CN108767316A - A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery - Google Patents

A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery Download PDF

Info

Publication number
CN108767316A
CN108767316A CN201810470161.5A CN201810470161A CN108767316A CN 108767316 A CN108767316 A CN 108767316A CN 201810470161 A CN201810470161 A CN 201810470161A CN 108767316 A CN108767316 A CN 108767316A
Authority
CN
China
Prior art keywords
lithium
ion battery
electrolyte
material system
ternary material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810470161.5A
Other languages
Chinese (zh)
Inventor
朱学全
潘立宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Shanshan Battery Materials Co Ltd
Original Assignee
Dongguan Shanshan Battery Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Shanshan Battery Materials Co Ltd filed Critical Dongguan Shanshan Battery Materials Co Ltd
Priority to CN201810470161.5A priority Critical patent/CN108767316A/en
Publication of CN108767316A publication Critical patent/CN108767316A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to technical field of lithium ion, more particularly to a kind of ternary material system lithium-ion battery electrolytes and lithium ion battery, electrolyte includes Non-aqueous Organic Solvents, lithium salts and additive, and the additive includes boracic lithium salts, difluorophosphate and the compound with structural formula I.Compared with the prior art, the present invention uses boracic lithium salts, difluorophosphate and compound triple combination with structural formula I, the analog of the double oxalic acid lithium phosphates of difluoro is formed in situ in battery, the combination of above-mentioned three classes additive can not only achieve the purpose that substitute the double oxalic acid lithium phosphate additives of difluoro, and the impedance more low and high temperature of the electrolyte containing the above three classes additive is stored with cycle performance more preferably, can be widely used for nickelic positive electrode and silicon-carbon battery system.

