CN108550914A - A kind of additive of non-aqueous electrolyte for lithium ion cell and its preparation method and application - Google Patents
A kind of additive of non-aqueous electrolyte for lithium ion cell and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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Abstract
The present invention proposes a kind of additive of non-aqueous electrolyte for lithium ion cell and its preparation method and application, and the additive has the molecular structure as shown in formula (1)：Wherein, R1, R2The fluorine-based or trifluoromethyl of separate expression, n and m it is separate be 0,1 or 2, the one kind of A in having structure：
Description
Technical field
The present invention relates to a kind of additives and its preparation method and application of lithium ion nonaqueous electrolytic solution, more particularly to a kind of
Non-water electrolytic solution additive for improving charge-discharge performance and cycle-index performance under high-temperature lithium ion battery.
Background technology
Lithium ion battery because have many advantages, such as it is higher than energy, have extended cycle life, self discharge it is small, be widely used in consumer
In electronic product and energy storage and power battery.With the extensive use of lithium ion battery, cycle life becomes lithium-ion electric
A kind of important indicator in pond, in addition to this, since lithium ion battery shows unstable phenomenon after cycling, for example, through
The thermal stability for the lithium ion battery crossed after cycle can be deteriorated, safe to use in order to ensure, improve lithium ion battery cycle
While performance, it is also necessary to improve the thermal stability of lithium ion battery after cycling.
Carrier of the nonaqueous electrolytic solution as ion motion in lithium ion battery, ingredient is basicly stable, predominantly EC, PC,
Methyl ethyl carbonate, DEC etc., it is more next to meet the research of additive of different performance requirement with the continuous popularization of battery applications
It is more, wherein the additive in terms of being especially used for improving cell safety characteristic is in the majority, such as prevents the additive of over-charging of battery, prevents
The only additive etc. of battery hot tank failure, the security performance to improve lithium battery are made that huge contribution.
In recent years, it deepens continuously to the understanding of battery use condition with people, finds the use of battery in many cases
All under conditions of higher than room temperature so that battery consumer and manufacture commercial city are drawn to improving the electrical property of battery under the high temperature conditions
Attention has been played, many battery manufacturers have all carried out battery the test of high-temperature storage performance and high temperature cyclic performance etc.,
And it is improved to a certain extent.Often all start with from the basic component of electrolyte however, many electrolyte improve formula,
High-temperature behavior is improved, but still cannot meet the needs of using battery well.Therefore, set about from additive, improve battery
Cycle performance and hot properties become the important topic for improving stability test at present.
Invention content
In order to solve the present situation of current lithium battery electrical property Shortcomings under the high temperature conditions, the applicant has carried out with keen determination
Research, providing a kind of can improve the electrical property of lithium battery under high temperature and suitable for the additive of non-aqueous electrolyte for lithium cell and should
The preparation method and application of additive.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of additive of non-aqueous electrolyte for lithium ion cell has the molecular structure as shown in formula (1)：
Wherein, R1, R2The fluorine-based or trifluoromethyl of separate expression, n and m it is separate be 0,1 or 2, A is selected from down
One kind in array structure：
* connection site is indicated.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the additive is selected from one of having structure：
The advantageous effect of additive provided by the invention is：Electrolyte of the additive application of the present invention to lithium ion battery
In after, can inhibit the decline of battery initial capacity, increase initial discharge capacity and reduce the cell expansion after high temperature is placed, improve
The charge-discharge performance and cycle-index of battery.
