CN109273764A - 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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- CN109273764A CN109273764A CN201811074959.4A CN201811074959A CN109273764A CN 109273764 A CN109273764 A CN 109273764A CN 201811074959 A CN201811074959 A CN 201811074959A CN 109273764 A CN109273764 A CN 109273764A
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- 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
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- H01M10/0567—Liquid materials characterised by the additives
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- 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
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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
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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 invention are made of lithium salts, Non-aqueous Organic Solvents and additive, are one or more cyclic annular unsaturated phosphate esters of M or N containing structure in additive, and additional amount accounts for the 0.05-5% of electrolyte total weight.This kind ring-type unsaturated phosphate ester can occur reduction in cathode interface and form SEI film, can also form passivation layer in positive interface decomposition, inhibit the generation of side reaction.Additive of the present invention also may include fluorinated ethylene carbonate, vinylene carbonate, sulfuric acid vinyl ester, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, LiBF4, the double oxalic acid lithium phosphates of difluoro, vinylethylene carbonate, 1,3- propene sultone etc., it can inhibit battery producing gas by using additive of the invention, promote the high-temperature storage performance of nickelic ternary battery, and promote the cyclical stability of battery.
Description
Technical field
The present invention relates to technical field of lithium ion, it is specifically related to a kind of lithium-ion battery electrolytes and contains the electricity
Solve the lithium ion battery of liquid.
Background technique
Improving lithium ion battery energy density is power battery product and digital or eternal energy-storage battery product pursuit.Hair
The method of the currently used relatively mainstream of exhibition lithium ion battery with high energy density is to promote the operating voltage of battery and using capacity
Higher positive and negative anodes active material.
Cobalt nickel lithium manganate ternary material is relatively popular one of the material in current market, and the content by improving nickel can be big
The big specific capacity for promoting material, while reducing the cost of battery.However, taking high-nickel material as the lithium-ion battery system of anode
In, as the electrical property of the increase battery of nickel content is affected, be mainly reflected in: 1. the thermostabilization of material is deteriorated, and influences electricity
The high-temperature behavior and security performance in pond；2. positive electrode surface alkalinty enhances, it is more harsh to environmental requirement simultaneously to be easy water suction；③
Nickel is in the nickelic system of ternary mainly with Ni3+Form exists, and can further be oxidized to Ni4+, to show stronger
Oxidisability is easy that oxidative decomposition occurs with electrolyte, and positive electrode is easy to produce crackle, and companion in charge and discharge process
As the release of Lattice Oxygen forms the O of high activity state2, it be easy to cause battery to produce gas during use or storage, shortens electricity
The service life in pond increases the security risk in battery use process.
Summary of the invention
It, can be by controlling the production gas of battery, inhibiting in order to improve with the performance for the lithium ion battery that high-nickel material is anode
The increase of active material end internal resistance in use.Present invention discover that by constructing stable protection in cathode and positive electrode surface
Membrane component can be obviously improved the production gas problem of battery, according to the model of solid electrolyte film, the component tool rich in inorganic salts film
There are preferable thermal stability and suitable impedance, small molecule organic film class component good toughness but non-refractory, there is certain polymerization
The organic component high-temperature behavior and mechanical stability of degree more preferably, dielectric film under conditions of organic component and inorganic component coexist
Stability gets a promotion.In addition to being formed in cathode terminal other than anode tap forms solid electrolyte protective film in battery system
Stable passivating film is by being promoted, battery high-temperature behavior is also particularly important, and conventional high temperature modification additive generates in nickelic system
Passivating film it is unstable, be easy the metal ion oxygenolysis for being thermal decomposited or being dissolved, show thermal instability and electrification
Learn the problems such as unstability or high temperature additive film forming are excessively thick and solid to cause capacity to play not enough, and impedance increase is larger.
In order to achieve the object of the present invention, lithium-ion battery electrolytes of the invention by lithium salts, Non-aqueous Organic Solvents and
Additive composition is one or more cyclic annular unsaturated phosphate esters of M or N containing structure in additive, wherein
M isN isR in M and N1, R2, R3, R4, R5Respectively independent choosing
From methyl, ethyl, propyl, isopropyl, trifluoromethyl, trifluoroethyl, Polyfluoroalkyl, perfluoroalkyl, phenyl, p-methylphenyl,
P-fluorophenyl, poly-fluorine phenyl, perfluorophenyl, acrylic, allyl, methylene.
