CN109888386A - A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte - Google Patents
A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte Download PDFInfo
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- CN109888386A CN109888386A CN201910104215.0A CN201910104215A CN109888386A CN 109888386 A CN109888386 A CN 109888386A CN 201910104215 A CN201910104215 A CN 201910104215A CN 109888386 A CN109888386 A CN 109888386A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium-ion battery electrolytes and contain the lithium ion battery of the electrolyte.Lithium-ion battery electrolytes of the present invention include lithium salts, organic solvent and additive, wherein comprising sulfur-containing compound M and N as additive in additive.The additive M can participate in the formation of passivating film at positive and negative anodes interface, it promotes high-temperature behavior and inhibits battery producing gas, additive N has preferable effect to cycle performance of battery and adjusting impedance is promoted, the cycle performance and storge quality of battery system can be optimized by being used in combination for compound M and N, and makes battery system that there is lower impedance, reach the resultant effect that battery high temperature performance is taken into account.
Description
Technical field
The present invention relates to field of lithium ion battery, it is specifically related to a kind of lithium-ion battery electrolytes and contains the electrolyte
Lithium ion battery.
Background technique
High-energy density ternary lithium ion battery is the main exploitation and application of current motive force of development battery and energy storaging product
Direction.With the promotion of nickel content in ternary material LiNi1-x-y-zCoxMnyAlzO2, the gram volume of battery material gradually increases
Add, but the thermal instability of simultaneous battery material increases, transition metal ions dissolution phenomenon is obvious under high temperature, holds
Side reaction easily occurs with electrolyte, so that easy production gas, high temperature circulation decaying are obvious during high-temperature storage.
In order to improve the high-temperature behavior of nickelic ternary lithium ion battery, introducing sulfonic compound in electrolyte system is
Presently preferred a solution, such as 1,3 propane sultones can effectively inhibit battery producing gas, but study and find that this adds
Agent is added to be easy to cause the increase of battery DC internal resistance, and in the room temperature and high temperature cyclic performance of nickelic lower deterioration battery.Containing not
The functional group of saturated bond can be adsorbed on cathode and participate in the formation of passivating film, while can gather under hot environment at positive interface
It closes and forms the activity that passivating film inhibits cathode material, reduce the generation of side reaction, but study the compound of discovery unsaturated bond class
Although the high-temperature storage performance of battery can be effectively improved, often there are degradation effects to impedance and cycle performance.In view of to mentioning
The demand of high-lithium ion battery energy density is more more and more urgent, preferable in order to have nickelic ternary system under long calendar life
High-temperature storage performance while have both preferable cryogenic property and long-life energy, it is necessary to develop a kind of new electrolyte.
Summary of the invention
In order to overcome the shortcomings of above-mentioned background technique, the present invention provides a kind of lithium-ion battery electrolytes and contain the electricity
Solve the lithium ion battery of liquid.Lithium-ion battery electrolytes of the invention include sulfur-containing compound M and N as additive.Additive M
The formation of passivating film can be participated at positive and negative anodes interface, promote high-temperature behavior and inhibits battery producing gas, and additive N is to promotion battery
It cycle performance and adjusts impedance and has preferable effect, the circulation of battery system can be optimized by being used in combination for compound M and N
Performance and storge quality, and make battery system that there is lower impedance, reach the resultant effect that battery high temperature performance is taken into account.
To achieve the goals above, lithium-ion battery electrolytes of the invention include lithium salts, organic solvent and additive,
In, it include sulfur-containing compound M and N in the additive；
The compound M is chain sulfur-bearing esters structure:Wherein R1Selected from phenyl, fluorine-containing
Phenyl, 1-4 carbon fluorine-containing are free of fluoroalkyl, wherein R2Replace selected from vinyl, acetenyl, itrile group, isocyanate group, silicon
Functional group at least containing a unsaturated bond；
The compound N is cyclic sulfonic acid ester, and structure isWherein R3Alkyl, alkylene for 2-6 carbon
Base or fluorine-substituted alkylidene compound.