The preparation method of above-mentioned additive is as follows：
(1) under inert atmosphere and -10~40 DEG C of temperature condition, thionyl chloride is added to having containing raw material 1
Reacted in machine solution, react 1~4 hour, obtain the reaction solution containing intermediate 1, wherein raw material 1 as shown in following formula 2,
Intermediate 1 is as shown in following formula 3；
(2) under inert atmosphere and -10~10 DEG C of temperature condition, by what is obtained in step (1) containing intermediate 1
Reaction solution is added into the aqueous solution containing catalyst and alkaline matter, after oxidising agent is added dropwise thereto, it is permanent after being added dropwise
Temperature reaction 1~4 hour obtains the reaction system containing additive, and the reaction system is post-treated to obtain additive, wherein described
One or more mixtures of the catalyst in hydrate ruthenium trichloride, hydration manganese acetate and methyl rhenium trioxide；
Its reaction route is as follows：
Further, the one kind or more of the oxidising agent in sodium hypochlorite, sodium chlorite, hydrogen peroxide and urea peroxide
The mixture of kind.
Further, the alkaline matter is in sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus and dipotassium hydrogen phosphate
One or more mixtures.
Further, the organic solvent of dissolving raw material 1 is one in dichloromethane, dichloroethanes and chlorobenzene in step (1)
Kind or a variety of mixtures.
Further, in the step (1), the molar ratio of thionyl chloride and raw material 1 is thionyl chloride：Raw material 1=(1~
1.2)：1；In the step (2), the ratio between catalyst and the mole of intermediate 1 are catalyst：Intermediate 1=(0.1 ‰~
1‰)：1；The ratio between alkaline matter and the mole of intermediate 1 are alkaline matter：Intermediate 1=(0.2~2.0)：1；Oxidising agent
It is oxidative reagent with the ratio between the mole of intermediate 1：Intermediate 1=(1.0~1.3)：1.
The advantageous effect of above-mentioned preparation method is：Raw material is cheap and easy to get, reaction condition is mild, easy to operate safe and environment-friendly
Efficiently.
A kind of non-aqueous electrolyte for lithium ion cell is also claimed in the present invention, which is characterized in that comprising at least one aforementioned
Non-aqueous electrolyte for lithium ion cell additive.
Further, the non-aqueous electrolyte for lithium ion cell includes lithium salts, organic solvent and additive, wherein described to add
It is the 0.05~2% of non-aqueous electrolyte for lithium ion cell total weight to add the dosage of agent.
Further, the lithium salts is lithium hexafluoro phosphate；The solvent is selected from ethylene carbonate, propylene carbonate, carbon
Sour butylene, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, carbonic acid dipropyl
Ester, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and fourth
One or more mixtures in acetoacetic ester.
The advantageous effect of non-aqueous electrolyte for lithium ion cell provided by the invention is：The electrolyte system can effectively improve
The high temperature storage and cycle performance of battery, not only effectively ensure that the high-temperature behavior of battery, but also the low temperature properties of battery have been effectively ensured
Can, so that the movement of lithium ion is become smooth, therefore also reduce the increase of membrane impedance in cyclic process, meets consumer well
Demand to battery performance.
Specific implementation mode
The application is further described below by way of specific example.But these examples are only exemplary, not to this
The protection domain of application constitutes any restrictions.
In following embodiments, comparative example, reagent, material and the instrument such as not special explanation used,
It is commercially available for conventional reagent, conventional material and conventional instrument, wherein involved reagent also can be by being conventionally synthesized
Method synthesis obtains.
One, the synthetic example of additive
Embodiment 1：The synthesis of compound L T01：
Weigh 2,3- dihydroxy sulfolane 76.0g (0.5mol), dichloroethanes 250mL is added in 1L there-necked flasks.Logical nitrogen
It protects, 71.5g (0.6mol) thionyl chloride is slowly added dropwise to reaction system at 20~25 DEG C, about 1.0hr drops finish.25~30 DEG C of guarantors
Warm 2.5hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three trichloride hydrates of 0.1035g (0.0005mol)
Ruthenium, 150g mass fractions be 8% sodium bicarbonate (0.12mol) aqueous solution mixed liquor in.It is added dropwise under the conditions of 0~5 DEG C
323.3g sodium hypochlorite (0.50mol) aqueous solution.About 3.0hrs drops finish, 0~5 DEG C of heat preservation 1.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 42.8g white solid powders, yield 40.0%.MS analyzes the compound, molecular formula
C4H6O6S2, theoretical value：213.961, detected value：213.960.Elemental analysis (C4H6O6S2), theoretical value C：22.44%, H：
2.81%, O：29.95%.Detected value C：22.33%, H：2.85%, O：29.93%.