Preferably, to reach the good performance of electrolyte, the additional amount of cyclic annular unsaturated phosphate ester M or N compound accounts for electricity
Solve the 0.05-5% of liquid total weight.
Preferably, the structural formula of cyclic annular unsaturated phosphate ester M or N compound are as follows:
It preferably, is the performance for further improving above-mentioned electrolyte, the additive also includes fluorinated ethylene carbonate, carbon
Sour vinylene, 1,3 propane sulfonic acid lactones, sulfuric acid vinyl ester, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, LiBF4,
In the double oxalic acid lithium phosphates of difluoro, vinylethylene carbonate, 1,3- propene sultone, double fluorine sulfimide lithiums and difluorophosphate
It is one or more, it is further preferred that its content be electrolyte gross mass 0.05~20%.
Preferably, the lithium salts includes lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, three oxalic acid lithium phosphates, two
Fluorine Lithium bis (oxalate) borate, double fluorine sulfimide lithiums, double trifluoromethanesulfonimide lithiums, difluorophosphate, four lithium fluophosphates and difluoro
One of double oxalic acid lithium phosphates are a variety of.
It is further preferred that the content of the lithium salts is the 8~20% of electrolyte gross mass.
Preferably, the Non-aqueous Organic Solvents include cyclic carbonate solvents, linear carbonate solvent, chain carboxylate
One of the siliceous carbonate solvent of solvent, chain, chain fluoro carbonic ester solvent and cyclic annular fluorine-containing carbonic ester solvent are a variety of.
It is furthermore preferred that the non-aqueous organic solvent is ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate
Ester, propyl propionate, ethyl propionate, methyl propyl carbonate, tetrahydrofuran, dioxy cycloalkanes, gamma-butyrolacton, ethyl acetate, acetic acid third
Ester, methyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, (trimethyl silicane ylmethyl) methyl carbonic, two (trimethyl silicanes
Ylmethyl), (trimethyl silicane ylmethyl) ethyl carbonate ester, two (trimethyl silicane ylmethyl) ethyl carbonate esters, one in carbonic ester
Kind is a variety of.
It is further preferred that the content of the non-aqueous organic solvent is the 50~85% of electrolyte gross mass.
The present invention also provides a kind of lithium ion battery containing electrolyte of the present invention, which includes anode pole piece, bears
Pole pole piece, the diaphragm being set between anode pole piece and cathode pole piece and electrolyte of the present invention.
Preferably, the anode pole piece includes plus plate current-collecting body and the positive diaphragm coated on plus plate current-collecting body surface, institute
Stating positive diaphragm includes positive active material, positive conductive agent and positive electrode binder.
Preferably, the positive active material be cobalt acid lithium, it is LiMn2O4, LiFePO 4, nickel cobalt mangaic acid aluminium, lithium-rich manganese-based
Solid solution and nickelic ternary material LiNi1-x-y-zCoxMnyAlzO2, in which: 0≤x≤1,0≤y≤1,0≤z≤1 and 0≤x+y+z
≤ 1,
It is furthermore preferred that nickel cobalt manganese ratio is classified as 424,333,523,701,811,515 in the ternary material.
Preferably, the material system of the anode can be mono-crystalline structures, second particle, and surface can be by three oxidations two
Aluminium, graphene, carbon nanotube, carbon material, electroconductive polymer layer are coated, and can further use alkaline-earth metal beryllium, magnesium,
Calcium, strontium, barium, rare earth metal scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, which are doped, to be changed
Property.
Electrolyte provided by the invention containing cyclic annular unsaturated phosphate ester compound can both be restored in negative terminal surface to be divided
Solution forms stable SEI membrane component, while the effect for inhibiting material activity is played in positive electrode surface ring-opening polymerisation, it is suppressed that high temperature
The side reaction of active material and electrolyte under environment reduces production gas of battery during using and storing.In addition, the present invention adds
Add agent to construct stable protection membrane structure at nickelic battery system positive and negative anodes interface, interface tool is kept by additive specific combination
There is good permeability, conducive to the diffusion and suitable impedance of lithium ion, meets the requirement of high/low temperature and cycle performance.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
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.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment 1
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, propene carbonate are uniformly mixed with 30:70 mass ratio, and it is unsaturated that the ring-type that mass fraction is 1% is added in mixed solution
Phosphate compound (1), then adds 13.5% LiPF6, stir and be completely dissolved to it, obtain lithium ion battery electrolysis
Liquid.The electrolyte is injected into following NCM622/AG-4.3V batteries, and it is encapsulated, shelve, be melted into, aging, secondary encapsulation,
The processes such as partial volume obtain the tertiary cathode material soft bag lithium ionic cell of the nickelic NCM622/AG-4.2V of model.
