CN104332653B - A kind of nonaqueous electrolytic solution and the lithium ion battery using this electrolyte - Google Patents
A kind of nonaqueous electrolytic solution and the lithium ion battery using this electrolyte Download PDFInfo
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- CN104332653B CN104332653B CN201410440678.1A CN201410440678A CN104332653B CN 104332653 B CN104332653 B CN 104332653B CN 201410440678 A CN201410440678 A CN 201410440678A CN 104332653 B CN104332653 B CN 104332653B
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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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The application be related to a kind of nonaqueous electrolytic solution and using this nonaqueous electrolytic solution lithium ion battery, described nonaqueous electrolytic solution include non-aqueous organic solvent, lithium salts and additive it is characterised in that：Described additive contains phosphonic acid cyclic compound anhydride and LiBF4, and described phosphonic acid cyclic compound anhydride mass fraction in the electrolytic solution is 0.05%～3%, and described LiBF4 mass fraction in the electrolytic solution is 0.01%～2%.Compared with prior art, using the lithium ion battery of this electrolyte, there is excellent cold cycle characteristic and high-multiplying-power discharge performance.
Description
Technical field
The application belongs to field of batteries, more particularly, to a kind of nonaqueous electrolytic solution and the lithium ion battery using this electrolyte.
Background technology
Lithium ion battery has the remarkable advantages such as specific energy is high, specific power is big, have extended cycle life, self discharge is little, extensively
General be applied in the electronic products such as mobile communication, digital camera, video camera, and become the focus of energy storage and electrokinetic cell development.
With the extensive application of lithium ion battery, higher requirement is proposed to its environmental suitability, lithium ion battery has been used for respectively
In the environment of planting various kinds.As in the severe cold area of bad environments it is desirable to lithium ion battery also can normal work under extreme low temperature.
However, lithium ion battery charge-discharge performance at low ambient temperatures is decreased obviously compared with normal temperature environment.
Electrolyte, as the important component part of lithium ion battery, has great impact to the cryogenic property of battery.From
The cryogenic property that the angle of electrolyte improves lithium ion battery mainly has two approach.First, optimizing solvent composition, make electrolyte
Viscosity under low temperature reduces, and electrical conductivity improves, and such as by adding a large amount of low viscosity solvents, can improve the low temperature of lithium ion battery
Performance.But, the high-temperature behavior of battery would generally be deteriorated it is impossible to finally solve the problems, such as lithium ion battery in the application.Second,
By optimizing electrolysis additive, reduce the impedance of anode SEI film, also can improve lithium ion battery kinetics at low temperature
Energy.
In view of this, it is necessory to develop one kind under conditions of not affecting high-temperature behavior, improve lithium ion battery low
The electrolyte of warm dynamic performance and lithium ion battery.
Content of the invention
A kind of one side according to the application, there is provided nonaqueous electrolytic solution, this nonaqueous electrolytic solution can ensure battery
While high-temperature behavior, significantly improve lithium ion battery cold cycle performance and high rate performance.
Described nonaqueous electrolytic solution is characterised by, including non-aqueous organic solvent, lithium salts and additive it is characterised in that：Institute
The additive stated contains LiBF4 and at least one phosphonic acid cyclic compound anhydride.
In the application, described phosphonic acid cyclic compound anhydride is formed through intermolecular dehydrating condensation for one or more organic phospho acid
The compound with circulus, described circulus is alternately made up of P atom and O atom, and it is double to be connected with phosphorus oxygen on P atom
Key.
Described phosphonic acid cyclic compound anhydride has the chemical structural formula shown in formula (I)：
R in formula (I)1, R2, R3Independently optionally from carbon number be 1～20 alkyl, carbon number be 6～26 and contain
The group of at least one phenyl ring.
Described carbon number is 6～26 and the group containing at least one phenyl ring, refers to total carbon number and is 6～26 and changes
Learn and in structural formula, comprise the group of benzene ring structure, including the group containing a phenyl ring, the group containing multiple phenyl ring or contain
The group of the aromatic condensed ring of six-membered carbon ring.Preferably, the carbon number of the described group containing at least one phenyl ring is 6～20.
It is highly preferred that the carbon number of the described group containing at least one phenyl ring is 6～18.It is further preferred that described containing extremely
The carbon number of the group of a few phenyl ring is 6～12.