Embodiment 2：The synthesis of compound L T02
Weigh 3,4- dihydroxy sulfolane 76.0g (0.5mol), dichloromethane 250mL is added in 1L there-necked flasks.It is passed through nitrogen
Gas shielded, 15~20 DEG C are slowly added dropwise 64.5g (0.525mol) thionyl chloride to reaction system, and about 1.0hr drops finish.20~25 DEG C
Keep the temperature 2.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three trichloride hydrates of 0.1035g (0.0005mol)
Ruthenium, 150g mass fractions be 9.3% potassium carbonate (0.10mol) aqueous solution mixed liquor in.388g is added dropwise under the conditions of 0~5 DEG C
Sodium hypochlorite (0.6mol) aqueous solution.About 3.0hrs drops finish, 0~5 DEG C of heat preservation 0.5hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 53.6g white solid powders, yield 50.0%.MS analyzes the compound, molecular formula
C4H6O6S2, theoretical value：213.961, detected value：213.958.Elemental analysis (C4H6O6S2), theoretical value C：22.44%, H：
2.81%, O：29.95%, C：22.41%, H：2.80%, O：29.96%.
Embodiment 3：The synthesis of compound L T03
3-F-4 is weighed, 1L is added in 5- dihydroxy -2- trifluoromethyl sulfolane 119.0g (0.5mol), dichloromethane 250mL
In there-necked flask.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 64.5g (0.525mol) thionyl chloride to reaction system, about
1.0hr drops finish.20~25 DEG C of heat preservation 2.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to and is hydrated manganese acetate containing 0.029g (0.00006mol) four,
In the mixed liquor of sodium carbonate (0.21mol) aqueous solution that 150g mass fractions are 15.0%.It is bis- that 200g is added dropwise under the conditions of 0~5 DEG C
Oxygen water (0.6mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 4.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains white solid powder 67.5g, yield 45.0%.MS analyzes the compound, molecular formula
C5H4F4O6S2, theoretical value：299.939, detected value：299.936.Elemental analysis (C5H4F4O6S2) theoretical value C:20.00%, H:
1.34%, O:31.98%, detected value C:20.02%, H:1.34%, O:31.95%.
Embodiment 4：The synthesis of compound L T04
3-F-4 is weighed, 1L is added in 5- dihydroxy -2- trifluoromethyl sulfolane 119.0g (0.5mol), dichloroethanes 250mL
In there-necked flask.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 71.5g (0.6mol) thionyl chloride, about 1.0hr to reaction system
Drop finishes.20~25 DEG C of heat preservation 1.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three trichloride hydrates of 0.012g (0.00006mol)
Ruthenium, 150g mass fractions be 8% sodium bicarbonate (0.12mol) aqueous solution mixed liquor in.It is added dropwise under the conditions of 0~5 DEG C
323.3g sodium hypochlorite (0.5mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 1.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains white solid powder 58.6g, yield 39.0%.MS analyzes the compound, molecular formula
C5H4F4O6S2, detected value 299.939, theoretical value 299.940.Elemental analysis (C5H4F4O6S2) theoretical value C:20.00%, H:
1.34%, O:31.98%.Detected value C:20.06%, H:1.32%, O:31.92%.