Description

A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of ternary material system lithium-ion battery electrolytes And lithium ion battery.
Background technology
Lithium ion battery is due to the features such as operating voltage is high, energy density is high, have extended cycle life, environmentally friendly, extensively Applied to fields such as 3C digital products, electric vehicles.Lithium ion battery will be in the coming years in applying for new-energy automobile The trend that high-volume formula increases.
Currently, there are two main classes for the lithium ion battery in new-energy automobile field, one kind is that positive electrode is LiFePO4, One kind is that positive electrode is ternary material.Wherein, the nickelic battery system of ternary is the hot spot studied at present.To further increase energy Metric density, nickelic collocation silicon-carbon system are the inevitable choices of power battery development, but with the raising of nickel content, the cycle of battery Performance declines, and especially after silicon-carbon system of arranging in pairs or groups, high temperature performance, cycle life are difficult to take into account.Traditional silicon-carbon electrolyte System is used as film for additive usually using a large amount of fluorinated ethylene carbonate (FEC), but actually uses and find with the height of FEC bases Nisiloy carbon battery system be easy to happen the behavior of aerogenesis, high temperature circulation and storge quality it is difficult to ensure that.Therefore, high nisiloy is improved The high temperature circulation and storage performance of carbon battery system need to reduce the additive amount of FEC or substitute FEC using other additive.
Invention content
It is an object of the present invention to：In view of the deficiencies of the prior art, a kind of ternary material system lithium ion is provided Battery electrolyte, the storage of impedance low and high temperature and cycle performance are good, can be widely used for nickelic positive electrode and silicon-carbon battery system.
To achieve the goals above, the present invention uses following technical scheme：
A kind of ternary material system lithium-ion battery electrolytes, including Non-aqueous Organic Solvents, lithium salts and additive, it is described Additive includes boracic lithium salts, difluorophosphate and the compound with structural formula I
Preferably, the M in the compound with structural formula I1And M2Respectively in fluorine atom, methyl, trifluoromethyl It is a kind of.The compound with structural formula I includes but not limited to specifically difluoro sulfimide lithium and double fluoroform sulphonyl At least one of imine lithium.
Preferably, the addition of the compound with structural formula I accounts for the 0.1~10% of electrolyte total weight；It is described The addition of boracic lithium salts is the 0.1~5% of electrolyte total weight；The addition of the difluorophosphate is electrolyte total weight 0.1~3%.
Preferably, the additive further includes gamma-butyrolacton, vinylene carbonate, fluorinated ethylene carbonate, sulfuric acid Asia second At least one of enester and 1,3- propane sulfonic acid lactones.
Preferably, the boracic lithium salts include in di-oxalate lithium borate, LiBF4 and difluorine oxalic acid boracic acid lithium extremely Few one kind.
Preferably, the Non-aqueous Organic Solvents are dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate At least two in ester, ethylene carbonate, propyl propionate and ethyl propionate.At least two non-aqueous organic solvent is with arbitrary proportion It is mixed.
Preferably, the content of the Non-aqueous Organic Solvents accounts for the 65%~85% of electrolyte gross mass.
Preferably, the lithium salts is lithium hexafluoro phosphate, and the content of the lithium salts accounts for the 10%~18% of electrolyte gross mass.
It is another object of the present invention to provide a kind of ternary material system lithium ion battery, including it is anode pole piece, negative Pole pole piece, diaphragm and electrolyte, the anode pole piece include plus plate current-collecting body and the positive diaphragm on plus plate current-collecting body surface, institute It includes positive active material, conductive agent and binder to state positive diaphragm, and the electrolyte is previously described electrolyte, it is described just Pole active material is LiNi1-x-y-zCoxMnyAlzO2, wherein：0≤x≤1,0≤y≤1,0≤z≤1 and 0≤x+y+z≤1, it is described The operating voltage of lithium ion battery is greater than or equal to 4.2V.In the positive active material ratio of nickel cobalt manganese be preferably 424, 333,523,701,811 and 515 or the positive active material be nickel cobalt aluminium NCA.
The beneficial effects of the present invention are：The present invention is by boracic lithium salts, difluorophosphate and compound with structural formula I Triple combination uses, and the analog of the double oxalic acid lithium phosphates of difluoro is formed in situ in battery, compared to containing the double oxalic acid phosphoric acid of difluoro The electrolyte of lithium, the combination of above-mentioned three classes additive can not only achieve the purpose that substitute the double oxalic acid lithium phosphates of difluoro, but also be somebody's turn to do The impedance of electrolyte more low and high temperature is stored with cycle performance more preferably, can be widely used for nickelic positive electrode and silicon-carbon battery system.
Description of the drawings
Fig. 1 is that di-oxalate lithium borate forms the cyclic voltammetry curve of SEI films on graphite cathode surface.