Group containing a phenyl ring is the group that the compound containing a phenyl ring loses the formation of any one hydrogen atom,
Lose the phenyl that any hydrogen atom formed as benzene, benzene compound loses the benzene alkyl of any hydrogen atom formation, alkane on alkyl
Base benzene compound loses the alkane phenyl that on phenyl ring, any hydrogen atom is formed.As methylbenzene, lose a hydrogen atom on methyl and formed
Benzyl, or lose the p-methylphenyl that methyl para-position hydrogen atom on phenyl ring is formed.
Group containing multiple phenyl ring is not share carbon atom between phenyl ring and phenyl ring, and loses any one hydrogen atom institute
The group being formed.
It is former that the group of the aromatic condensed ring containing six-membered carbon ring is that the condensed-nuclei aromatics containing six-membered carbon ring loses any one hydrogen
The group that son is formed.As 1- methyl naphthalene, lose the 1- menaphthyl that on methyl, a hydrogen atom is formed, or lose on naphthalene nucleus the
1- methyl -2- the naphthyl of the hydrogen evolution of 2 positions.
The higher limit of the carbon number of described alkyl can be also 16,12,8,6,4,3.For example, in the higher limit of carbon number
In the case of 16, the carbon atom number range of described alkyl refers to 1～16.
Described alkyl can be alkyl group or cycloalkyl.Described alkyl group comprises straight chained alkyl and the alkyl with side chain；Institute
Stating cycloalkyl is the saturated alkyl containing alicyclic structure, and alicyclic ring can contain or not contain substituent group.
Preferably, R in described formula (I)1, R2, R3Independently optionally from carbon number be 1～20 alkyl, phenyl；Enter one
Walk preferably, R in described formula (I)1, R2, R3Independently optionally from carbon number be 1～3 alkyl, phenyl.
Preferably, R in described formula (I)1, R2, R3For identical group.
Preferably, described phosphonic acid cyclic compound anhydride is selected from triphenyl phosphonic acids cyclic anhydride, tripropyl phosphonic acids cyclic anhydride, triethyl phosphine
At least one in sour cyclic anhydride, trimethyl phosphonic acids cyclic anhydride.
Shown in the structural formula such as formula (II) of described triphenyl phosphonic acids cyclic anhydride：
Shown in the structural formula such as formula (III) of described tripropyl phosphonic acids cyclic anhydride：
Shown in the structural formula such as formula (IV) of described triethyl group phosphonic acids cyclic anhydride：
Shown in the structural formula such as formula (V) of described trimethyl phosphonic acids cyclic anhydride：
The application passes through phosphonic acid cyclic compound anhydride and LiBF4As electrolysis additive, significantly improve lithium ion
The cold cycle characteristic of battery and rate discharge characteristic.Its reason is by being simultaneously introduced LiBF in the electrolytic solution4And phosphonic acid cyclic
Compound anhydride, forms stable and the high solid electrolyte interface film of ionic conductivity in the anode surface of lithium ion battery
(solid electrolyte interface, abbreviation SEI film) so that the movement of lithium ion becomes smooth, thus reaching excellent
Low temperature charge-discharge performance and high rate performance.
It is individually added into LiBF in electrolyte4High temperature storage and the low temperature performance of battery during additive, can be improved,
Its reason is LiBF4The electron deficiency of middle boron element makes it easily have an effect with the oxygen atom of cathode surface, the B-O key of formation
Cathode surface can be stablized, reduce the oxidation activity to electrolyte, thus effectively suppressing battery expansion at high temperature.Meanwhile,
LiBF4Effect with negative electrode advantageously reduces electrochemical cathode reaction impedance, improves negative electrode dynamic performance, thus reaching raising
The effect of the low temperature performance of battery.However, on the other hand, LiBF4In anode, reduction decomposition can occur, catabolite covers
Anodic surface, causes anode embedding lithium impedance to increase, is unfavorable for the dynamic performance of anode.Especially charge at low ambient temperatures
When, higher embedding lithium impedance easily causes anode surface lithium metal to separate out, thus deteriorating the low temperature charging performance of lithium ion battery.