Embodiment 5：The synthesis of compound L T05
Weigh 2,3-, bis- fluoro- 4,5- dihydroxy trifluoromethyl sulfolane 94.0g (0.5mol), 1L tri- is added in chlorobenzene 250mL
In mouth bottle.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 59.6g (0.5mol) thionyl chloride, about 1.0hr drops to reaction system
Finish.20~25 DEG C of heat preservation 2.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three trichloride hydrates of 0.012g (0.00006mol)
Ruthenium, 150g mass fractions be 9.3% potassium carbonate (0.10mol) aqueous solution mixed liquor in.It is added dropwise under the conditions of 0~5 DEG C
420.3g sodium hypochlorite (0.65mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 3.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 43.8g white solid powders, yield 35.0%.MS analyzes the compound, molecular formula
C5H4F2O6S2, theoretical value 249.942, detected value 249.940.Elemental analysis (C5H4F2O6S2) theoretical value C：19.20%, H：
1.61%, O：38.37%.Detected value C：19.20%, H：1.60%, O：38.36%.
Embodiment 6：The synthesis of compound L T06
Weigh 2,3 dihydroxy -4,5-, bis- (trifluoromethyl) sulfolane 144.0g (0.5mol), dichloromethane 250mL is added
In 1L there-necked flasks.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 71.5g (0.6mol) thionyl chloride to reaction system, about
1.0hr drops finish.20~25 DEG C of heat preservation 2.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three trichloride hydrates of 0.1035g (0.0005mol)
Ruthenium, 400g mass fractions be 25% saleratus (1mol) aqueous solution mixed liquor in.200g mistakes are added dropwise under the conditions of -5~0 DEG C
Aoxidize urea (0.6mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 1.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 85.8g white solid powders, yield 49.0%.MS analyzes the compound, molecular formula
C6H4F6O6S2, theoretical value 349.935, detected value 349.936.Elemental analysis (C6H4F6O6S2) theoretical value C：20.58%, H：
1.15%, O：27.41%.Detected value C：20.55%, H：1.12%, O：27.45%.
Embodiment 7：The synthesis of compound L T07
2-F-3 is weighed, 4- dihydroxy -5- (trifluoromethyl) sulfolane 119.0g (0.5mol), dichloroethanes 250mL are added
In 1L there-necked flasks.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 71.5g (0.6mol) thionyl chloride to reaction system, about
1.0hr drops finish.20~25 DEG C of heat preservation 3.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three trichloride hydrates of 0.1035g (0.0005mol)
Ruthenium, 150g mass fractions be 15.0% sodium carbonate (0.21mol) aqueous solution mixed liquor in.388g is added dropwise under the conditions of 0~5 DEG C
Sodium hypochlorite (0.6mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 2.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 62.5g white solid powders, yield 41.6%.MS analyzes the compound, molecular formula
C5H4F4O6S2, detected value 299.939, theoretical value 299.938.Elemental analysis (C5H4F4O6S2) theoretical value C：20.00%, H：
1.34%, O：31.98%.Detected value C：20.10%, H：1.33%, O：31.95%.
Embodiment 8：The synthesis of compound L T08
Weigh 2,5-, bis- fluoro- 3,4- dihydroxy sulfolane 94.0g (0.5mol), 1L there-necked flasks are added in dichloromethane 250mL
In.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 71.5g (0.6mol) thionyl chloride to reaction system, and about 1.0hr drops finish.
20~25 DEG C of heat preservation 2.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing three hydrate ruthenium trichlorides of 0.012g (0.0006mol),
In the mixed liquor of potassium carbonate (0.11mol) aqueous solution that 150g mass fractions are 10%.200g dioxygens are added dropwise under the conditions of 0~5 DEG C
Water (0.6mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 1.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 45g white solid powders, yield 36.3%.MS analyzes the compound, molecular formula
C4H4F2O6S2, detected value 249.940, theoretical value 249.942.Elemental analysis (C4H4F2O6S2) theoretical value C：19.20%, H：
1.61%, O：38.37%.Detected value C：19.23%, H：1.64%, O：38.35%.