The preparation of lithium ion battery:
(1) NCM622/AG-4.3V battery production (production of the battery of comparative example 1-5 and embodiment 1-25 is identical with this): will
Positive active material LiNi0.6Co0.2Mn0.2O2(622), conductive agent acetylene black, binder polyvinylidene fluoride (PVDF) press quality
After being thoroughly mixed in N-Methyl pyrrolidone dicyandiamide solution than 95:3:2 uniformly, it is coated on drying on Al foil, cold pressing, is obtained
To anode pole piece, compacted density 3.50g/cm3。
By negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (SBR), thickener carbon Methyl cellulose
After plain sodium (CMC) is thoroughly mixed in deionized water solvent system uniformly according to mass ratio 96:2:1:1, it is coated on Cu foil
Upper drying, cold pressing, obtain cathode pole piece.With polyethylene (PE) for basement membrane (14 μm), and applied in coating on base films nano aluminium oxide
(2 μm) of layer are used as diaphragm.
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 tertiary cathode material Soft Roll lithium ion of the nickelic NCM622/AG-4.3V of model
Battery.
(2) NCM811/AG-4.2V battery production (production of the battery of comparative example 1-5 and embodiment 1-25 is identical with this): will
Positive active material LiNi0.8Co0.1Mn0.1O2(811), conductive agent acetylene black, carbon nanotube, binder polyvinylidene fluoride
(PVDF) 95:2.8:0.2:2 in mass ratio fills in the dry environment full of nitrogen in N-Methyl pyrrolidone dicyandiamide solution
Divide after being uniformly mixed, 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.With polyethylene (PE) for basement membrane (14 μm) and in coating on base films
(2 μm) of nano oxidized aluminized coating are used as diaphragm.
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 tertiary cathode material Soft Roll lithium ion of the nickelic NCM811/AG-4.2V of model
Battery.
Comparative example 1
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, propene carbonate are uniformly mixed with 30:70 mass ratio, and the LiPF that mass fraction is 13.5% is added in mixed solution6, stir
It mixes to it and is completely dissolved, obtain lithium-ion battery electrolytes.The electrolyte is injected into NCM622/AG-4.3V battery, and is passed through
It encapsulates, shelve, being melted into, aging, secondary encapsulation, the processes such as partial volume, obtaining the ternary of the nickelic NCM622/AG-4.3V of model just
Pole material soft bag lithium ionic cell.
Comparative example 2
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, propene carbonate are uniformly mixed with 30:70 mass ratio, and the ethylene carbonate that mass fraction is 1% is added in mixed solution,
Then 13.5% LiPF is added6, stir and be completely dissolved to it, obtain lithium-ion battery electrolytes.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 model
The tertiary cathode material soft bag lithium ionic cell of nickelic NCM622/AG-4.3V.
Comparative example 3
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, propene carbonate are uniformly mixed with 30:70 mass ratio, and the fluoro carbonic acid second that mass fraction is 1% is added in mixed solution
Then enester adds 13.5% LiPF6, stir and be completely dissolved to it, obtain lithium-ion battery electrolytes.By the electrolyte
Be 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 type
Number be 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, propene carbonate are uniformly mixed with 30:70 mass ratio, and the sulfuric acid vinyl ester that mass fraction is 1% is added in mixed solution
(DTD), double fluorine sulfimide lithiums (FSI) of mass fraction 1%, the 1 of 1%, 3 propane sulfonic acid lactones, 1% difluorophosphate,
Then 13.5% LiPF is added6, stir and be completely dissolved to it, obtain lithium-ion battery electrolytes.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 model
The tertiary cathode material soft bag lithium ionic cell of nickelic NCM622/AG-4.3V.
Comparative example 5
The preparation of electrolyte: in the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate
Ester, propene carbonate are uniformly mixed with 30:70 mass ratio, and the sulfuric acid vinyl ester that mass fraction is 1% is added in mixed solution
(DTD), double fluorine sulfimide lithiums (FSI) of mass fraction 2%, the 1 of 0.5%, 3 propane sulfonic acid lactones, 1% difluorophosphoric acid
Lithium, the double oxalic acid lithium phosphates of 1% difluoro, then adds 13.5% LiPF6, stir and be completely dissolved to it, obtain embodiment 1
Lithium-ion battery electrolytes.The electrolyte is injected into NCM811/AG-4.2V battery, and it is encapsulated, shelve, be melted into, always
The processes such as change, secondary encapsulation, partial volume obtain the tertiary cathode material Soft Roll lithium-ion electric of the nickelic NCM811/AG-4.2V of model
Pond.