Containing LiBF4Electrolyte in introduce phosphonic acid cyclic compound anhydride when, can anode surface formed ionic conductance
The high SEI film of rate, the formation mechenism of this SEI film is explained as follows, but is not limited to this.Phosphonic acid cyclic compound anhydride has high reaction
Activity, during battery initial charge, can be in LiBF4Before there is reduction decomposition, there is electrochemical reduction first and open
Cyclopolymerization is reacted, and forms stable SEI film in anode, effectively suppresses LiBF4Reduction decomposition, thus reducing LiBF4To anode
The dynamic (dynamical) adverse effect of process of intercalation.The SEI film that phosphonic acid cyclic compound anhydride is formed contains P-O hetero atom, is conducive to increasing
The ionic conductivity of SEI film, improves Lithium-ion embeding/abjection kinetics, thus improving cold cycle and the high rate performance of battery.
Preferably, described phosphonic acid cyclic compound anhydride mass fraction in the electrolytic solution is 0.05%～3%.Work as phosphonic acid cyclic
Compound anhydride mass fraction in the electrolytic solution is less than when 0.05% it is impossible to form complete SEI film in anode surface, thus
LiBF can not effectively be suppressed4Reduction decomposition effect；And work as phosphonic acid cyclic compound anhydride mass fraction in the electrolytic solution and be more than
When 3%, thicker SEI film can be formed in anode surface, lead to lithium ion mobility resistance to increase, be unfavorable for the low temperature and again of battery
Rate performance.It is further preferred that the upper limit of described phosphonic acid cyclic compound anhydride mass fraction scope in the electrolytic solution is optionally certainly
2.8%th, 2.5%, 2.0%, 1.5%, 1.0%, lower limit is optionally from 0.08%, 0.1%, 0.3%, 0.5%, 0.6%.More enter one
Preferably, described phosphonic acid cyclic compound anhydride mass fraction in the electrolytic solution is 0.1%～2% to step.
Preferably, described LiBF4 LiBF4Mass fraction in the electrolytic solution is 0.01%～2%.LiBF4In electricity
Mass fraction in solution liquid is less than it is impossible to effectively suppress thickness swelling during high temperature storage for the battery when 0.01%,
Its improvement to cryogenic discharging characteristic can not be embodied；And work as LiBF4Mass fraction be higher than 2% when, LiBF4Effect to anode
Too strong, the dynamic performance of meeting severe exacerbation anode, causes very detrimental effect to cold cycle performance.Further preferably
Ground, described LiBF4 LiBF4Mass fraction range limit in the electrolytic solution is optionally from 1.5%, 1.0%, 0.8%,
0.5%th, 0.3%, lower limit is optionally from 0.03%, 0.05%, 0.10%, 0.15%, 0.20%.It is further preferred that it is described
LiBF4 LiBF4Mass fraction in the electrolytic solution is 0.05%～0.5%.
Preferably, described non-aqueous organic solvent be carbon number be 1～8 and the compound containing at least one ester group.
Preferably, described non-aqueous organic solvent has the chemical structural formula shown in formula (VI)：
Wherein R4One of alkyl being optionally 1～4 from carbon number；R5Optionally from carbon number be 1～4 alkyl,
Carbon atom is one of 1～4 alkoxyl.
Preferably, described non-aqueous organic solvent has the chemical structural formula shown in formula (VII)：
Wherein R6, R7The alkyl being optionally independently 1～20 from halogen atom, carbon number；Described halogen atom is optionally certainly
One of F, Cl, Br, I.
Preferably, described non-aqueous organic solvent has the chemical structural formula shown in formula (VIII)：
Wherein R8, R9, R10The alkyl being optionally independently 1～4 from hydrogen, carbon number.
Preferably, described non-aqueous organic solvent is selected from ethylene carbonate, Allyl carbonate, butylene, fluoro carbonic acid
Vinyl acetate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-
At least one in butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl n-butyrate..
At least one optionally from organic lithium salt or inorganic lithium salt for the described lithium salts.
In a detailed embodiment, described lithium salts does not comprise LiBF4.
Preferably, containing at least one in fluorine element, boron element, P elements in described lithium salts.
Preferably, described lithium salts is selected from lithium hexafluoro phosphate LiPF6, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(letter
Be written as LiTFSI), double (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(letter
Be written as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) at least one in (being abbreviated as LiDFOB).