Fig. 2 is that the double oxalic acid lithium phosphates of difluoro form the cyclic voltammetry curve of SEI films on graphite cathode surface.
Fig. 3 is that difluorophosphate forms the cyclic voltammetry curve of SEI films on graphite cathode surface.
Fig. 4 is that double fluorine sulfimide lithiums form the cyclic voltammetry curve of SEI films on graphite cathode surface.
Fig. 5 is the cyclic voltammetry curve that double fluorine sulfimide lithiums form SEI films with di-oxalate lithium borate in graphite surface.
Fig. 6 is the cyclic voltammetry curve that di-oxalate lithium borate forms SEI films with difluorophosphate in graphite surface.
Fig. 7 is the cyclic voltammetry curve of di-oxalate lithium borate, difluorophosphate and double fluorine sulfimide lithiums formation SEI films.
Specific implementation mode
With reference to embodiment and Figure of description, the present invention is described in further detail, but the present invention Embodiment be not limited to this.
Comparative example 1
The preparation of electrolyte：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and 1% di-oxalate lithium borate additive is further added, obtain the lithium ion battery battery of comparative example 1 Solve liquid.
The making of half-cell：
It is artificial graphite that lithium-ion battery electrolytes made from comparative example 1, which are added dropwise to anode, and cathode is lithium piece, and diaphragm is In the button cell of the polyethylene of 16um, the button half-cell of comparative example 1 is obtained for its test.
The making of full battery：
It is nickle cobalt lithium manganate (nickel cobalt manganese ratio by lithium-ion battery electrolytes injection positive electrode active material made from comparative example 1 It is 6:2:2, compacted density 3.45g/cm3), negative electrode active material is that (silicon carbon material is the mixing of oxidation sub- silicon and graphite to silicon-carbon Object, cathode gram volume are 420mah/g), the Soft Roll lithium ion for 504848 models that diaphragm is formed using polyethylene as matrix (16um) The processes such as in battery, battery after fluid injection is encapsulated, shelve, be melted into, aging, secondary encapsulation, partial volume, obtain ternary to be tested Silicon-carbon lithium ion battery.
Comparative example 2
The preparation of electrolyte unlike comparative example 1：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and the 1% double oxalic acid lithium phosphate additives of difluoro is further added, obtain the lithium-ion electric of comparative example 2 Pond electrolyte.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 3
The preparation of electrolyte unlike comparative example 1：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and 1% difluorophosphate additive is further added, obtain the lithium ion battery electrolysis of comparative example 3 Liquid.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 4
The preparation of electrolyte unlike comparative example 1：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and 1% double fluorine sulfimide lithium additives is further added, obtain the lithium ion battery of comparative example 4 Electrolyte.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 5
The preparation of electrolyte unlike comparative example 1：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and 1% double fluorine sulfimide lithium additives and the addition of 1% di-oxalate lithium borate is further added Agent obtains the lithium-ion battery electrolytes of comparative example 5.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 6
The preparation of electrolyte unlike comparative example 1：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and 1% difluorophosphate and 1% di-oxalate lithium borate additive is further added, compared The lithium-ion battery electrolytes of example 6.
Embodiment 1
The preparation of electrolyte：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, methyl ethyl carbonate, Diethyl carbonate is with 1:1:1 mass ratio is uniformly mixed, and the LiPF that mass fraction is 12.5% is added in mixed solution6, stirring It is completely dissolved to it, and 1% difluorophosphate and 0.5% di-oxalate lithium borate and 1% double fluorine sulphonyl is further added Imine lithium additive obtains the lithium-ion battery electrolytes of embodiment 1.
The making of half-cell：
It is artificial graphite that lithium-ion battery electrolytes made from embodiment 1, which are added dropwise to anode, and cathode is lithium piece, and diaphragm is In the button cell of the polyethylene of 16um, the button half-cell of embodiment 1 is obtained for its test.
The making of full battery：
Lithium-ion battery electrolytes injection positive electrode active material prepared by embodiment 1 is nickle cobalt lithium manganate (nickel cobalt manganese ratio It is 6:2:2, compacted density 3.45g/cm3), negative electrode active material is that (silicon carbon material is the mixing of oxidation sub- silicon and graphite to silicon-carbon Object, cathode gram volume are 420mah/g), the Soft Roll lithium ion for 504848 models that diaphragm is formed using polyethylene as matrix (16um) The processes such as in battery, battery after fluid injection is encapsulated, shelve, be melted into, aging, secondary encapsulation, partial volume, obtain ternary to be tested Silicon-carbon lithium ion battery.
Embodiment 2