Embodiment 9：The synthesis of compound L T09
Weigh (trifluoromethyl) the sulfolane 144.0g of 3,4- dihydroxy -2,5- bis- (0.5mol), dichloroethanes 250mL is added
In 1L there-necked flasks.It is passed through nitrogen protection, 15~20 DEG C are slowly added dropwise 71.5g (0.6mol) thionyl chloride to reaction system, about
1.0hr drops finish.20~25 DEG C of heat preservation 4.0hrs.
Under the conditions of 25~30 DEG C, above-mentioned reaction solution is added dropwise to containing 0.125g (0.0005mol) methyl rhenium trioxide,
In the mixed liquor of dipotassium hydrogen phosphate (0.17mol) aqueous solution that 180g mass fractions are 21%.388g is added dropwise under the conditions of 0~5 DEG C
Sodium hypochlorite (0.6mol) aqueous solution.About 3.0hrs drops finish, 0~10 DEG C of heat preservation 1.0hr.
Saturation aqueous solution of sodium bisulfite is added dropwise into reaction system, reaction is quenched.Liquid separation, organic phase use anhydrous slufuric acid
Sodium is dried.Column is crossed, desolventizing is depressurized, obtains 61.3g white solid powders, yield 35.2%.MS analyzes the compound, molecular formula
C6H4F6O6S2, theoretical value 349.935, detected value 349.933.Elemental analysis (C6H4F6O6S2) theoretical value C：20.58%, H：
1.15%, O：27.41%.Detected value C：20.56%, H：1.16%, O：27.45%.
The method prepare compound 1~9 of in accordance with the above-mentioned embodiment 1~embodiment 9, chemical combination is detected using elemental analysis
Object, detects elemental analysis detected value that each compound obtains and theoretical value is as shown in Table 1 below.
The elemental analysis detected value and theoretical value of 1 compound 1~9 of table
According to the method prepare compound 1~9 of 1~embodiment of embodiment 9, carry out detection compound using MS, then detection is each
The detected value and theoretical value that a compound obtains are as shown in Table 2 below.
The MS detected values and theoretical value of 2 compound 1~9 of table
Two, the preparation embodiment of lithium ion battery
Substance involved in following embodiment is described below：
Organic solvent：Ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), fluoroethylene carbonate
(FEC)。
Lithium salts：LiPF6。
Additive：
Lithium battery diaphragm：Polyethylene porous thin polymer film.Zhong Ke Science and Technology Ltd.s produce, and film thickness range 15~
20 μm, porosity 30%~50%, air penetrability≤7s/20ml, tensile strength (Mpa)：Longitudinal >=90, laterally≤30.
For battery performance, make following comparative example and embodiment experiment, comparative analysis non-water electrolytic solution additive is to battery
The influence of high temperature storage and cycle performance：
Embodiment 1：The preparation of battery 1
(1) prepared by positive plate
By cobalt acid lithium (LiCoO2), binder (Kynoar), conductive agent (acetylene black) according to weight ratio be LiCoO2∶
Kynoar: N-Methyl pyrrolidone (NMP) is added in acetylene black=96: mixed at 2: 2, under de-airing mixer effect
Stirring, at transparent and homogeneous shape, obtains anode sizing agent to system；Anode sizing agent is evenly applied on the aluminium foil that thickness is 12 μm；It will
Aluminium foil is transferred to 120 DEG C of oven drying 1.0hr after room temperature is dried, and then obtains positive plate by cold pressing, cutting.
(2) prepared by negative plate
By graphite, acetylene black, thickener sodium carboxymethylcellulose (CMC), binder butadiene-styrene rubber according to weight ratio be stone
Ink: acetylene black: binder butadiene-styrene rubber: thickener sodium carboxymethylcellulose (CMC)=95: 2: 2: 1 is mixed, and is added to
After ionized water, negative electrode slurry is obtained under the stirring action of de-airing mixer stirring；Negative electrode slurry is coated uniformly on copper foil；
Copper foil is transferred to 120 DEG C of oven drying 1.0hr after room temperature is dried, then obtains negative plate by cold pressing, cutting.