Preferably, in described nonaqueous electrolytic solution, the concentration of lithium salts is 0.5M～1.5M.It is further preferred that described non-water power
In solution liquid, the concentration of lithium salts is 0.8M～1.2M.
According to further aspect of the application, additionally provide a kind of lithium ion battery it is characterised in that：Its electrolyte is selected from
At least one in described nonaqueous electrolytic solution.
Described lithium ion battery includes plus plate current-collecting body and is coated on positive pole diaphragm on plus plate current-collecting body, anode collector
And it is coated on anode diaphragm in anode collector, isolating membrane, electrolyte and package foil.
Described positive pole diaphragm includes positive electrode active materials, binding agent and conductive agent.
Described anode diaphragm includes active material of positive electrode, binding agent and conductive agent.
Described positive electrode active materials are optionally from cobalt acid lithium LiCoO2, lithium-nickel-manganese-cobalt ternary material, phosphonic acids ferrous lithium, LiMn2O4
In at least one.As a kind of embodiment of the application, described positive electrode active materials are cobalt acid lithium and lithium-nickel-manganese-cobalt ternary
The mixture of material.
Described active material of positive electrode is graphite and/or silicon.
With respect to prior art, the invention has the advantages that：
The application is by using phosphonic acid cyclic compound anhydride and LiBF4As feature additive package, can ensure
On the premise of high-temperature storage performance of lithium ion battery, significantly improve cold cycle characteristic and rate discharge characteristic.
Specific embodiment
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application and not
For limiting scope of the present application.
In embodiment, phosphonic acid cyclic compound anhydride abbreviation phosphonic acids cyclic anhydride.
Comparative example 1
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by ethylene carbonate (being abbreviated as EC),
Allyl carbonate (being abbreviated as PC), fluorinated ethylene carbonate (being abbreviated as FEC), diethyl carbonate (being abbreviated as DEC) are according to 30:
10:5:After 55 quality is than mix homogeneously, obtain nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Solvent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.
The preparation of lithium ion battery：
By positive active material cobalt acid lithium, (molecular formula is LiCoO2), conductive agent acetylene black, binding agent polyvinylidene fluoride
(being abbreviated as PVDF) by weight 96：2：2 are sufficiently stirred for mixing in appropriate N-Methyl pyrrolidone (being abbreviated as NMP) solvent
Close so as to form uniform anode sizing agent.This slurry is coated on plus plate current-collecting body Al paper tinsel, dries, cold pressing, obtain positive pole pole
Piece.
By anode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (being abbreviated as SBR), thickening agent carboxylic first
Base sodium cellulosate (being abbreviated as CMC) compares 95 according to weight：2：2：1 is thoroughly mixed in appropriate deionized water solvent, makes
It forms uniform anode slurry.This slurry is coated on anode collector Cu paper tinsel, dries, cold pressing, obtain anode pole piece.
Using PE porous polymer film as isolating membrane.
Anode pole piece, isolating membrane, anode pole piece are folded in order, so that isolating membrane is in and play isolation in the middle of positive anode
Effect, then winds and obtains naked battery core.Naked battery core is placed in outer packaging bag, the above-mentioned electrolyte preparing is injected into drying
In battery afterwards, through operations such as Vacuum Package, standing, chemical conversion, shapings, that is, complete the preparation of lithium ion battery.
Comparative example 2
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4, it is in electrolyte
In mass fraction be 0.3%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Comparative example 3
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, add triphenyl phosphonic acids cyclic anhydride in basic electrolyte,
Its mass fraction in the electrolytic solution is 0.5%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Comparative example 4
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4And triphenylphosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 3% and 0.5%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Comparative example 5
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4And triphenylphosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.3% and 5%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Comparative example 6
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4And triphenylphosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 3% and 5%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 1
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4And triphenylphosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 1%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 2
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 1%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 3
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4And triethyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 1%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 4
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4And trimethyl-phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 1%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 5
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 0.05%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 6
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 0.1%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 7
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 0.5%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 8
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 2%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 9
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.2% and 3%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 10
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.01% and 0.6%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 11
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.05% and 0.6%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 12
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.1% and 0.6%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 13
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 0.5% and 0.6%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 14
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 1% and 0.6%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Embodiment 15
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, FEC, DEC according to 30:
10:5:55 quality, than mix homogeneously, obtains nonaqueous solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned non-aqueous
Agent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.Then, basic electrolyte adds LiBF4With tripropyl phosphine
Sour cyclic anhydride, the two mass fraction in the electrolytic solution is respectively 2% and 0.6%.