Embodiment 2-25
Battery system used in embodiment 2-25 and electrolyte prescription do not exist herein according to being configured in the following table 1
It describes one by one.
The battery system and electrolyte of table 1 comparative example 1-5 and embodiment 1-25 forms
The test of battery properties
1. room temperature 1C/1C cycle performance: battery obtained by comparative example 1-5 and embodiment 1-25 is 25 DEG C ± 2 DEG C in temperature
It is nickle cobalt lithium manganate (nickel: cobalt: manganese=6:2:2) battery (capacity 1.2AH) and nickel cobalt mangaic acid by above-mentioned positive electrode under environment
Lithium (nickel: cobalt: manganese=8:1:1) battery (capacity 1.5AH) is changed to perseverance after filling Constant Electric Current to 4.3V and 4.2V pressure respectively with 1.0C
Pressure charging, until charging current≤cut-off current 0.05C, stands 5min, then 1.0C is discharged to blanking voltage 3.0V, stands
5min carries out charge-discharge test by above-mentioned operation, and progress 500 weeks or more circulations, the data obtaineds are shown in Table 2 altogether.
2.45 DEG C of 1C/1C loop tests: battery obtained by comparative example 1-5 and embodiment 1-25 is 45 DEG C ± 2 DEG C in temperature
It is nickle cobalt lithium manganate (nickel: cobalt: manganese=6:2:2) battery (capacity 1.2AH) and nickel cobalt mangaic acid by above-mentioned positive electrode under environment
Lithium (nickel: cobalt: manganese=8:1:1) battery (capacity 1.5AH) is changed to perseverance after filling Constant Electric Current to 4.3V and 4.2V pressure respectively with 1.0C
Pressure charging, until charging current≤cut-off current 0.05C, stands 5min, then 1.0C is discharged to blanking voltage 3.0V, stands
5min carries out charge-discharge test by above-mentioned operation, altogether progress 500 weeks or more circulations, and experiment institute's test data is shown in Table 2.
3. it is 25 DEG C of ± 2 DEG C of environment that 60 DEG C of high temperature, which go out battery obtained by 7 days: comparative example 1-5 and embodiment 1-25 in temperature,
Under, it is nickle cobalt lithium manganate (nickel: cobalt: manganese=6:2:2) battery (capacity 1.2AH) and nickle cobalt lithium manganate by above-mentioned positive electrode
(nickel: cobalt: manganese=8:1:1) battery (capacity 1.5AH) fills Constant Electric Current to 4.3V and 4.2V to full power state with 1.0C respectively
Then battery is placed on to open a way in the environment that environment temperature is 60 ± 2 DEG C and shelve 7 days, takes out immediately after by (100%SOC)
Battery Thickness Measurement by Microwave is restored to room temperature after placing 4h then with 0.2C discharge test residual capacity, then with 0.2C charge-discharge test electricity
The recovery capacity in pond.The hot thickness measuring of high-temperature storage of battery is calculated by thickness change, the volume change before and after battery storage
Degree variation, residual capacity change rate and restore Capacitance Shift Rate, testing the data of test, see Table 2 for details.
4. -20 DEG C of -1C electric discharges of low temperature: battery obtained by comparative example 1-5 and embodiment 1-25 is 25 DEG C of ± 2 DEG C of rings in temperature
It is nickle cobalt lithium manganate (nickel: cobalt: manganese=6:2:2) battery (capacity 1.2AH) and nickle cobalt lithium manganate by above-mentioned positive electrode under border
(nickel: cobalt: manganese=8:1:1) battery (capacity 1.5AH) fills Constant Electric Current to 4.3V and 4.2V to full power state with 1.0C respectively
Then battery is placed on open circuit in the environment that environment temperature is -20 ± 2 DEG C and shelves 4H, then carries out 1C times by (100%SOC)
The discharge test of rate records 1C discharge capacity at -20 DEG C of low temperature, passes through the discharge capacities for calculating -20 DEG C of low temperature and room temperature discharges
The ratio of capacity is 1C discharging efficiency at -20 DEG C of low temperature, and testing the data of test, see Table 2 for details.
