i.e. NO2 -Molar fraction and the molar fraction sum of alkane alkenyl and carbonyl ratio be 2:1；Fluoro-ether
The molar fraction of class is 0.4, the molar fraction of borate is 0.1；Heating water bath and quickly stirred under 40 DEG C of cryogenic conditions；
PH value is adjusted during heating water bath to 9.6, makes NO after nitrite ion decomposition2 -With ethylene carbonate and propylene carbonate
The alkane alkenyl and Carbonyl addition of ester；Kept for 15 minutes reaction time completed the preparation of electrolyte；Measure electrolyte anti oxidation time
T6-1 and electrolysis fluid viscosity D6-1, and be recorded in table 2.
The embodiment of table 2 and comparative example electrolyte anti oxidation time and viscosity
By the optimization to above-mentioned different schemes, and Binding experiment data can be drawn, influenceed electrolyte antioxygenic property and glued
The leading indicator of degree is being catalyzed NO in electrolyte2 -Number alkane alkenyl and the ratio of carbonyl number and the acid-base property of electrolyte, once
Alkane alkenyl and carbonyl number are more than NO2 -Number, the viscosity of electrolyte are increased slightly；And in the case of alkalescent electrolyte it is anti-oxidant
Performance is higher than acid or strong alkaline electrolytes.
Claims (7)
1. the preparation method of the nitroso grafting carbonic ester electrolyte of a kind of lithium battery, it is characterised in that comprise the following steps：
S01：By nitrous acid lithium salts to organic solvent ethylene carbonate and propene carbonate mixed processing, while add auxiliary agent；
S02：Heating water bath and quickly stirred under 40 DEG C~50 DEG C of cryogenic conditions；
S03：PH value is adjusted during heating water bath to alkalescent, makes NO after nitrite ion decomposition2 -With ethylene carbonate
The alkane alkenyl and Carbonyl addition of ester and propene carbonate；
S04：Kept for 10~30 minutes reaction time completed the preparation of electrolyte.
2. a kind of preparation method of the nitroso grafting carbonic ester electrolyte of lithium battery, its feature exist according to claim 1
In：The pH value is 7~8.5.
3. a kind of preparation method of the nitroso grafting carbonic ester electrolyte of lithium battery, its feature exist according to claim 1
In：NO in the nitrous acid lithium salts2 -The ratio of ion and alkane alkenyl and carbonyl molal quantity sum is 1：（1~3）.
4. a kind of preparation method of the nitroso grafting carbonic ester electrolyte of lithium battery, its feature exist according to claim 1
In：The mixing molar ratio of the ethylene carbonate and propene carbonate is 1：（0.5~1）.
5. a kind of preparation method of the nitroso grafting carbonic ester electrolyte of lithium battery, its feature exist according to claim 1
In：The auxiliary agent is fluoro ethers, and the mol ratio of the auxiliary agent and organic solvent is（0.1~0.5）：1.
6. a kind of preparation method of the nitroso grafting carbonic ester electrolyte of lithium battery, its feature exist according to claim 1
In：The auxiliary agent is fluoro ethers and borate in molar ratio 1：0.3 mixing, the mol ratio of the auxiliary agent and organic solvent are
（0.1~0.5）：1.
7. electrolyte prepared by any one of claim 1-6 methods described.
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| EP0850920A2 (en) * | 1996-12-30 | 1998-07-01 | Centre National De La Recherche Scientifique (Cnrs) | Salts of perfluorinated amides and their uses as ionic conductive materials |
| US20040161671A1 (en) * | 2003-02-13 | 2004-08-19 | Medtronic, Inc. | Liquid electrolyte for an electrochemical cell |
| CN1949581A (en) * | 2005-10-13 | 2007-04-18 | 比亚迪股份有限公司 | Electrolyte, lithium ion cell containing same and preparing process thereof |
| CN104541388A (en) * | 2012-06-19 | 2015-04-22 | 纳幕尔杜邦公司 | Electrochemical cells comprising electrolyte additives, and methods for making and using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850920A2 (en) * | 1996-12-30 | 1998-07-01 | Centre National De La Recherche Scientifique (Cnrs) | Salts of perfluorinated amides and their uses as ionic conductive materials |
| US20040161671A1 (en) * | 2003-02-13 | 2004-08-19 | Medtronic, Inc. | Liquid electrolyte for an electrochemical cell |
| CN1949581A (en) * | 2005-10-13 | 2007-04-18 | 比亚迪股份有限公司 | Electrolyte, lithium ion cell containing same and preparing process thereof |
| CN104541388A (en) * | 2012-06-19 | 2015-04-22 | 纳幕尔杜邦公司 | Electrochemical cells comprising electrolyte additives, and methods for making and using the same |
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