The preparation of lithium ion battery, with comparative example 1, repeats no more here.
Electrolysis additive in comparative example 1～6 and embodiment 1～15 and respective addition refer to table 1.
Electrolysis additive in table 1. comparative example and embodiment and addition
Test event in comparative example 1～6 and embodiment 1～15 and test result are described in detail below.
Test one：Cold cycle is tested
By the battery of each embodiment and comparative example after the completion of preparation, at 25 DEG C with 0.5C electric current constant-current charge extremely
4.35V, under 4.35V, constant-voltage charge to 0.05C；Battery stands 5 minutes after completely filling, then with 0.2C multiplying power discharging to 3.0V；?
At 0 DEG C, battery standing 30 minutes, with 0.2C constant-current charge to 4.35V, then constant-voltage charge, to 0.05C, stands 5 minutes, then with
0.2C is discharged to 3.0V, stands 5 minutes；Carry out repeated charge by identical condition at 0 DEG C, write down different cycle-indexes
Discharge capacity, and calculate capability retention.
Discharge capacity/25 DEG C discharge capacity × 100% of cold cycle capability retention=difference cycle-index
Cold cycle test result is shown in as table 2 below.
The capability retention of 0 DEG C of circulation of table 2. low temperature
From table 2 it can be seen that compared with comparative example 1, being individually added into 0.3%LiBF in comparative example 2 electrolyte4, lithium ion
0 DEG C of cycle performance of the low temperature of battery is not improved；It is individually added into 0.5% phosphonic acids cyclic anhydride, 0 DEG C of the low temperature of battery in electrolyte
Cycle performance is significantly improved；And in embodiment 1～15, it is less than 2% when being simultaneously introduced mass fraction in the electrolytic solution
LiBF4With mass fraction be less than 3% phosphonic acids cyclic anhydride when, the capability retention of the cold cycle of battery is significantly improved.So
And, as LiBF in electrolyte4Content more than 2% or phosphonic acids cyclic anhydride content more than 3% when, 0 DEG C of the low temperature of lithium ion battery follows
Ring performance fails to be improved, on the contrary can 0 DEG C of cycle performance of impaired low temperature.Particularly electrolyte adds 3%LiBF4With 5% phosphine
During sour cyclic anhydride, after 0 DEG C of circulation 100 times, capability retention only has 45.3% to battery, far below other groups.
Test two：Discharge-rate is tested
By the battery of each embodiment and comparative example after the completion of preparation, at 25 DEG C with 0.5C electric current constant-current charge extremely
4.35V, under 4.35V, constant-voltage charge to 0.05C；Battery stands 5 minutes, then according to certain discharge-rate is put after completely filling
Electricity is to 3.0V.After electric discharge terminates every time, battery standing 5 minutes, then charged with identical condition.The multiplying power of electric discharge is respectively
0.2C, 0.5C, 1.0C, 1.5C, 2.0C, with the capacity of 0.2C electric discharge for 100%, electric discharge under different multiplying for the record battery is held
Amount ratio.
Different multiplying discharge capacity is than discharge capacity/0.2C discharge capacity × 100% under=different multiplying
The test result of multiplying power discharging is shown in Table 3.
3.25 DEG C of different multiplying electric discharge results of table
From table 3 it is observed that compared with comparative example 1, being individually added into 0.3%LiBF in the electrolyte of comparative example 2 and 34
Or during 0.5% phosphonic acids cyclic anhydride, the discharge-rate performance of lithium ion battery is slightly improved.In embodiment 1～15, when same in electrolyte
When add mass fraction be less than 2% LiBF4With mass fraction be less than 3% phosphonic acids cyclic anhydride when, battery is under different multiplying
Discharge capacity all have lifting.However, as LiBF in electrolyte4Content more than 2% or phosphonic acids cyclic anhydride content more than 3% when,
Not only the discharge-rate performance of battery is not improved, or even can be deteriorated.