Preferably, the compound M be selected from one of following compound or more than one:
The compound N is selected from sulfuric acid vinyl ester (DTD), 1,3- propylene glycol Cyclic Sulfate (PCS), 4- propyl sulfuric acid Asia second
Ester (PEGLST), sulfuric acid acrylic ester (TS), 4- methylsulfuric acid vinyl acetate, 4- ethyl sulfuric acid vinyl acetate, 4- propyl sulfuric acid vinyl ester,
One of 4- fluorosulfuric acid vinyl acetate, 4- trifluoromethyl sulfuric acid vinyl ester or more than one.
It is further preferred that the additional amount of the compound M accounts for the 0.1-3% of electrolyte total weight；The compound N
Additional amount accounts for the 0.1-4% of electrolyte total weight；It is highly preferred that the additional amount ratio of the additional amount of the compound N and compound M
Value is (10-1): 1, such as (4-1): 1.
Lithium salts of the present invention is lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, three oxalic acid lithium phosphates, difluoro
Lithium bis (oxalate) borate, double fluorine sulfimide lithiums, double trifluoromethanesulfonimide lithiums, difluorophosphate, four lithium fluophosphates and difluoro are double
At least one of oxalic acid lithium phosphate, it is preferable that the content of the lithium salts is the 8-20% of electrolyte gross mass.
Further, organic solvent of the present invention is selected from cyclic carbonates solvent, linear carbonate class solvent, carboxylic acid
One of esters solvent, fluoro carbonic ester class solvent and fluorocarboxylic acid esters solvent are a variety of.
Further, the cyclic carbonates solvent is selected from one of ethylene carbonate, propene carbonate or a variety of；
The linear carbonate class solvent is selected from one of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate or a variety of；The carboxylic
Esters of gallic acid solvent is selected from ethyl acetate, ethyl propionate, ethyl butyrate, methyl propionate, propyl butyrate, propyl acetate；The fluoro
Carbonate solvent and fluorocarboxylic acid ester solvent are selected from fluorinated ethylene carbonate, 1,2- difluorinated ethylene carbonate, methyl trifluoro second
Base carbonic ester, methyl trifluoro ethyl carbonate ester (MTFEC), double trifluoroethyl carbonic esters (DTFEC), ethyl difluoro
(DFEA), one of Trifluoroacetic Acid Ethyl Ester (TFEA) or a variety of.
The present invention also provides a kind of lithium ion battery, the lithium ion battery includes anode pole piece, cathode pole piece, setting
Diaphragm and electrolyte of the present invention between anode pole piece and cathode pole piece.
Further, the anode pole piece includes the positive diaphragm on plus plate current-collecting body and plus plate current-collecting body surface, it is described just
Pole diaphragm includes positive active material, conductive agent and binder；The cathode pole piece includes negative electrode active material.
Further, the positive active material is LiNi1-x-y-zCoxMnyAlzO2, nickel ion doped, cobalt acid lithium, Fu Li
Manganese based solid solution or LiMn2O4, wherein 0≤x≤1,0≤y≤1,0≤z≤1 and 0≤x+y+z≤1；Negative electrode active material is behaved
Make graphite, cladded type natural graphite, silicon-carbon cathode or silicium cathode.
Lithium-ion battery electrolytes of the invention include sulfur-containing compound M and N as additive, and additive M will increase electricity
Pond internal resistance, and compound N has the effect of reducing internal resistance, additive M and additive N are combined use and can be played respectively adds
Add the advantage of agent, reduces counter productive.In cathode interface the shape that reduction reaction participates in SEI film can occur for one side additive M
At, inhibit contact of the electrolyte with negative electrode active material, is that the cycle performance of battery provides safeguard, another aspect additive M
The formation of cathode passivating film can be participated in, passivation cathode activity inhibits the side reaction of electrode interface and electrolyte, inhibits nickelic electricity
The high-temperature storage performance that pond produces gas, improves battery；Additive N has preferable effect to cycle performance of battery and adjusting impedance is promoted
Fruit, while having the effect further promoted to normal-temperature circulating performance, battery can be optimized by being used in combination for compound M and N
The cycle performance and storge quality of system, and make battery system that there is lower impedance, to the normal of the nickelic soft-package battery of improvement
It is effective in terms of temperature circulation, high temperature circulation and high-temperature storage and low temperature performance.