Following table, which is listed, is using above-mentioned comparative example 1-5 using arrangement 622/AG high potential 4.3V and 811/AG soft-package battery
With 45 DEG C of -1C/1C circulations of room temperature, high temperature of embodiment 1-25 electrolyte, the property of 60 DEG C of storages electric discharge in 7 days and -20 DEG C of 1C of low temperature
Energy data:
Cycle performance, high-temperature storage performance and the low temperature discharge property of the battery of table 2. comparative example 1-5 and embodiment 1-25
It can data
The data from upper table are it can be seen that be directed to 622/AG high potential 4.3V battery system, additive is vinylene carbonate
The high temperature cyclic performance of 3,45 DEG C of comparative example 2, the comparative example of fluorinated ethylene carbonate of ester is worse compared to comparative example 1,
The unstable easy production gas under high potential is related with VC for main cause, and FEC is easy abjection HF acidification battery system and causes SEI
The destruction of film and the decomposition of electrolyte, after cyclic annular unsaturated phosphate ester compound 1% provided by the invention is added in the system
Embodiment 1-3, compared to above-mentioned additive be VC and FEC comparative example, high-temperature storage performance be improved significantly, 60 DEG C storage
7 days thickness changes are substantially reduced, and residual capacity and reply capacity significantly improve, and the cycle performance that 45 DEG C of high temperature also obtains obviously
It is promoted, illustrates that such additive has more preferably high-temperature behavior to 622/AG-4.3V system, the reason is that itself and cyclic annular unsaturated phosphorus
Acid esters forms stable SEI film in cathode interface, while can form protective layer passivation anode in positive interface ring-opening polymerisation
Material activity inhibits the generation of side reaction.
The composition for advanced optimizing additive in the above system, using room temperature, the height of the comparative example 4 of composite additive
Warm nature can be obviously improved compared to the introducing of above-mentioned one pack system additive, it is shown that combined additive is solving high nickel-based battery
The effect of system further adds unsaturated phosphate ester compound (1) of the invention, compound (2) on the basis of comparative example 4
After compound (8), high-temperature behavior is further increased.It can be seen that from embodiment 5-7 when cyclic annular unsaturated phosphate ester chemical combination
The additive amount of object (2) is promoted from 0.5% to after 1%, 3%, and the high-temperature behavior of battery makes moderate progress, but the low temperature discharge property of low temperature
It can decline, illustrate that additive addition excessively causes cryogenic property to reduce, because such additive is unsaturated functional group, formed
Passivation membrane impedance increase it is related, through testing, the optimal addn of the additive is 0.1-1%.
The cryogenic property that data can be seen that the compound (8) of benzene substitution in further contrast table is better than methyl and hydrogen takes
The compound (1) in generation and (2), this has delocalization related electronics with the substitution of benzene, calculates molecule after benzene replaces by DFT
Reduction potential can be promoted compared to lithium piece, and oxidizing potential can be declined.This aspect illustrates that such additive can be
Negative terminal surface restores earlier than solvent and forms SEI film, on the other hand more than ethylene carbonate in solvent due to oxidizing potential
It is low, therefore decompose prior to solvent and form protective layer at positive interface, while provided by the present invention is unsaturated phosphate ester
Compound can ring-opening polymerisation at high temperature so that battery have preferable high-temperature behavior.Further in just extremely nickel cobalt manganese
811 battery systems of sour lithium further demonstrate the function and effect of such additive, can be seen that from upper table data in comparative example 4
On the basis of further add cyclic annular unsaturated phosphate ester used in the present invention after, the high-temperature storage performance of battery further mentions
Liter, 60 DEG C of hot Thickness Measurement by Microwave of storage are obviously reduced, and in the amount for controlling additive, cryogenic property is substantially unaffected when within 1%,
It is slightly promoted in terms of a small amount of additive normal-temperature circulating performance, is improved significantly in terms of high temperature cyclic performance, it is shown that such
Additive has preferable function and effect in nickelic system.
It is tested with comparative example through the foregoing embodiment it can be found that the tertiary cathode material using electrolyte of the invention is electric
Pond can work normally in ternary high voltage and nickelic battery system, and battery is inhibited to produce gas in the high temperature environment, effectively
The expansion for reducing battery has a better role to the high temperature circulation of battery.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of lithium-ion battery electrolytes, which is characterized in that the lithium-ion battery electrolytes are by lithium salts, Non-aqueous Organic Solvents
It is formed with additive, is one or more cyclic annular unsaturated phosphate esters of M or N containing structure in additive, wherein
M isN isR in M and N1, R2, R3, R4, R5It is each independently selected from first
Base, ethyl, propyl, isopropyl, trifluoromethyl, trifluoroethyl, Polyfluoroalkyl, perfluoroalkyl, phenyl, p-methylphenyl, to fluorine
Phenyl, poly-fluorine phenyl, perfluorophenyl, acrylic, allyl, methylene.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that ring-type the unsaturated phosphate ester M or N
The additional amount of compound accounts for the 0.05-5% of electrolyte total weight.