Test three：High temperature storage is tested
By the battery of each embodiment and comparative example after the completion of preparation, at 25 DEG C with 0.5C electric current constant-current charge extremely
4.35V, 4.35V constant-voltage charge to electric current is 0.025C, then with 0.5C multiplying power discharging to 3.0V, this discharge capacity is designated as battery and deposits
Discharge capacity before storage.Afterwards, with 0.5C multiplying power constant-current charge to 4.35V, then 4.35V constant-voltage charge to electric current is 0.025C,
It is at 4.35V fully charged state, the thickness before test battery storage and internal resistance；Then, full electricity battery is put into 85 DEG C of constant temperature
In case, after storage 6h, take out the thickness surveying battery and internal resistance.It is calculated as follows thickness and the internal resistance increase rate of battery.
Thickness × 100% before thickness increment rate (%)=(thickness before thickness-storage after storage) ÷ storage
Internal resistance × 100% before internal resistance increase rate (%)=(internal resistance before internal resistance-storage after storage) ÷ storage
Battery after storage is placed to being cooled to after room temperature, with 0.5C current discharge to 3.0V, this discharge capacity is
Residual capacity after battery storage.Then, with 0.5C multiplying power constant-current charge to 4.35V, 4.35V constant-voltage charge to electric current is
0.025C, then with 0.5C multiplying power discharging to 3.0V, this discharge capacity is the reversible discharge capacity after battery storage.Battery is deposited
Discharge capacity before storage and the residual capacity after storage and reversible discharge capacity substitute in following formula, after calculating battery high-temperature storage
Capability retention and capacity restoration rate.
Discharge capacity (mAh) × 100% before residual capacity (mAh) ÷ storage after capability retention (%)=storage
Discharge capacity (mAh) × 100% before reversible capacity (mAh) ÷ storage after capacity restoration rate (%)=storage
High temperature storage test result is shown in as table 4 below.
4.85 DEG C of storage test results of table
| Group | Thickness increment rate | Internal resistance increase rate | Capability retention | Capacity restoration rate |
| Comparative example 1 | 45.3% | 47.8% | 45.7% | 49.8% |
| Comparative example 2 | 19.8% | 18.0% | 67.3% | 72.1% |
| Comparative example 3 | 34.1% | 38.5% | 55.3% | 60.1% |
| Comparative example 4 | 11.3% | 12.3% | 78.5% | 82.2% |
| Comparative example 5 | 16.2% | 17.3% | 75.1% | 78.1% |
| Comparative example 6 | 7.8% | 6.9% | 82.3% | 85.0% |
| Embodiment 1 | 13.8% | 14.1% | 77.9% | 80.6% |
| Embodiment 2 | 13.0% | 14.3% | 78.1% | 81.3% |
| Embodiment 3 | 13.5% | 14.1% | 77.6% | 79.9% |
| Embodiment 4 | 13.5% | 15.7% | 78.0% | 79.3% |
| Embodiment 5 | 16.5% | 14.8% | 73.8% | 76.9% |
| Embodiment 6 | 15.3% | 13.6% | 76.2% | 78.6% |
| Embodiment 7 | 12.3% | 15.6% | 79.8% | 82.3% |
| Embodiment 8 | 11.4% | 12.3% | 80.2% | 82.8% |
| Embodiment 9 | 10.6% | 11.5% | 80.9% | 83.4% |
| Embodiment 10 | 32.1% | 33.7% | 56.3% | 61.3% |
| Embodiment 11 | 30.5% | 31.6% | 58.3% | 62.6% |
| Embodiment 12 | 14.5% | 14.1% | 76.9% | 79.8% |
| Embodiment 13 | 11.6% | 13.8% | 80.8% | 82.5% |
| Embodiment 14 | 9.8% | 10.4% | 81.2% | 84.5% |
| Embodiment 15 | 8.0% | 9.7% | 82.3% | 85.7% |
As can be seen from Table 4, phosphonic acids cyclic anhydride is as electrolysis additive and LiBF4When collocation uses simultaneously, can't
Reduce the high-temperature storage performance of battery.