Detailed description of the invention
Fig. 1 is 1% CV curve of the compound 3 in AG/Li half-cell
Fig. 2 is that 1%DTD and 1% compound 3 and combinations thereof are compared in the EIS of AG/Li half-cell 50%SOC.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, part
It will become apparent from the description below, or practice through the invention is recognized.It is only used to solve it should be appreciated that being described below
The present invention is released, is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " containing " or its any other deformation, it is intended that covering non-exclusionism
Include.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those elements, but
It may include not expressly listed other elements or such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
In addition, term " one embodiment " disclosed below, " some embodiments ", " example ", " specific example " or
The description of " some examples " etc. means that particular features, structures, materials, or characteristics described in conjunction with this embodiment or example include
In at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms are not required
For identical embodiment or example.As long as moreover, technical characteristic involved in each embodiment of the present invention each other it
Between do not constitute conflict and can be combined with each other.
Comparative example 1
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, it stirs to it and is completely dissolved, 1,3 propane sulfonic acid lactones (PS) of electrolyte total weight 1% are then added,
Obtain the lithium-ion battery electrolytes of comparative example 1.The electrolyte is injected into NCM622/AG-4.3V battery, and encapsulated,
Shelve, be melted into, aging, secondary encapsulation, the processes such as partial volume, obtain nickelic NCM622/AG-4.3V tertiary cathode material Soft Roll lithium from
Sub- battery.
Comparative example 2
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound 1 of electrolyte total weight 1% is then added, obtains comparative example 2
Lithium-ion battery electrolytes.The electrolyte is injected into NCM622/AG-4.3V battery, and it is encapsulated, shelve, be melted into, always
The processes such as change, secondary encapsulation, partial volume obtain nickelic NCM622/AG-4.3V tertiary cathode material soft bag lithium ionic cell.
Comparative example 3
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound 3 of electrolyte total weight 1% is then added, obtains comparative example 3
Lithium-ion battery electrolytes.The electrolyte is injected into NCM622/AG-4.3V battery, and it is encapsulated, shelve, be melted into, always
The processes such as change, secondary encapsulation, partial volume obtain nickelic NCM622/AG-4.3V tertiary cathode material soft bag lithium ionic cell.
Comparative example 4
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound 7 of electrolyte total weight 1% is then added, obtains comparative example 4
Lithium-ion battery electrolytes.The electrolyte is injected into NCM622/AG-4.3V battery, and it is encapsulated, shelve, be melted into, always
The processes such as change, secondary encapsulation, partial volume obtain nickelic NCM622/AG-4.3V tertiary cathode material soft bag lithium ionic cell.
Comparative example 5
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound 9 of electrolyte total weight 1% is then added, obtains comparative example 5
Lithium-ion battery electrolytes.The electrolyte is injected into NCM622/AG-4.3V battery, and it is encapsulated, shelve, be melted into, always
The processes such as change, secondary encapsulation, partial volume obtain nickelic NCM622/AG-4.3V tertiary cathode material soft bag lithium ionic cell.
Comparative example 6
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound DTD of electrolyte total weight 1% is then added, obtains comparative example 6
Lithium-ion battery electrolytes.The electrolyte is injected into NCM622/AG-4.3V battery, and it is encapsulated, shelve, be melted into, always
The processes such as change, secondary encapsulation, partial volume obtain nickelic NCM622/AG-4.3V tertiary cathode material soft bag lithium ionic cell.