3. lithium-ion battery electrolytes according to claim 1 or 2, which is characterized in that cyclic annular unsaturated phosphate ester M or N
The structural formula of compound are as follows:
4. lithium-ion battery electrolytes according to claim 1, which is characterized in that the additive also includes fluoro carbonic acid
Vinyl acetate, vinylene carbonate, 1,3 propane sulfonic acid lactones, sulfuric acid vinyl ester, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, four
The double oxalic acid lithium phosphates of lithium fluoroborate, difluoro, vinylethylene carbonate, 1,3- propene sultone, double fluorine sulfimide lithiums and two
One of lithium fluophosphate is a variety of, it is preferred that its content is the 0.05~20% of electrolyte gross mass.
5. lithium-ion battery electrolytes according to claim 1-4, which is characterized in that the lithium salts includes hexafluoro
It is lithium phosphate, LiBF4, di-oxalate lithium borate, three oxalic acid lithium phosphates, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide lithiums, double
One of double oxalic acid lithium phosphates of trifluoromethanesulfonimide lithium, difluorophosphate, four lithium fluophosphates and difluoro are a variety of, preferably
, the content of the lithium salts is the 8~20% of electrolyte gross mass.
6. lithium-ion battery electrolytes according to claim 1-5, which is characterized in that described non-aqueous organic molten
Agent includes cyclic carbonate solvents, linear carbonate solvent, chain carboxylate solvent, the siliceous carbonate solvent of chain, chain fluorine
For one of carbonate solvent and cyclic annular fluorine-containing carbonic ester solvent or a variety of, it is preferred that the non-aqueous organic solvent is carbonic acid
Vinyl acetate, propene carbonate, diethyl carbonate, methyl ethyl carbonate, propyl propionate, ethyl propionate, methyl propyl carbonate, tetrahydro furan
Mutter, dioxy cycloalkanes, gamma-butyrolacton, ethyl acetate, propyl acetate, methyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate,
(trimethyl silicane ylmethyl) methyl carbonic, two (trimethyl silicane ylmethyls), (trimethyl silicane ylmethyl) ethyl carbonate ester, two
One of (trimethyl silicane ylmethyl) ethyl carbonate ester, carbonic ester are a variety of, it is furthermore preferred that the non-aqueous organic solvent contains
Amount is the 50~85% of electrolyte gross mass.
7. a kind of lithium ion battery containing any one of the claim 1-6 electrolyte, which is characterized in that the battery includes just
Described in pole pole piece, cathode pole piece, the diaphragm being set between anode pole piece and cathode pole piece and claim any one of 1-6
Electrolyte, it is preferred that the anode pole piece includes plus plate current-collecting body and the positive diaphragm coated on plus plate current-collecting body surface, institute
Stating positive diaphragm includes positive active material, positive conductive agent and positive electrode binder.
8. lithium ion battery according to claim 7, which is characterized in that the positive active material is cobalt acid lithium, mangaic acid
Lithium, LiFePO 4, nickel cobalt mangaic acid aluminium, rich lithium manganese base solid solution and nickelic ternary material LiNi1-x-y-zCoxMnyAlzO2, in which:
0≤x≤1,0≤y≤1,0≤z≤1 and 0≤x+y+z≤1.
9. lithium ion battery according to claim 7, which is characterized in that in the ternary material nickel cobalt manganese ratio be classified as 424,
333、523、701、811、515。
10. lithium ion battery according to claim 7, which is characterized in that the material system of the anode be mono-crystalline structures,
Second particle, it is preferred that surface is coated by aluminum oxide, graphene, carbon nanotube, carbon material, electroconductive polymer layer, more
Preferably, further use alkaline-earth metal beryllium, magnesium, calcium, strontium, barium, rare earth metal scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium,
Gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium are doped modification.
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| CN201811074959.4A CN109273764A (en) | 2018-09-14 | 2018-09-14 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
| PCT/CN2018/119971 WO2020052118A1 (en) | 2018-09-14 | 2018-12-10 | Lithium ion battery electrolyte, and lithium ion battery containing electrolyte |
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