(3) prepared by electrolyte
In the nitrogen atmosphere glove box of water content ＜ 1ppm, by EC, DEC, PC and FEC be uniformly mixed formed it is organic molten
Fully dry lithium salts is dissolved in above-mentioned organic solvent, is then added in organic solvent provided by the invention novel by agent
Lithium-ion battery electrolytes additive LT01 is completely dissolved as additive, is uniformly mixed, and electrolyte is obtained.Wherein, hexafluoro phosphorus
The weight ratio of a concentration of 1mol/L of sour lithium, EC, DEC, PC, FEC are EC: DEC: PC: FEC=30: 50: 15: 5, and the present invention carries
The content of the Novel lithium-ion battery electrolyte additive LT01 of confession is the total weight 1% of electrolyte.
(4) preparation of lithium ion battery
Positive plate, lithium battery isolation membrane, negative plate are folded in order, make lithium battery isolation membrane be in positive and negative plate it
Between play the role of isolation, then winding obtain naked battery core；Naked battery core is placed in outer packing foil, by the above-mentioned electrolysis prepared
Liquid is injected into the battery after drying, and by processes such as Vacuum Package, standing, chemical conversion, shapings, it is (following to obtain lithium ion battery 1
Abbreviation battery 1).
Embodiment 2：The preparation of battery 2
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT02 is additive, obtains battery 2.
Embodiment 3：The preparation of battery 3
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT03 is additive, obtains battery 3.
Embodiment 4：The preparation of battery 4
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT04 is additive, obtains battery 4.
Embodiment 5：The preparation of battery 5
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT05 is additive, obtains battery 5.
Embodiment 6：The preparation of battery 6
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT06 is additive, obtains battery 6.
Embodiment 7：The preparation of battery 7
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT07 is additive, obtains battery 7.
Embodiment 8：The preparation of battery 8
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT08 is additive, obtains battery 8.
Embodiment 9：The preparation of battery 9
The preparation of the present embodiment and battery 1 the difference is that：Chemical combination provided by the present invention is used when preparing electrolyte
Object LT09 is additive, obtains battery 9.
Embodiment 10：The preparation of battery 10
The preparation of the present embodiment and battery 1 the difference is that：The content of additive is 2% in the electrolyte of preparation, is obtained
Obtain battery 10.
Embodiment 11：The preparation of battery 11
The preparation of the present embodiment and battery 2 the difference is that：The content of additive is 0.05% in the electrolyte of preparation,
Obtain battery 11.
Embodiment 12：The preparation of battery 12
The preparation of the present embodiment and battery 4 the difference is that：The content of additive is 0.1% in the electrolyte of preparation,
Obtain battery 12.
Embodiment 13：The preparation of battery 13
The preparation of the present embodiment and battery 5 the difference is that：The content of additive is 0.1% in the electrolyte of preparation,
Obtain battery 13.
Embodiment 14：The preparation of battery 14
The preparation of the present embodiment and battery 6 the difference is that：The content of additive is 0.1% in the electrolyte of preparation,
Obtain battery 14.
Comparative example 1：The preparation of battery 1#
The preparation of this comparative example and battery 1 the difference is that：It uses T3P for additive in the electrolyte of preparation, obtains
Battery 1#.
Comparative example 2：The preparation of battery 2#
The preparation of this comparative example and battery 1 the difference is that：It uses HMPN for additive in the electrolyte of preparation, obtains
Battery 2#.
Comparative example 3：The preparation of battery 3#
The preparation of this comparative example and battery 1# the difference is that：The content of additive is 0.5% in electrolyte.
Comparative example 4：The preparation of battery 4#
The preparation of this comparative example and battery 2# the difference is that：The content of additive is 0.5% in electrolyte.
Comparative example 5：The preparation of battery 5#
The preparation of this comparative example and battery 1# the difference is that：The content of additive is 2% in electrolyte.Comparative example 6：The preparation of battery 6#
The preparation of this comparative example and battery 2# the difference is that：The content of additive is 2% in electrolyte.Comparative example 7：The preparation of battery 7#
The preparation of this comparative example and battery 2# the difference is that：It is additive-free in electrolyte.