Comparative example 7
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound 4- methylsulfuric acid Asia second of electrolyte total weight 1% is then added
Ester (PCS), obtains the lithium-ion battery electrolytes of comparative example 7.The electrolyte is injected into NCM622/AG-4.3V battery, and
It is encapsulated, shelve, be melted into, aging, secondary encapsulation, the processes such as partial volume, obtain nickelic NCM622/AG-4.3V tertiary cathode material
Soft bag lithium ionic cell.
Comparative example 8
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound 4- propyl sulfuric acid Asia second of electrolyte total weight 1% is then added
Ester (PEGLST), obtains the lithium-ion battery electrolytes of comparative example 8.The electrolyte is injected into NCM622/AG-4.3V battery
In, and it is encapsulated, shelve, be melted into, aging, secondary encapsulation, the processes such as partial volume, obtain nickelic NCM622/AG-4.3V tertiary cathode
Material soft bag lithium ionic cell.
Embodiment 1
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound DTD of electrolyte total weight 1%, 0.5% chemical combination is then added
Object 1 obtains the lithium-ion battery electrolytes of embodiment 1.The electrolyte is injected into NCM622/AG-4.3V battery, and through sealing
It fills, shelve, being melted into, aging, secondary encapsulation, the processes such as partial volume, obtaining nickelic NCM622/AG-4.3V tertiary cathode material Soft Roll
Lithium ion battery.
Embodiment 2
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate are uniformly mixed with the mass ratio of 30:10:60, and mass fraction is added in mixed solution and is
12.5% LiPF6, stir to it and be completely dissolved, the compound DTD of electrolyte total weight 1%, 0.5% chemical combination is then added
Object 3 obtains the lithium-ion battery electrolytes of embodiment 2.The electrolyte is injected into NCM622/AG-4.3V battery, and through sealing
It fills, shelve, being melted into, aging, secondary encapsulation, the processes such as partial volume, obtaining nickelic NCM622/AG-4.3V tertiary cathode material Soft Roll
Lithium ion battery.
Similarly, the preparation method of the electrolyte of embodiment 3-16 is same as above.
In each comparative example and embodiment NCM622/AG-4.3V battery the production method is as follows: by positive active material
LiNi0.6Co0.2Mn0.2O2(622), conductive agent acetylene black, carbon nanotube, binder polyvinylidene fluoride (PVDF) be in mass ratio
95:2.8:0.2:2 is thoroughly mixed uniformly in the dry environment full of nitrogen in N-Methyl pyrrolidone dicyandiamide solution
Afterwards, it is coated on drying on Al foil, cold pressing, obtains anode pole piece, compacted density 3.50g/cm3。
By negative electrode active material graphite, conductive agent acetylene black, carbon nanotube, binder butadiene-styrene rubber (SBR), thickener carbon
Sodium carboxymethylcellulose pyce (CMC) is thoroughly mixed in deionized water solvent system uniformly according to mass ratio 96:1.8:0.2:1:1
Afterwards, it is coated on drying on Cu foil, cold pressing, obtains cathode pole piece, cathode compacted density is 1.60g/cm3, it is with polyethylene (PE)
Basement membrane (14 μm), and diaphragm is used as at (2 μm) of the nano oxidized aluminized coating of coating on base films.
Anode pole piece, diaphragm, cathode pole piece are folded in order, diaphragm is made to be among positive/negative plate the work for playing isolation
With, and wind and obtain naked battery core.Naked battery core is placed in outer packing, inject the electrolyte of preparation and it is encapsulated, shelve, be melted into,
The processes such as aging, secondary encapsulation, partial volume obtain the nickelic NCM622/AG-4.3V tertiary cathode material Soft Roll lithium-ion electric of model
Pond.
The formula of each comparative example and embodiment electrolyte is shown in Table shown in 3.