In summary it can be seen, by being simultaneously introduced the LiBF that mass fraction is less than 2% in the electrolytic solution4Low with mass fraction
In 3% phosphonic acids cyclic anhydride, cold cycle characteristic and the rate discharge characteristic of lithium ion battery can be significantly improved.LiBF4Energy
Enough and cathodic process, improves the interface stability of negative electrode and electrolyte, appropriate LiBF4Also help reduction electrochemical cathode resistance
Anti-, improve the dynamic performance of negative electrode.And simultaneously, appropriate phosphonic acids cyclic anhydride can form the high SEI of ionic conductivity in anode
Film, is conducive to improving the dynamic performance under anode low temperature.Therefore, additive phosphonic acids cyclic anhydride and LiBF4When being applied in combination, permissible
Significantly improve cold cycle characteristic and the rate discharge characteristic of lithium ion battery, the height that battery has simultaneously again been effectively ensured is gentle
Storage performance.
The announcement of book according to the above description, those skilled in the art in the invention can also be carried out to above-mentioned embodiment
Suitable change and modification.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's
In the protection domain that some modifications and changes should also be as fall into claims hereof.
Claims (8)
1. a kind of nonaqueous electrolytic solution, containing non-aqueous organic solvent, lithium salts and additive it is characterised in that：Described additive contains
There are LiBF4 and at least one phosphonic acid cyclic compound anhydride, described LiBF4 mass fraction in the electrolytic solution is
0.01%～2%；Described lithium salts is selected from lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithium, double (fluorine sulphonyl) imine lithium, double grass
At least one in sour Lithium biborate, difluorine oxalic acid boracic acid lithium；
Described phosphonic acid cyclic compound anhydride has the chemical structural formula shown in formula (I)：
In formula (I), R1、R2、R3Independently optionally from carbon number be 1～20 alkyl, carbon number be 6～26 and containing extremely
The group of a few phenyl ring.
2. nonaqueous electrolytic solution according to claim 1 it is characterised in that：In formula (I), R1、R2、R3For identical group.
3. nonaqueous electrolytic solution according to claim 1 it is characterised in that：Described phosphonic acid cyclic compound anhydride is selected from triphenyl
At least one in phosphonic acids cyclic anhydride, tripropyl phosphonic acids cyclic anhydride, triethyl group phosphonic acids cyclic anhydride, trimethyl phosphonic acids cyclic anhydride.
4. nonaqueous electrolytic solution according to claim 1 it is characterised in that：Described phosphonic acid cyclic compound anhydride is in the electrolytic solution
Mass fraction be 0.05%～3%.
5. nonaqueous electrolytic solution according to claim 1 it is characterised in that：Described phosphonic acid cyclic compound anhydride is in the electrolytic solution
Mass fraction be 0.1%～2%.
6. nonaqueous electrolytic solution according to claim 1 it is characterised in that：Described LiBF4 quality in the electrolytic solution
Fraction is 0.05%～0.5%.
7. nonaqueous electrolytic solution according to claim 1 it is characterised in that：Described non-aqueous organic solvent is carbon number is 1
～7 and the compound containing at least one ester group.
8. a kind of lithium ion battery it is characterised in that：Its electrolyte is selected from nonaqueous electrolytic solution any one of claim 1-7
In at least one.
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| CN106340670B (en) * | 2015-07-07 | 2018-12-04 | 宁德时代新能源科技股份有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN105047992B (en) * | 2015-07-21 | 2018-05-08 | 宁德新能源科技有限公司 | Electrolyte and the lithium ion battery including the electrolyte |
| CN105226321A (en) * | 2015-09-14 | 2016-01-06 | 宁德新能源科技有限公司 | Electrolyte and comprise the lithium ion battery of this electrolyte |
| CN105449279B (en) * | 2015-12-30 | 2018-08-24 | 东莞新能源科技有限公司 | Nonaqueous electrolytic solution and the lithium ion battery for using the nonaqueous electrolytic solution |
| CN110168797B (en) * | 2017-03-17 | 2023-03-31 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN109301326B (en) | 2018-09-21 | 2020-11-27 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| CN111740161B (en) * | 2018-09-21 | 2022-10-25 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| CN112002942B (en) | 2018-09-21 | 2022-08-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device containing same |
| CN110783626B (en) * | 2019-10-18 | 2021-01-05 | 宁德时代新能源科技股份有限公司 | Electrolyte, lithium ion battery, battery module, battery pack and device |
| CN116154101A (en) * | 2021-05-24 | 2023-05-23 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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