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas In 1ppm), by ethylene carbonate, methyl ethyl carbonate, diethyl carbonate with 1:1:1 mass ratio is uniformly mixed, in mixed solution The LiPF that mass fraction is 12.5% is added6, stirring is completely dissolved to it, and be further added 0.3% difluorophosphate and 0.5% di-oxalate lithium borate and 1% double fluorine sulfimide lithium additives, obtain the lithium-ion battery electrolytes of embodiment 2.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 3
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas In 1ppm), by ethylene carbonate, methyl ethyl carbonate, diethyl carbonate with 1:1:1 mass ratio is uniformly mixed, in mixed solution The LiPF that mass fraction is 12.5% is added6, stirring is completely dissolved to it, and be further added 0.1% difluorophosphate and 0.5% di-oxalate lithium borate and 1% double fluorine sulfimide lithium additives, obtain the lithium-ion battery electrolytes of embodiment 2.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 4
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas In 1ppm), by ethylene carbonate, methyl ethyl carbonate, diethyl carbonate with 1:1:1 mass ratio is uniformly mixed, in mixed solution The LiPF that mass fraction is 12.5% is added6, stirring is completely dissolved to it, and be further added 1% difluorophosphate and 0.5% di-oxalate lithium borate and 0.5% double fluorine sulfimide lithium additives, obtain embodiment 2 lithium ion battery electrolysis Liquid.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 5
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas In 1ppm), by ethylene carbonate, methyl ethyl carbonate, diethyl carbonate with 1:1:1 mass ratio is uniformly mixed, in mixed solution The LiPF that mass fraction is 12.5% is added6, stirring is completely dissolved to it, and be further added 1% difluorophosphate and 0.5% di-oxalate lithium borate and 0.1% double fluorine sulfimide lithium additives, obtain embodiment 2 lithium ion battery electrolysis Liquid.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 6
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas In 1ppm), by ethylene carbonate, methyl ethyl carbonate, diethyl carbonate with 1:1:1 mass ratio is uniformly mixed, in mixed solution The LiPF that mass fraction is 12.5% is added6, stirring is completely dissolved to it, and be further added 0.1% difluorophosphate and 0.5% di-oxalate lithium borate and 0.1% double fluorine sulfimide lithium additives, obtain embodiment 2 lithium ion battery electrolysis Liquid.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 7
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas In 1ppm), by ethylene carbonate, methyl ethyl carbonate, diethyl carbonate with 1:1:1 mass ratio is uniformly mixed, in mixed solution The LiPF that mass fraction is 12.5% is added6, stirring is completely dissolved to it, and be further added 1% difluorophosphate and 0.5% di-oxalate lithium borate and 0.5% double trifluoromethanesulfonimide lithium additives, obtain the lithium-ion electric of embodiment 2 Pond electrolyte.
Remaining is with embodiment 1, and which is not described herein again.
The following terms performance test is carried out to lithium ion battery made from comparative example 1~6 and Examples 1 to 7 respectively：
(1) room temperature 1C/1C cycle performances：Battery obtained by comparative example 1-6 and embodiment 1-7 is 25 DEG C ± 2 DEG C in temperature Under environment, ternary battery and cobalt acid lithium battery are respectively with 1.0C (ternary battery capacity 1C=1000mAh, cobalt acid lithium battery 1C= It 1300mAh) fills after Constant Electric Current limits voltage to 4.2V and is changed to constant-voltage charge, until charging current≤cut-off current 0.02C, stands 5min, then 1.0C be discharged to blanking voltage 3.0V, stand 5min, carry out charge-discharge test by above-mentioned operation, altogether progress 400 weeks The above cycle, the capacity retention ratio of each group is as shown in table 1 at 400 weeks.
(2) 60 DEG C of 622 silicon-carbon ternary battery high-temperature of nickle cobalt lithium manganate storage 7 days is tested：Comparative example 1-6 and embodiment 1-7 Obtained battery is changed to constant-voltage charge after charging to 4.2V limitation voltages with 0.2C, until charging current≤cut-off current 0.02C, and it is quiet 5min is set, then 0.2C discharges, this discharge capacity is initial capacity；It is changed to constant pressure after charging to 4.2V limitation voltages with 0.5C Charging, until charging current≤cut-off current, open circuit shelves 2h, measures original depth and initial internal resistance；Battery core is stored in temperature It opens a way and shelves 7 days under conditions of being 60 DEG C ± 2 DEG C；Battery core is then taken out, thickness 1 is tested immediately, restores 2h at room temperature, is tested The internal resistance of cell；Then battery core is first discharged according to 0.2C, then with 0.2C charge and discharge, test residual capacity and recovery capacity.Calculate electricity Pond storage front and back hot Thickness Measurement by Microwave, internal resistance Equal variation, the results are shown in Table 1.
(3) -20 DEG C of low temperature discharge experiments of nickle cobalt lithium manganate ternary battery high-temperature：Comparative example 1-6 and embodiment 1-7 are made It obtains after battery charges to 4.2V limitation voltages with 0.2C and is changed to constant-voltage charge, until charging current≤cut-off current 0.02C, stands 5min, then 0.2C be discharged to 2.5V, this discharge capacity be 25 DEG C at initial capacity C1；4.2V limitation electricity is charged to 0.5C Constant-voltage charge is changed to after pressure, until charging current≤cut-off current, open circuit shelves 2h, measures original depth and initial internal resistance；Electricity Core, which is stored in open circuit under conditions of temperature is -20 DEG C, shelves 4h；Then battery core is first discharged to 2.5V according to 1.0C, and discharge capacity is C2, discharging efficiency=(C1/C2) * 100% of -20 DEG C of low temperature.The results are shown in Table 1 for electric discharge.