The electrolyte prescription of table 3 comparative example 1-8 and embodiment 1-16
Performance of lithium ion battery test
1. normal-temperature circulating performance
Under the conditions of room temperature (25 ± 2 DEG C), above-mentioned NCM622/AG lithium ion battery is charged to 4.3V in 1C constant current constant voltage；
5min is shelved, then constant-current discharge to 3.0V, shelves 5min, and so circulation carries out charge and discharge, when charge and discharge to circulation volume reach
The cycle life (all numbers) of battery is recorded after to the 80% of initial capacity.
2. high temperature cyclic performance
Under the conditions of high temperature (45 DEG C), above-mentioned NCM622/AG lithium ion battery is charged to 4.3V in 1C constant current constant voltage respectively
Full electricity；5min is shelved, then 3.0V is discharged under 1C constant current conditions, shelves 5min, so circulation carries out charge and discharge, works as charge and discharge
Electricity to circulation volume reach initial capacity 80% after record battery cycle life (all numbers).
3. high-temperature storage performance
Under the conditions of room temperature (25 ± 2 DEG C), a 1C/1C is carried out to lithium ion battery and is charged and discharged (discharge capacity note
For DC0), record original depth is denoted as D1, then respectively charges to above-mentioned NCM622/AG battery under the conditions of 1C constant current constant voltage
4.3V；The lithium ion battery of full electricity is placed in 55 DEG C of high-temperature cabinets and is saved 7 days, Thickness Measurement by Microwave is D2 immediately after taking-up, in room temperature item
1C electric discharge is carried out under part, and (discharge capacity is denoted as DC1)；Then 1C/1C charging and discharging (discharge capacity is carried out under normal temperature conditions
It is denoted as DC2), thickness change, capacity retention ratio and the capacity restoration rate of lithium ion battery are calculated by following formula:
4. -20 DEG C of discharge performances of low temperature
Under the conditions of room temperature (25 DEG C), NCM622/AG battery, which is charged to 4.3V, respectively under the conditions of 1C constant current constant voltage expires
Electricity；Then by the lithium ion battery of full electricity again with 1C electric current constant-current discharge to 2.5V, record room temperature discharge capacity is A1；Then it presses
It is according to same way that above-mentioned battery is full electric again, it is placed at -20 DEG C after ambient shelf 6H, with 1C constant-current discharge to 2.5V, note
The discharge capacity A2 of -20 DEG C of low temperature of record is calculated 1C discharging efficiency under the conditions of -20 DEG C of lithium ion battery by following formula:
Table 2: the performance test results of comparative example 1-18 and embodiment 1-16 battery
Test result can be seen that comparative example of the comparative example 2 compared to addition 1%PS of the compound M of addition 1% from table
1, there is promotion by a small margin in terms of the normal temperature circulation service life, performance boost is obvious in terms of 45 DEG C of circulations of high temperature, at 60 DEG C of high temperature
Storage aspect battery core thickness change significantly reduces, and corresponding high-temperature storage residual capacity and recovery Capacitance Shift Rate also significantly change
It is good.
It can be seen that additive of the present invention M, i.e. property in terms of the storage of 1,3,7,9 pair of compound, 60 DEG C of high temperature from comparative example 1-5
Energy improvement is more significant, and thickness change drops within 20% from 40% or more of comparative example 1, it will be apparent that inhibits battery
Gas is produced, remaining and recovery capacity has promotion by a relatively large margin.
On the one hand in addition it can contain insatiable hunger in the compound in cathode film formation containing sulfonic acid group in additive M structure
It can be rolled into a ball with hat, passivating film can be formed at positive interface under high potential and hot environment, to promote the storge quality of battery, from
CV curve of 1% compound 3 of Fig. 1 in half-cell can be seen that the type additive, and in graphite interface, there are two reduction
Peak is located near 1.0V and 1.5V, and may respectively correspond sulfonic acid group and unsaturated group goes back original position, illustrates such
Additive can form stable SEI film in cathode interface, so that the side reaction of electrolyte and electrode be inhibited to occur, follow to battery
Ring stability plays positive effect.