The lithium ion battery of 1~7 gained of embodiment 1~14 and comparative example following test has been subjected to：
Test one, the cycle performance test of battery
The battery being prepared respectively is subjected to following tests：
At 25 DEG C, by battery with 1C constant-current charges to 4.35V, then constant-voltage charge to electric current is 0.05C, then permanent with 1C
Stream is discharged to 3.0V, at this time to recycle for the first time, carried out respectively according to above-mentioned cycling condition 50 times, 100 times, 200 times, 300 times,
500 cycle charging/electric discharges, calculate separately and obtain circulating battery 50 times, 100 times, 200 times, 300 times, 500 times cycle after appearance
Measure conservation rate, wherein the capacity retention ratio after cycle is calculated according to the following formula.Obtained dependence test number in each battery
According to referring to table 1.
Capacity retention ratio after cycle=(discharge capacity after corresponding cycle-index/discharge capacity recycled for the first time) ×
100%
The capacity retention ratio of 1 battery 1~14 of table and battery 1#~7# after different number of cycles
From the related data in above-mentioned table 1 it is known that battery 1#~battery 7#, battery 1~14 pass through respectively compared to
After 50 times, 100 times, 200 times, 300 times, 500 times recycle, higher capacity retention ratio is all had.
It is possible thereby to learn, by it is provided by the present application include sulfolane ethyl sulfate class compound electrolyte, answer
After using in lithium ion battery, the cycle performance of battery can be significantly improved.
Thermostability test after test two, circulating battery
Battery under the conditions of above-mentioned test one after 500 cycles is subjected to following tests：
With 0.5C electric current constant-current charges to 4.35V at 25 DEG C, then with 4.35V constant-voltage charges to electric current it is 0.025C, makes
It is in 4.35V fully charged states, and then battery is placed in 85 DEG C of high temperature furnace and is stored 15 days, while testing battery in high temperature furnace
The volume change of battery after middle voltage drop and test, results are shown in Table 2.
Voltage drop change rate (%)=(voltage-before high-temperature lithium ion battery storage after high-temperature lithium ion battery storage
High-temperature lithium ion battery storage after voltage)/high-temperature lithium ion battery storage before voltage × 100%.
Volume change (%)=(volume-lithium after high-temperature lithium ion battery storage after high-temperature lithium ion battery storage
Volume before ion battery high temperature storage)/high-temperature lithium ion battery storage before volume × 100%.
Voltage drop and the volume change of table 2 battery 1~14 and battery 1#~7#
From the correlated results in above-mentioned table 2 it is known that compared to comparative example battery 1#~7# carry out after 500 cycles by
Thermostability is tested presented state and is compared, and battery 1~14 is tested after carrying out 500 cycles using the thermostabilization under high temperature
Afterwards, cell voltage drop change rate is only 4~5%, and comparative example 1~7# of battery, voltage drop change rate reach 18~20%, especially
It is that battery 7# voltage drop change rates reach 25%.In addition, equally existing larger difference, comparative example battery for volume change
1#~7# volume expansions, which become larger, reaches 40~60%, not additivated battery 7# even occur it is on fire, and it is provided by the invention
Sulfolane ethyl sulfate class compound is applied in the electrolyte of lithium battery, and gained lithium ion battery is through multiple charge and discharge cycles
Afterwards, high-temperature storage volume change is only 4~6%, is much smaller than comparative example data.It is possible thereby to learn, ring provided by the present application
After fourth sulfone ethyl sulfate class compound is applied in lithium ion battery, the lithium after multiple charge and discharge cycles can be greatly improved
The thermal stability of ion battery.
The announcement of book according to the above description, the application those skilled in the art can also carry out the above embodiment
Change and modification appropriate.Therefore, the application is not limited to specific implementation mode disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection domain of claims hereof.