(4) button half-cell cyclic voltammetry：Comparative example 1-6 and embodiment 1 half-cell made are subjected to cycle volt Peace test, with graphite be anode, lithium piece be to electrode and reference electrode, under the conditions of 25 ± 2 DEG C, using electrochemical workstation into Row test, scanning voltage ranging from 0-3.0V, sweep speed 0.1mV/s carry out the loop test of 1-3 cycle.It measures Cyclic voltammetry curve is recycled as shown in Fig. 1~7.
1 properties test result of table
From the data of table 1 can be seen that when individually added in electrolyte difluorophosphate (comparative example 3) or have structural formula When I compound pair fluorine sulfimide lithium (comparative example 4), the cycle performance of battery obtained is poor, this is because individually Difluorophosphate and the double fluorine sulfimide lithiums of compound with structural formula I stable SEI films can not be formed in negative terminal surface, Cycle cannot be guaranteed；And when individually adding di-oxalate lithium borate (comparative example 1) in electrolyte, circulating battery obtained The double fluorine sulfimide lithiums of compound containing difluorophosphate or with structural formula I can be substantially better than；When containing in electrolyte When difluoro pair oxalic acid lithium phosphate (comparative example 2), performance is preferable during cycle performance of battery obtained matches silicon-carbon system 622, often Capacity retention ratio is up to 73.5% after temperature 400 weeks；It is added with difluorophosphate when being not only added with di-oxalate lithium borate in electrolyte When double fluorine sulfimide lithium (comparative examples 5) of (comparative example 6) or compound with structural formula I, the cycle performance of battery obtained It gets a promotion, but still it is undesirable.And in Examples 1 to 7, when in electrolyte simultaneously added with dioxalic acid lithium phosphate, difluoro phosphorus When sour lithium and compound (double fluorine sulfimide lithiums or double trifluoromethanesulfonimide lithiums) with structural formula I, electricity obtained The cycle performance in pond is best.
Data can also be seen that when di-oxalate lithium borate, difluorophosphate, sulfimide lithium any type object from table 1 When matter is very few, the cycle performance of battery is obviously deteriorated；Show indispensable between three's additive, there is apparent collaborations Effect.
In addition, from upper table each group battery 55 DEG C of storge qualities of high temperature it is found that battery made from Examples 1 to 7 thickness Expansion rate is spent significantly lower than battery made from comparative example 1~6, that is to say, that adds double oxalic acid in electrolyte of the invention simultaneously Lithium borate, difluorophosphate and the compound with structural formula I, the high-temperature behavior of battery obtained are substantially better than existing.
In addition to this, double by can be seen that in the cyclic voltammetry curve analysis of graphite cathode to above-mentioned various additives The initial reduction current potential of Lithium bis (oxalate) borate is in 1.88V or so；Difluorophosphate and double fluorine sulfimide lithiums high potential (1.0V with On) state do not observe reduction process；The initial reduction current potential of the double oxalic acid lithium phosphates of difluoro is in 2.0V；Di-oxalate lithium borate with The initial reduction current potential of the combination of double fluorine sulfimide lithiums is down toward 1.749V；The combination of di-oxalate lithium borate and difluorophosphate Initial reduction current potential is chivalrous in 1.73V；And di-oxalate lithium borate, difluorophosphate, double fluorine sulfimide lithium three classes additive groups 2.0V is moved to when conjunction on reduction potential, it is very close with the reduction potential of the double oxalic acid lithium phosphates of difluoro, this is because double oxalic acid boron There is interaction between sour lithium, difluorophosphate and double fluorine sulfimide lithium three classes compound anion of structural formula I, in electricity It is chemically reacted in the charging process of pond so that the performance of battery system had both been similar to the spy containing the double oxalic acid lithium phosphates of difluoro The characteristics of levying, while also remaining classes of compounds, passes through the group of the compound of boracic lithium salts, difluorophosphate and structural formula I It closes so that the cycle performance of battery is more excellent, high temperature performance more preferably, has preferable application prospect.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is changed.Therefore, the invention is not limited in above-mentioned specific implementation mode, every those skilled in the art exist Made any conspicuously improved, replacement or modification all belongs to the scope of protection of the present invention on the basis of the present invention.This Outside, although having used some specific terms in this specification, these terms are merely for convenience of description, not to the present invention Constitute any restrictions.