It can also be seen that the battery core in comparative example 2-5 in terms of low temperature discharging efficiency compared to comparative example 1 from upper table data
In PS it is low, illustrate that an additive M is only added, and be added without additive N, can bring the increase of impedance, additive M with it is low-impedance
Additive, which is used cooperatively, can bring better effect.
Further, it can be seen that the normal temperature circulation of cyclic annular sulfonic compound from the electrical performance data of comparative example 6-8
Can there be promotion by a relatively large margin compared to comparative example 1 and comparative example 2-5, it is shown that additive N has battery performance promotion bright
Aobvious effect further compares high temperature cyclic performance test result, finds high-temperature behavior of such additive compared to additive M
It is poor, the even lower than high temperature cyclic performance of 1%PS；Find that additive N can not inhibit the production gas of battery in terms of 60 DEG C of storages,
The thickness change of its battery core is higher, and with ring-type outside branch growth, high-temperature behavior has the tendency that variation, and low
Warm -20 DEG C of discharging efficiencies are all higher than comparative example 1-5, illustrate that such compound mainly acts on cathode interface, protect to nickelic anode
Shield and passivation have no help.
Additive M and additive N are applied in combination the further present invention, and to the additional amount of additive M and N
Modulation is carried out, it is high to improving to can be seen that being applied in combination for additive M and N from the electric performance test result of embodiment 1-11
It is effective in terms of normal temperature circulation, high temperature circulation and the high-temperature storage and low temperature performance of nickel soft-package battery, it is listed compared with
Also there is bright its high temperature cyclic performance after the compound 4 (0.1%) and compound 9 (0.2%) of low content are combined with sulfuric acid vinyl ester
It is aobvious to be promoted, it is kept in terms of normal temperature circulation and low temperature discharging efficiency preferable horizontal.But the additional amount of additive M is compared with Gao Ertian
When adding agent N lower, it is smaller that normal-temperature circulating performance improves amplitude, and high temperature circulation and storge quality improve more obvious, the present invention
Research thinks that the additional amount of additive N is one times or more of additive M and taking into account for the high/low temperature comprehensive performance of battery may be implemented,
Additive M may not can guarantee the high-temperature storage and cycle performance of battery when too low, high-temperature behavior is mentioned when additive N is excessively high
It rises but room temperature and low temperature performance is unable to reach optimum level.1%DTD and 1% compound 3 and combinations thereof exchange from Fig. 2
Impedance can be seen that additive M used in the present invention and increase the internal resistance of cell, and compound N has the effect of reduction internal resistance, and two
Person reduces counter productive with merging according to ratio of the present invention using the advantage that can play each additive.
Cell interface bring impedance may be increased based on additive M, in order to enhance lithium ion in the expansion of cell interface
The ability of dissipating, the present invention further joined a certain amount of fluoro carbonic ester or fluorocarboxylic acid ester compounds in electrolyte system,
Such as embodiment 11-16, it can further improve the performance of high nickel-based battery from the aspect of normal-temperature circulating performance, and corresponding high temperature stores up
It deposits aspect of performance and has no negative effect, illustrate that fluoro carbonic ester provided by the invention and alpha-fluorocarboxylate ester compare under high temperature environment
It is stable, it may the complexity of defluorinate be related at high temperature with it.
The present invention only lists combination and the changes of contents problem of emphasis additive to illustrate the content of invention, for reality
Existing nickelic system more preferably comprehensive performance, those skilled in the art in the invention can also according to the above description the announcement of book and
Introduction, changes and modifies the above embodiment, and does further according to present invention additive above-mentioned in the above system
Modification and improvement, it is not limited to a specific embodiment of the invention, all those skilled in the art are in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., should be included within the present invention.In addition, although this theory
It is used some specific terms in bright book, these terms are merely for convenience of description, does not constitute any limit to the present invention
System.