Claims (10)
1. a kind of additive of non-aqueous electrolyte for lithium ion cell, which is characterized in that have the molecular structure as shown in formula (1)：
Wherein, R1, R2The fluorine-based or trifluoromethyl of separate expression, n and m it is separate be 0,1 or 2, A be selected from following knot
One kind in structure：
* connection site is indicated.
2. additive according to claim 1, which is characterized in that have the molecular structure as shown in LT01~LT09：
3. a kind of preparation method of additive as claimed in claim 1 or 2, which is characterized in that including following reaction step：
(1) under inert atmosphere and -10~40 DEG C of temperature condition, thionyl chloride is added to containing the organic molten of raw material 1
It is reacted, is reacted 1~4 hour in liquid, obtain the reaction solution containing intermediate 1, wherein raw material 1 is intermediate as shown in following formula 2
Body 1 is as shown in following formula 3；
It (2), will the middle reaction containing intermediate 1 obtained of step (1) under inert atmosphere and -10~10 DEG C of temperature condition
Liquid is added into the aqueous solution containing catalyst and alkaline matter, after oxidising agent is added dropwise thereto, after being added dropwise, constant temperature is anti-
It answers 1~4 hour, obtains the reaction system containing additive, the reaction system is post-treated to obtain additive, wherein the catalysis
One or more mixtures of the agent in hydrate ruthenium trichloride, hydration manganese acetate and methyl rhenium trioxide, reaction route is such as
Under：
4. the preparation method of additive according to claim 3, which is characterized in that the oxidising agent is selected from hypochlorous acid
One or more mixtures in sodium, sodium chlorite, hydrogen peroxide and urea peroxide.
5. the preparation method of additive according to claim 3, which is characterized in that the alkaline matter is sodium carbonate, carbon
One or more mixtures in sour potassium, sodium bicarbonate, saleratus and dipotassium hydrogen phosphate.
6. the preparation method of the additive according to any one of claim 3~5, which is characterized in that the step (1)
In, the molar ratio of thionyl chloride and raw material 1 is thionyl chloride：Raw material 1=(1~1.2)：1.
7. the preparation method of the additive according to any one of claim 3~5, which is characterized in that the step (2)
In, the ratio between catalyst and the mole of intermediate 1 are catalyst：Intermediate 1=(0.1 ‰~1 ‰)：1；Alkaline matter and centre
The ratio between mole of body 1 is alkaline matter：Intermediate 1=(0.2~2.0)：1；The ratio between the mole of oxidising agent and intermediate 1
For oxidising agent：Intermediate 1=(1.0~1.3)：1.
8. a kind of non-aqueous electrolyte for lithium ion cell, which is characterized in that described at least one any one of claims 1 to 3
Non-aqueous electrolyte for lithium ion cell additive.
9. non-aqueous electrolyte for lithium ion cell according to claim 8, which is characterized in that including lithium salts, organic solvent and
Additive, wherein the dosage of the additive is the 0.05~2% of non-aqueous electrolyte for lithium ion cell total weight.
10. non-aqueous electrolyte for lithium ion cell according to claim 9, which is characterized in that the lithium salts is hexafluorophosphoric acid
Lithium；The organic solvent is selected from ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, carbonic acid diformazan
Ester, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, in 1,4- fourths
One or more mixtures in ester, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate or ethyl butyrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740160A (en) * | 2018-09-21 | 2020-10-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| CN112467219A (en) * | 2020-12-03 | 2021-03-09 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
-
2018
- 2018-05-31 CN CN201810550680.2A patent/CN108550914A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740160A (en) * | 2018-09-21 | 2020-10-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| US11888120B2 (en) | 2018-09-21 | 2024-01-30 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device comprising the same |
| US11901513B2 (en) | 2018-09-21 | 2024-02-13 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device comprising the same |
| CN112467219A (en) * | 2020-12-03 | 2021-03-09 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
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