Claims (9)

1. a kind of ternary material system lithium-ion battery electrolytes, including Non-aqueous Organic Solvents, lithium salts and additive, feature It is：The additive includes boracic lithium salts, difluorophosphate and the compound with structural formula I
2. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：It is described that there is structure M in the compound of Formulas I1And M2One kind respectively in fluorine atom, methyl, trifluoromethyl.
3. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：It is described that there is structure The addition of the compound of Formulas I accounts for the 0.1~10% of electrolyte total weight；The addition of the boracic lithium salts is electrolyte gross weight The 0.1~5% of amount；The addition of the difluorophosphate is the 0.1~3% of electrolyte total weight.
4. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：The additive is also Including in gamma-butyrolacton, vinylene carbonate, fluorinated ethylene carbonate, sulfuric acid vinylene and 1,3- propane sulfonic acid lactones extremely Few one kind.
5. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：The boracic lithium salts Including at least one of di-oxalate lithium borate, LiBF4 and difluorine oxalic acid boracic acid lithium.
6. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：Described non-aqueous have Solvent is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, ethylene carbonate, propyl propionate and propionic acid At least two in ethyl ester.
7. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：Described non-aqueous have The content of solvent accounts for the 65%~85% of electrolyte gross mass.
8. ternary material system lithium-ion battery electrolytes according to claim 1, it is characterised in that：The lithium salts is six Lithium fluophosphate, the content of the lithium salts account for the 10%~18% of electrolyte gross mass.
9. a kind of ternary material system lithium ion battery, including anode pole piece, cathode pole piece, diaphragm and electrolyte, it is described just Pole pole piece includes plus plate current-collecting body and the positive diaphragm on plus plate current-collecting body surface, the anode diaphragm include positive active material, Conductive agent and binder, it is characterised in that：The electrolyte is claim 1~8 any one of them electrolyte, the anode Active material is LiNi1-x-y-zCoxMnyAlzO2, wherein：0≤x≤1,0≤y≤1,0≤z≤1 and 0≤x+y+z≤1, the lithium The operating voltage of ion battery is greater than or equal to 4.2V.
CN201810470161.5A 2018-05-16 2018-05-16 A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery Pending CN108767316A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810470161.5A CN108767316A (en) 2018-05-16 2018-05-16 A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810470161.5A CN108767316A (en) 2018-05-16 2018-05-16 A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery

Publications (1)

Publication Number Publication Date
CN108767316A true CN108767316A (en) 2018-11-06

Family

ID=64008269

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810470161.5A Pending CN108767316A (en) 2018-05-16 2018-05-16 A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery

Country Status (1)

Country Link
CN (1) CN108767316A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112310473A (en) * 2019-07-30 2021-02-02 东莞市杉杉电池材料有限公司 High-low temperature lithium ion battery electrolyte and lithium ion battery
CN112909335A (en) * 2020-12-07 2021-06-04 苏州经贸职业技术学院 Lithium ion battery and lithium ion battery pack

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848404A (en) * 2017-02-22 2017-06-13 中航锂电（洛阳）有限公司 A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery
CN107195966A (en) * 2017-04-26 2017-09-22 湛江市金灿灿科技有限公司 The high voltage tertiary cathode material system lithium-ion battery electrolytes that a kind of high/low temperature performance is taken into account

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848404A (en) * 2017-02-22 2017-06-13 中航锂电（洛阳）有限公司 A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery
CN107195966A (en) * 2017-04-26 2017-09-22 湛江市金灿灿科技有限公司 The high voltage tertiary cathode material system lithium-ion battery electrolytes that a kind of high/low temperature performance is taken into account

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112310473A (en) * 2019-07-30 2021-02-02 东莞市杉杉电池材料有限公司 High-low temperature lithium ion battery electrolyte and lithium ion battery
CN112909335A (en) * 2020-12-07 2021-06-04 苏州经贸职业技术学院 Lithium ion battery and lithium ion battery pack
CN112909335B (en) * 2020-12-07 2021-11-12 苏州经贸职业技术学院 Lithium ion battery and lithium ion battery pack

Similar Documents

Publication Publication Date Title
CN105591158B (en) A kind of tertiary cathode material lithium ion battery and its electrolyte
CN105375066B (en) One kind is applied to silicon-carbon cathode lithium-ion battery electrolytes and silicon-carbon cathode lithium ion battery
EP3699997B1 (en) Lithium secondary battery electrolyte and lithium secondary battery comprising the same
CN107275676A (en) A kind of electrolyte and silicon substrate lithium secondary battery for silicon substrate lithium secondary battery
CN108598574A (en) A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte
CN111883839B (en) High-voltage electrolyte and lithium ion battery based on same
CN109473719B (en) Lithium ion battery electrolyte and lithium ion battery containing same
KR20200103807A (en) Additive for battery electrolyte, lithium ion battery electrolyte, lithium ion battery
CN110611121B (en) Electrolyte and lithium ion battery containing same
CN109309226A (en) Electrochemical energy storage device
CN106159330A (en) A kind of PC base high-voltage electrolyte and a kind of lithium ion battery
CN109119686A (en) Lithium iron phosphate battery
CN108808089A (en) A kind of iron manganese phosphate lithium battery and its electrolyte
CN109687026B (en) High-voltage ternary lithium ion battery electrolyte and lithium ion battery containing same
CN116995303B (en) Electrolyte for sodium ion battery and sodium ion battery
CN111525190A (en) Electrolyte and lithium ion battery
CN108390098B (en) High-voltage lithium ion battery electrolyte and high-voltage lithium ion battery
CN112786964A (en) High-voltage high-energy-density electrolyte and lithium battery thereof
EP3996180A1 (en) Electrolytic solution, and preparation method therefor and application thereof
CN108417894A (en) A kind of lithium secondary cell electrolyte and lithium secondary battery
CN109659617A (en) Lithium ion secondary battery and its electrolyte
CN108767316A (en) A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery
CN112490505A (en) Electrolyte additive, non-aqueous electrolyte and lithium ion battery thereof
CN109309249A (en) Electrolyte and electrochemical energy storage device
CN116487697A (en) Lithium ion battery electrolyte and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20181106