Claims (10)
1. a kind of lithium-ion battery electrolytes, which includes lithium salts, organic solvent and additive, feature
It is, includes sulfur-containing compound M and N in the additive；
The compound M is chain sulfur-bearing esters structure:Wherein R1Selected from phenyl, contain fluorobenzene
Base, 1-4 carbon fluorine-containing are free of fluoroalkyl, wherein R2Replace extremely selected from vinyl, acetenyl, itrile group, isocyanate group, silicon
Few functional group containing a unsaturated bond；
The compound N is cyclic sulfonic acid ester, and structure isWherein R3For the alkyl of 2-6 carbon, alkylidene or
Fluorine-substituted alkylidene compound.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that the compound M is selected from following chemical combination
One of object or more than one:
The compound N is selected from sulfuric acid vinyl ester (DTD), 1,3- propylene glycol Cyclic Sulfate (PCS), 4- propyl ethyl sulfate
(PEGLST), sulfuric acid acrylic ester (TS), 4- methylsulfuric acid vinyl acetate, 4- ethyl sulfuric acid vinyl acetate, 4- propyl sulfuric acid vinyl ester, 4-
One of fluorosulfuric acid vinyl acetate, 4- trifluoromethyl sulfuric acid vinyl ester or more than one.
3. lithium-ion battery electrolytes according to claim 1 or 2, which is characterized in that the additional amount of the compound M accounts for
The 0.1-3% of electrolyte total weight；The additional amount of the compound N accounts for the 0.1-4% of electrolyte total weight；Preferably, described
The additional amount of compound N and the additional amount ratio of compound M are (10-1): 1, such as (4-1): 1.
4. lithium-ion battery electrolytes according to claim 1, which is characterized in that the lithium salts is lithium hexafluoro phosphate, four
Lithium fluoroborate, di-oxalate lithium borate, three oxalic acid lithium phosphates, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide lithiums, double fluoroform sulphurs
At least one of double oxalic acid lithium phosphates of imide li, difluorophosphate, four lithium fluophosphates and difluoro.
5. lithium-ion battery electrolytes according to claim 4, which is characterized in that the content of the lithium salts is that electrolyte is total
The 8-20% of quality.
6. lithium-ion battery electrolytes according to claim 1, which is characterized in that the organic solvent is selected from cyclic carbonate
In esters solvent, linear carbonate class solvent, carboxylic acid esters solvent, fluoro carbonic ester class solvent and fluorocarboxylic acid esters solvent
It is one or more.
7. lithium-ion battery electrolytes according to claim 6, which is characterized in that the cyclic carbonates solvent is selected from
One of ethylene carbonate, propene carbonate are a variety of；The linear carbonate class solvent is selected from methyl ethyl carbonate, carbonic acid two
One of methyl esters, diethyl carbonate are a variety of；The carboxylic acid esters solvent be selected from ethyl acetate, ethyl propionate, ethyl butyrate,
Methyl propionate, propyl butyrate, propyl acetate；The fluoro carbonic ester solvent and fluorocarboxylic acid ester solvent are selected from fluoro ethylene carbonate
Ester, 1,2- difluorinated ethylene carbonate, methyl trifluoro ethyl carbonate ester, double trifluoroethyl carbonic esters, ethyl difluoro, trifluoro
One of ethyl acetate is a variety of.
8. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode pole piece, cathode pole piece, is set to just
Diaphragm and the described in any item lithium-ion battery electrolytes of claim 1-7 between pole pole piece and cathode pole piece.
9. lithium ion battery according to claim 8, which is characterized in that the anode pole piece includes plus plate current-collecting body and just
The positive diaphragm of pole collection liquid surface, the anode diaphragm includes positive active material, conductive agent and binder；The cathode pole
Piece includes negative electrode active material.
10. lithium ion battery according to claim 9, which is characterized in that the positive active material is LiNi1-x-y- zCoxMnyAlzO2, nickel ion doped, cobalt acid lithium, rich lithium manganese base solid solution or LiMn2O4, wherein 0≤x≤1,0≤y≤1,0≤z≤
1 and 0≤x+y+z≤1；The negative electrode active material is artificial graphite, cladded type natural graphite, silicon-carbon cathode or silicium cathode.
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